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Sample records for vocs peroxides photolysis

  1. Hydrogen peroxide evolution during V-UV photolysis of water.

    Science.gov (United States)

    Azrague, Kamal; Bonnefille, Eric; Pradines, Vincent; Pimienta, Véronique; Oliveros, Esther; Maurette, Marie-Thérèse; Benoit-Marquié, Florence

    2005-05-01

    Hydrogen peroxide evolution during the vacuum-ultraviolet (V-UV, 172 nm) photolysis of water is considerably affected by the presence of oxalic acid (employed as a model water pollutant) and striking differences are observed in the absence and in the presence of dioxygen.

  2. Postantibiotic effect of disinfection treatment by photolysis of hydrogen peroxide.

    Science.gov (United States)

    Odashima, Yu; Nakamura, Keisuke; Ikai, Hiroyo; Kanno, Taro; Meirelles, Luiz; Sasaki, Keiichi; Niwano, Yoshimi

    2014-04-01

    The purpose of the present study was to evaluate the postantibiotic effect (PAE) of the disinfection treatment by photolysis of H2O2. Postantibiotic effect was induced in Staphylococcus aureus and Streptococcus salivarius by exposing the bacteria to H2O2 at concentrations of 250-1000 mmol/l, laser irradiation at a wavelength of 405 nm, and the combination of both (photolysis of H2O2) for 10-30 seconds. The photolysis of H2O2 induced significantly longer PAE than other treatments. The PAE was augmented dependently on not only the concentration of H2O2 but the laser irradiation time. Electron spin resonance analysis showed that the hydroxyl radical was also generated dependently on both the concentration of H2O2 and the laser irradiation time, suggesting that the hydroxyl radicals contribute to the PAE. These results suggest that the disinfection treatment by photolysis of H2O2 induces PAE in S. aureus and S. salivarius even though they were treated for only 10-30 seconds.

  3. Hydroxyl radical consumption following photolysis of vapor-phase hydrogen peroxide at 266 nm: Implications for photofragmentation laser-induced fluorescence measurements of hydrogen peroxide

    Science.gov (United States)

    Johansson, O.; Bood, J.; Aldén, M.; Lindblad, U.

    2009-10-01

    The decay of OH concentration following photolysis of room-temperature vapor-phase hydrogen peroxide is studied as a function of photolysis fluence at 266 nm in an open air environment. The rate of decay is found to increase with increasing photolysis fluence, i.e., with increasing number of photodissociated H2O2(g) molecules. Single-exponential functions approximate the OH concentration decay rather well, even for higher photolysis levels, and the decay time is shown to be inversely proportional to the H2O2(g) concentration. For fluences of about 450 mJ/cm2 the difference between a single-exponential decay and measured data is becoming evident after approximately 150 μs. Calculations based on a chemical kinetics model agree well with experimental data also for times >150 μs. By combining the model with measurements, the actual photolysis levels used in experiments are estimated. The best fit between measured data and the model suggests that about 1.1% of the H2O2(g) molecules are dissociated with a photolysis fluence of ˜450 mJ/cm2, in reasonable agreement with a Beer-Lambert based estimation. Excitation scans did not unfold any differences between OH spectra recorded at different photolysis fluences.

  4. The effect of hydrogen peroxide and solvent on photolysis of PCBs to reduce occupational exposure

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    Hasan Asilian

    2010-09-01

    Full Text Available Background: Polychlorinated biphenyls (PCBs are toxic bio-accumulate components and may increase risk of adverse effects on human health and the environment. For different social, technical and economic reasons, significant quantities of PCBs contaminated transformer oil are still in use or storied. The study aimed to determine the effect of hydrogen peroxide and solvent on photolysis of PCBs to reduce occupational exposure. Methods: The photochemical annular geometry (500 ml volume reactor was designed with a cylindrical low-pressure mercury lamp (UV-C Cathodeon TUV 6WE with emission at 254 nm. The radiant power emitted by the lamp was 6w. The whole lamp was immersed in a reactor thermostat controlling of temperature at 32 ± 2 oC. The PCBs was determined using GC/ECD and data was analyzed by SPSS. Results: Degradation of total PCBs in terms of %10 and %20 of volume of H2O2 were 41%, 75% and 94%, respectively. The degradation of total PCBs in terms of ratio to solvent with oil transformer in 1:1, 2:1 and 3:1 was 61%, 75% and 94%, respectively. Conclusion: Our study show that UV-C photolysis of H2O2 leads to a degradation efficiency of PCBs only in the presence of isooctane, therefore indicating that the intermediates formation after ethanol oxidation are able to initiate PCBs degradation.

  5. Electrochemical peroxidation of PCBs and VOCs in superfund site water and sediments

    Energy Technology Data Exchange (ETDEWEB)

    Scrudato, R.J.; Chiarenzelli, J.R. [SUNY, Oswego, NY (United States)

    1996-12-31

    An electrochemical peroxidation (ECP) process has been developed and used to degrade polychlorinated biphenyls (PCB) and volatile organic compounds (VOC)-contaminated water, sludge, and sediments at a New York State Federal and State Superfund Site. The process involves passing an oscillating low-amperage (<10 amps) current through steel electrodes immersed in an acidified water or sediment slurry into which hydrogen peroxide (<1,000 ppm) is added. The generated free radicals attack organic compounds, including organo-metallic complexes and refractory compounds including PCBs. PCB degradation ranged from about 30% to 80% in experiments involving Federal Superfund Site sediments; total PCBs were reduced by {approximately}97% to 68%, respectively, in water and slurry collected from a State Superfund subsurface storage tank. VOC bench-scale experiments involved chloroethane, 1,1-dichloroethane, dichloromethane, 1,1,1-trichloroethane, and acetone and after a 3-min ECP treatment, degradation ranged from >94% to about 99.9%. Results indicate the ECP is a viable process to degrade organic contaminants in water and sediment suspensions. Because the treated water suspensions are acidified, select trace metal sorbed to the particulates is solubilized and therefore can be segregated from the particulates, offering a process that simultaneously degrades organic contaminants and separates trace metals. 19 refs., 1 fig., 4 tabs.

  6. Surface application of soybean peroxidase and calcium peroxide for reducing odorous VOC emissions from swine manure slurry

    Science.gov (United States)

    A laboratory experiment was conducted to evaluate and compare topical and fully mixed treatments of soybean peroxidase and calcium peroxide (SBP/CaO2) for reducing odorous volatile organic compound (VOC) emissions from swine manure slurry. The five treatments consisted of a control, the fully mixed ...

  7. Direct photolysis of α-pinene ozonolysis secondary organic aerosol: effect on particle mass and peroxide content.

    Science.gov (United States)

    Epstein, Scott A; Blair, Sandra L; Nizkorodov, Sergey A

    2014-10-07

    Primary and secondary organic aerosols (POA and SOA) contain a complex mixture of multifunctional chemicals, many of which are photolabile. Much of the previous work that aimed to understand the chemical evolution (aging) of POA and SOA has focused on the reactive uptake of gas-phase oxidants by particles. By stripping volatile compounds and ozone from α-pinene ozonolysis SOA with three 1-m-long denuders, and exposing the residual particles in a flow cell to near-ultraviolet (λ>300 nm) radiation, we find that condensed-phase photochemistry can induce significant changes in SOA particle size and chemical composition. The particle-bound organic peroxides, which are highly abundant in α-pinene ozonolysis SOA (22 ± 5% by weight), have an atmospheric photolysis lifetime of about 6 days at a 24-h average solar zenith angle (SZA) of 65° experienced at 34° latitude (Los Angeles) in the summer. In addition, the particle diameter shrinks 0.56% per day under these irradiation conditions as a result of the loss of volatile photolysis products. Experiments with and without the denuders show similar results, suggesting that condensed-phase processes dominate over heterogeneous reactions of particles with organic vapors, excess ozone, and gas-phase free radicals. These condensed-phase photochemical processes occur on atmospherically relevant time scales and should be considered when modeling the evolution of organic aerosol in the atmosphere.

  8. UV-C photolysis of endocrine disruptors. The influence of inorganic peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Rivas, Javier, E-mail: fjrivas@unex.es [Departamento de Ingenieria Quimica y Quimica Fisica, Facultad de Ciencias, Avenida de Elvas S/N, 06071 Badajoz (Spain); Gimeno, Olga; Borralho, Teresa; Carbajo, Maria [Departamento de Ingenieria Quimica y Quimica Fisica, Facultad de Ciencias, Avenida de Elvas S/N, 06071 Badajoz (Spain)

    2010-02-15

    Norfloxacin, doxycycline and mefenamic acid have been photolysed with UV-C radiation (254 nm) in the presence and absence of inorganic peroxides (hydrogen peroxide or sodium monopersulfate). Quantum yields in the range (1.1-4.5) x 10{sup -3} mol Einstein{sup -1} indicate the low photo-reactivity of these pharmaceuticals. Inorganic peroxides considerably enhanced the contaminants conversion, although no appreciable mineralization could be obtained. A simplistic reaction mechanism for the hydrogen peroxide promoted experiments allowed for a rough estimation of the rate constant between hydroxyl radicals and norfloxacin (k > 1 x 10{sup 9} M{sup -1} s{sup -1}), doxycycline (k > 1.5 x 10{sup 9} M{sup -1} s{sup -1}) and mefenamic acid (k > 11.0 x 10{sup 9} M{sup -1} s{sup -1}).

  9. In vitro evaluation of the risk of inducing bacterial resistance to disinfection treatment with photolysis of hydrogen peroxide.

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    Hiroyo Ikai

    Full Text Available The purpose of the present study was to evaluate the risk of inducing bacterial resistance to disinfection treatment with photolysis of H2O2 and comparing this with existing antibacterial agents. We tested seven antibacterial agents, including amoxicillin, cefepime hydrochloride, erythromycin, ofloxacin, clindamycin hydrochloride, ciprofloxacin hydrochloride, and minocycline hydrochloride, as positive controls for validation of the assay protocol. For all of the agents tested, at least one of the four bacterial species (Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, and Streptococcus salivarius was resistant to these agents by repeated exposure to subinhibitory concentrations of the agents up to 10 times. In contrast, antibacterial activity against any of the bacterial species tested (S. aureus, E. faecalis, E. coli, S. salivarius, Pseudomonas aeruginosa, Streptococcus mutans, and Aggregatibacter actinomycetemcomitans was not affected by repeated exposure to the disinfection treatment up to 40 times. This finding suggested that the risk of inducing bacterial resistance by disinfection treatment was low. The active ingredient of this disinfection treatment is hydroxyl radicals generated by photolysis of H2O2. Therefore, hydroxyl radicals interact with several cell structures and different metabolic pathways in microbial cells, probably resulting in a lack of development of bacterial resistance. In conclusion, disinfection treatment with photolysis of H2O2 appears to be a potential alternative for existing antimicrobial agents in terms of a low risk of inducing bacterial resistance.

  10. In vitro evaluation of the risk of inducing bacterial resistance to disinfection treatment with photolysis of hydrogen peroxide.

    Science.gov (United States)

    Ikai, Hiroyo; Odashima, Yu; Kanno, Taro; Nakamura, Keisuke; Shirato, Midori; Sasaki, Keiichi; Niwano, Yoshimi

    2013-01-01

    The purpose of the present study was to evaluate the risk of inducing bacterial resistance to disinfection treatment with photolysis of H2O2 and comparing this with existing antibacterial agents. We tested seven antibacterial agents, including amoxicillin, cefepime hydrochloride, erythromycin, ofloxacin, clindamycin hydrochloride, ciprofloxacin hydrochloride, and minocycline hydrochloride, as positive controls for validation of the assay protocol. For all of the agents tested, at least one of the four bacterial species (Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, and Streptococcus salivarius) was resistant to these agents by repeated exposure to subinhibitory concentrations of the agents up to 10 times. In contrast, antibacterial activity against any of the bacterial species tested (S. aureus, E. faecalis, E. coli, S. salivarius, Pseudomonas aeruginosa, Streptococcus mutans, and Aggregatibacter actinomycetemcomitans) was not affected by repeated exposure to the disinfection treatment up to 40 times. This finding suggested that the risk of inducing bacterial resistance by disinfection treatment was low. The active ingredient of this disinfection treatment is hydroxyl radicals generated by photolysis of H2O2. Therefore, hydroxyl radicals interact with several cell structures and different metabolic pathways in microbial cells, probably resulting in a lack of development of bacterial resistance. In conclusion, disinfection treatment with photolysis of H2O2 appears to be a potential alternative for existing antimicrobial agents in terms of a low risk of inducing bacterial resistance.

  11. Reduction of odorous VOC in phenolics solutions and swine manure slurry using soybean peroxidase and hydrogen peroxide

    Science.gov (United States)

    A research project was conducted to evaluate the efficacy of low-activity soybean peroxidase (SBP; 0.75 U/mg) and H2O2 for reducing emissions of odorous volatile organic compounds (VOC) from standard solutions (phenol and 4-methylphenol; 1 mM each) and swine manure slurry. VOC emissions were measu...

  12. Post-treatment of refinery wastewater effluent using a combination of AOPs (H2O2 photolysis and catalytic wet peroxide oxidation) for possible water reuse. Comparison of low and medium pressure lamp performance.

    Science.gov (United States)

    Rueda-Márquez, J J; Levchuk, I; Salcedo, I; Acevedo-Merino, A; Manzano, M A

    2016-03-15

    The main aim of this work was to study the feasibility of multi-barrier treatment (MBT) consisting of filtration, hydrogen peroxide photolysis (H2O2/UVC) and catalytic wet peroxide oxidation (CWPO) for post-treatment of petroleum refinery effluent. Also the possibility of water reuse or safe discharge was considered. The performance of MBT using medium (MP) and low (LP) pressure lamps was compared as well as operation and maintenance (O&M) cost. Decomposition of organic compounds was followed by means of gas chromatography-mass spectrometry (GC-MS), total organic carbon (TOC) and chemical oxygen demand (COD) analysis. After filtration step (25 μm) turbidity and concentration of suspended solids decreased by 92% and 80%, respectively. During H2O2/UVC process with LP lamp at optimal conditions (H2O2:TOC ratio 8 and UVC dose received by water 5.28 WUVC s cm(-2)) removal of phenolic compounds, TOC and COD was 100%, 52.3% and 84.3%, respectively. Complete elimination of phenolic compounds, 47.6% of TOC and 91% of COD was achieved during H2O2/UVC process with MP lamp at optimal conditions (H2O2:TOC ratio 5, UVC dose received by water 6.57 WUVC s cm(-2)). In order to compare performance of H2O2/UVC treatment with different experimental set up, the UVC dose required for removal of mg L(-1) of COD was suggested as a parameter and successfully applied. The hydrophilicity of H2O2/UVC effluent significantly increased which in turn enhanced the oxidation of organic compounds during CWPO step. After H2O2/UVC treatment with LP and MP lamps residual H2O2 concentration was 160 mg L(-1) and 96.5 mg L(-1), respectively. Remaining H2O2 was fully consumed during subsequent CWPO step (6 and 3.5 min of contact time for LP and MP, respectively). Total TOC and COD removal after MBT was 94.7% and 92.2% (using LP lamp) and 89.6% and 95%, (using MP lamp), respectively. The O&M cost for MBT with LP lamp was estimated to be 0.44 € m(-3) while with MP lamp it was nearly five

  13. Farm-scale testing of soybean peroxidase and calcium peroxide for surficial swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions

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    Maurer, Devin L.; Koziel, Jacek A.; Bruning, Kelsey; Parker, David B.

    2017-10-01

    The swine industry, regulatory agencies, and the public are interested in farm-tested methods for controlling gaseous emissions from swine barns. In earlier lab- and pilot-scale studies, a renewable catalyst consisting of soybean peroxidase (SBP) mixed with calcium peroxide (CaO2) was found to be effective in mitigating gaseous emissions from swine manure. Thus, a farm-scale experiment was conducted at the university's 178-pig, shallow-pit, mechanically-ventilated swine barn to evaluate SBP/CaO2 as a surficial manure pit additive under field conditions. The SBP was applied once at the beginning of the 42-day experiment at an application rate of 2.28 kg m-2 with 4.2% CaO2 added by weight. Gas samples were collected from the primary barn exhaust fans. As compared to the control, significant reductions in gaseous emissions were observed for ammonia (NH3, 21.7%), hydrogen sulfide (H2S, 79.7%), n-butyric acid (37.2%), valeric acid (47.7%), isovaleric acid (39.3%), indole (31.2%), and skatole (43.5%). Emissions of dimethyl disulfide/methanethiol (DMDS/MT) increased by 30.6%. Emissions of p-cresol were reduced by 14.4% but were not statistically significant. There were no significant changes to the greenhouse gas (GHG) emissions of methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O). The total (material + labor) treatment cost was 2.62 per marketed pig, equivalent to 1.5% of the pig market price. The cost of CaO2 catalyst was ∼60% of materials cost. The cost of soybean hulls (SBP source) was 0.60 per marketed pig, i.e., only 40% of materials cost.

  14. Ultraviolet and radical oxidation of airborne VOC`s. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Heinsohn, R.J.; Spaeder, T.A.; Albano, M.T.; Schmelzle, J.P.; Fetter, R.O.

    1994-03-18

    Airborne VOC`s reactions initiated by UV radiation at selected wavelengths from 185 to 308 nm have been studied. A simplified chemical kinetic mechanism is proposed incorporating photolysis and radical reactions. The concentration of HCHO and CH{sub 3}OH were predicted as a function of time, radiation wavelength, actinic flux and initial ozone concentration. The gas velocity and HCHO concentration were predicted in a gas stream flowing over a UV bulb. Experiments were conducted in which ethanol vapor and air were irradiated by low-pressure mercury bulbs. Ethanol disappeared in an overall first-order manner and an intermediate species, believed to be acetaldehyde, appeared and then disappeared.

  15. Ecotoxicity of ketoprofen, diclofenac, atenolol and their photolysis byproducts in zebrafish (Danio rerio)

    Energy Technology Data Exchange (ETDEWEB)

    Diniz, M.S., E-mail: mesd@fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Salgado, R., E-mail: r.salgado@campus.fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); ESTS-IPS, Escola Superior de Tecnologia de Setúbal do Instituto Politécnico de Setúbal, Rua Vale de Chaves, Campus do IPS, Estefanilha, 2910-761 Setúbal (Portugal); Pereira, V.J., E-mail: vanessap@itqb.unl.pt [Instituto de Biologia Experimental e Tecnológica (IBET), Av. da República (EAN), 2784-505 Oeiras (Portugal); Instituto de Tecnologia Química e Biológica (ITQB)—Universidade Nova de Lisboa (UNL), Estação Agronómica Nacional, Av. da República, 2780-157 Oeiras (Portugal); Carvalho, G., E-mail: gs.carvalho@fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Instituto de Biologia Experimental e Tecnológica (IBET), Av. da República (EAN), 2784-505 Oeiras (Portugal); Oehmen, A., E-mail: a.oehmen@fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Reis, M.A.M., E-mail: amr@fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Noronha, J.P., E-mail: jpnoronha@fct.unl.pt [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2015-02-01

    The occurrence of pharmaceutical compounds in wastewater treatment plants and surface waters has been detected worldwide, constituting a potential risk for aquatic ecosystems. Adult zebrafish, of both sexes, were exposed to three common pharmaceutical compounds (atenolol, ketoprofen and diclofenac) and their UV photolysis by-products over seven days. The results show that diclofenac was removed to concentrations < LOD after 5 min of UV irradiation. The oxidative stress response of zebrafish to pharmaceuticals and their photolysis by-products was evaluated through oxidative stress enzymes (glutathione-S-transferase, catalase, superoxide dismutase) and lipid peroxidation. Results suggest that the photolysis by-products of diclofenac were more toxic than those from the other compounds tested, showing an increase in GST and CAT levels, which are also supported by higher MDA levels. Overall, the toxicity of waters containing atenolol and ketoprofen was reduced after the parent compounds were transformed by photolysis, whereas the toxicity increased significantly from the by-products generated through diclofenac photolysis. Therefore, diclofenac photolysis would possibly necessitate higher irradiation time to ensure that the associated by-products are completely degraded to harmless form(s). - Highlights: • Toxicity evaluated for 3 common pharmaceuticals (atenolol, ketoprofen and diclofenac). • Toxicity assessed for the pharmaceuticals and UV photolysis by-products in zebrafish. • Diclofenac photolysis by-products are more toxic than the parent compound. • Ketoprofen and atenolol show stronger oxidative stress response than by-products. • UV photolysis should ensure full removal of diclofenac metabolites to avoid toxicity.

  16. Aqueous photolysis of niclosamide

    Science.gov (United States)

    Graebing, P.W.; Chib, J.S.; Hubert, T.D.; Gingerich, W.H.

    2004-01-01

    The photodegradation of [14C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 A? 1.0 A?C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising 40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

  17. VOC emissions chambers

    Data.gov (United States)

    Federal Laboratory Consortium — In order to support the development of test methods and reference materials for volatile organic compounds (VOC) emissions from building materials and furnishings,...

  18. Modeling of photolysis rates over Europe: impact on chemical gaseous species and aerosols

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    E. Real

    2010-07-01

    %. The decrease in OH leads to an increase of the life-time of several species such as VOC. For example, isoprene ground concentrations increase in average by around 10%. NO2 concentrations are not strongly impacted and O3 concentrations are mostly reduced at the ground with a monthly mean decrease of about 3%. O3 peaks are systematically decreased because of the NO2 photolysis rate decrease. Not only gas are impacted but also secondary aerosols, due to changes in gas precursors concentrations. Monthly mean concentrations of nitrate, ammonium, sulphate and secondary organic aerosol at the ground are modified by up to 4% but PM10 and PM2.5 only by 1 to 2%. However monthly mean local differences in PM10 and PM2.5 concentrations can reach 8% over regions with strong production of secondary aerosols such as the Po valley.

    In terms of air quality monitoring, ground concentrations of O3, NO2 and PM10 are compared with measurements from the EMEP stations. Statistics are usually better for simulation taking into account aerosol impact on photolysis rates, but changes are small. On the other hand, the systematic O3 peak reduction leads to large differences in the exceedances of the European O3 threshold as calculated by the model. The number of exceedances of the information and the alert threshold is divided by 2 when the aerosol impact on photochemistry is simulated. This shows the importance of taking into account aerosols impact on photolysis rates in air quality studies.

  19. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

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    K. M. Badali

    2015-02-01

    Full Text Available This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA material formed by terpene ozonolysis. The SOA aerosol is collected on filters, dissolved in water containing a radical trap (benzoic acid, and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH, the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF assay, which was calibrated using H2O2. The OH formation rates from SOA are five times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over three times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloudwater and aerosol chemistry.

  20. Dejima VOC dan rangaku

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    Bambang Wibawarta

    2008-10-01

    Full Text Available Japan and the Netherlands have maintained a special relationship for about 300years since the adoption of the National Seclusion policy, the so-called sakoku bythe Tokugawa shogunate (1603-1867. The Dutch began trading with Japan andengaging with Japanese society in 1600, when a Dutch ship, De Liefde, arrived inKyushu. The Tokugawa government measures regarding foreign policy includedregulations on foreign access to Japan and a prohibition on Japanese goingabroad. Between the middle of the seventeenth to the early nineteenth century,Japan was characterized by a stable political pattern in which representativesof the VOC (Dutch East India Company, were the only Europeans with a rightto trade in Japan. In the course of this period, the Japanese evaluation of theDutch changed from regarding them as commercial agents to seeing them asimporters of European knowledge. This paper is especially concerned with theinfluence of the so-called ‘Dutch Studies’ (rangaku on the early modernizationof Japan, especially with regard to medicine and the natural sciences. Thisresearch examines the development of rangaku and the trading between Japanand VOC at Dejima.

  1. On speciation of VOC localization

    Science.gov (United States)

    Chen, S.; Chang, J.; Wang, J.

    2011-12-01

    Most of the gas-phase chemical mechanisms successfully used in gas-phase atmospheric chemical processes, such as CBM-Z, RADM2 or SAPRC-07, treat hundreds of VOC as lumped organic species by their chemical characteristics. Most of the model results are compared with total VOC observations, and it is not appropriate to compare lumped VOC simulations to observations even if there are separate VOC observations like Photochemical Assessment Monitoring Stations (PAMS). While the PAMS Air Quality Model (PAMS-AQM) is developed, separate organic species observed by PAMS without a doubt can be directly compared with model simulations. From the past case study (Chen et al., 2010), it shows a major and very significant finding in that detailed emissions of VOC in the existing emissions database are often in error in Taiwan or other countries due to the fact that the annual VOC emissions are classified into hundreds of species-specific emissions by using the speciation factors following the protocol of the U.S. EPA (AP-42). Based on all PAMS observations from 2006-2007, four base cases with well comparable meteorological simulations were selected for the unified correction for all sources in Taiwan. After the PAMS species emissions are modified, the diurnal patterns and simulation-observation correlation for most of the PAMS species are improved, and the concentration levels are more comparable with those of observations. More expanded case studies also revealed necessary corrections for the PAMS species emissions. Sensitivity analyses for lumped organic species with modified PAMS species emissions are also conducted. After modified PAMS emissions are added into lumped VOC emissions, there is an increase of only 10% of totally VOC emissions. While the sources of the lumped VOC emissions are changed, ozone formation shows no significant change with modified lumped VOC emissions. This helps to support the argument that for ozone simulation, the lumped VOC processes balance out

  2. Aromatic VOCs global influence in the ozone production

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    Cabrera-Perez, David; Pozzer, Andrea

    2016-04-01

    Aromatic hydrocarbons are a subgroup of Volatile Organic Compounds (VOCs) of special interest in the atmosphere of urban and semi-urban areas. Aromatics form a high fraction of VOCs, are highly reactive and upon oxidation they are an important source of ozone. These group of VOCs are released to the atmosphere by processes related to biomass burning and fossil fuel consumption, while they are removed from the atmosphere primarily by OH reaction and by dry deposition. In addition, a branch of aromatics (ortho-nitrophenols) produce HONO upon photolysis, which is responsible of certain amount of the OH recycling. Despite their importance in the atmosphere in anthropogenic polluted areas, the influence of aromatics in the ozone production remains largely unknown. This is of particular relevance, being ozone a pollutant with severe side effects on air quality, health and climate. In this work the atmospheric impacts at global scale of the most emitted aromatic VOCs in the gas phase (benzene, toluene, xylenes, ethylbenzene, styrene, phenol, benzaldehyde and trimethylbenzenes) are analysed and assessed. Specifically, the impact on ozone due to aromatic oxidation is estimated, as this is of great interest in large urban areas and can be helpful for developing air pollution control strategies. Further targets are the quantification of the NOx loss and the OH recycling due to aromatic oxidation. In order to investigate these processes, two simulations were performed with the numerical chemistry and climate simulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model. The simulations compare two cases, one with ozone concentrations when aromatics are present or the second one when they are missing. Finally, model simulated ozone is compared against a global set of observations in order to better constrain the model accuracy.

  3. Decolorization of some azo dyes by direct photolysis and H2O2/UV processes

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    Keiko Takashima

    2009-03-01

    Full Text Available The decolorization of acid orange 7 (AO7, direct orange 34 (DO 34, direct red 23 (DR23 and direct yellow 86 (DY86 azo dyes was investigated by direct photolysis and hydrogen peroxide-assisted photodegradation respectively in closed and open reactor to the atmosphere under UV radiation at natural pHs and 30 ºC. Four azo dyes decolorization (1,5x10-4 mol L-1 was not significant in presence of H2O2 in closed reactor during 3 h irradiation, whereas in open reactor, the decolorization was respectively 96, 82, 32, and 45% for AO7, DO34, DR23 and DY86. The decolorization by direct photolysis in open reactor was significantly higher in comparison to closed one.

  4. Photolysis of a Benzyne Precursor Studied by Time-Resolved FTIR Spectroscopy.

    Science.gov (United States)

    Torres-Alacan, Joel

    2016-02-01

    The 266 nm laser flash photolysis of phtaloyl peroxide (2) in liquid acetonitrile solution at room temperature has been investigated. Upon 266 nm laser irradiation, 2 is effectively photodecarboxylated leading to the formation of o-benzyne (1) and two equivalents of CO2, yet a small fraction of photolyzed 2 follows a different pathway leading to 6-oxocyclohexa-2,4-dienylideneketene (3) and one equivalent of CO2. Compound 3 is kinetically reactive and reacts in the microsecond time scale following a first-order kinetic law. The presence of 1 in the photolysis experiment is confirmed by trapping experiments with methyl 1-methylpyrrole-2-carboxylate (6). The Diels-Alder reaction between 1 and 6 occurs under the selected experimental conditions on a time scale shorter than 100 ms.

  5. Laser Flash Photolysis Studies on Gallic Acid

    Institute of Scientific and Technical Information of China (English)

    ZHU Hong-Ping; ZHAO Hong-Wei; ZHANG Zhao-Xia; WANG Wen-Feng; YAO Si-De

    2006-01-01

    The transient species of gallic acid (GA) have been studied by 266 nm nanosecond laser flash photolysis in aqueous solution and acetonitrile. The intermediate with absorption at 320 nm was identified as excited triplet state (3GA*), the decay rates of which were obtained in aqueous solution and acetonitrile respectively. Energy transfer from 3GA* to β-carotene was observed and the energy transfer rate constant kent was determined to be 2.2 × 109 mol-1·L·s-1. GA underwent photoionization during photolysis and the quantum yield of photoionization was determined to be 0.12 at room temperature with KI as a reference.

  6. Tetrafluoroethylene telomerization initiated by benzoyl peroxide

    Science.gov (United States)

    Bolshakov, A. I.; Kuzina, S. I.; Kiryukhin, D. P.

    2017-03-01

    The radical telomerization of tetrafluoroethylene initiated by benzoyl peroxide (BP) photolysis at λ ≥ 365 nm is studied in acetone, dichloromethane, carbon tetrachloride, and Freon 114B2 at 25°C. The products of synthesis are a mixture of telomers of different molar masses, segregated into soluble and insoluble fractions. To characterize the radicals initiating telomerization, crystalline BP and its solution in ethanol are subjected to low-temperature (77 K) photolysis, with the liquid system serving as a model for BP behavior in solutions of telogens. It is established that radicals are not only initiators but also participate in chain termination reactions, lowering the telomers' molar mass and thus raising the proportion of the soluble fraction. Telomerization initiated by an initiator compound versus initiation by gamma radiation are compared and discussed.

  7. UV photolysis for accelerating pyridine biodegradation.

    Science.gov (United States)

    Zhang, Yongming; Chang, Ling; Yan, Ning; Tang, Yingxia; Liu, Rui; Rittmann, Bruce E

    2014-01-01

    Pyridine, a nitrogen-containing heterocyclic compound, is slowly biodegradable, and coupling biodegradation with UV photolysis is a potential means to accelerate its biotransformation and mineralization. The initial steps of pyridine biodegradation involve mono-oxygenation reactions that have molecular oxygen and an intracellular electron carrier as cosubstrates. We employed an internal circulation baffled biofilm reactor for pyridine biodegradation following three protocols: direct biodegradation (B), biodegradation after photolysis (P+B), and biodegradation with succinic acid added (B+S). Succinic acid was the main UV-photolysis product from pyridine, and its catabolic oxidation generates internal electron carriers that may accelerate the initial steps of pyridine biodegradation. Compared with direct biodegradation of pyridine (B), the removal rate for the same concentration of photolyzed pyridine (P+B) was higher by 15 to 43%, depending on the initial pyridine concentrations (increasing through the range of 130 to 310 mg/L). Adding succinic acid alone (B+S) gave results similar to P+B, which supports that succinic acid was the main agent for accelerating the pyridine biodegradation rate. In addition, protocols P+B and B+S were similar in terms of increasing pyridine mineralization over 10 h: 84% and 87%, respectively, which were higher than with protocol B (72%). The positive impact of succinic acid-whether added directly or produced via UV photolysis-confirms that its catabolism, which produced intracellular electron carriers, accelerated the initial steps of pyridine biotransformation.

  8. Nanosecond Laser Photolysis of Opaque Heterogeneous Photosensitizers.

    Science.gov (United States)

    1987-10-01

    Willsher spent two weeks in Spain during the Summer working on this project and presented a poster at the XIIth Recunion Bienal de Quimica Organica de la...Real Sociedad Espaiola de Quimica , Cordoba, Spain,23-25 September, entitled "Fase Solida : Contribuci6n de la "Laser Flash Photolysis" a la Elucidacion

  9. High winter ozone pollution from carbonyl photolysis in an oil and gas basin

    Science.gov (United States)

    Edwards, Peter M.; Brown, Steven S.; Roberts, James M.; Ahmadov, Ravan; Banta, Robert M.; Degouw, Joost A.; Dubé, William P.; Field, Robert A.; Flynn, James H.; Gilman, Jessica B.; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O.; Lefer, Barry L.; Lerner, Brian M.; Li, Rui; Li, Shao-Meng; McKeen, Stuart A.; Murphy, Shane M.; Parrish, David D.; Senff, Christoph J.; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R.; Trainer, Michael K.; Tsai, Catalina; Veres, Patrick R.; Washenfelder, Rebecca A.; Warneke, Carsten; Wild, Robert J.; Young, Cora J.; Yuan, Bin; Zamora, Robert

    2014-10-01

    The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts

  10. High winter ozone pollution from carbonyl photolysis in an oil and gas basin.

    Science.gov (United States)

    Edwards, Peter M; Brown, Steven S; Roberts, James M; Ahmadov, Ravan; Banta, Robert M; deGouw, Joost A; Dubé, William P; Field, Robert A; Flynn, James H; Gilman, Jessica B; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O; Lefer, Barry L; Lerner, Brian M; Li, Rui; Li, Shao-Meng; McKeen, Stuart A; Murphy, Shane M; Parrish, David D; Senff, Christoph J; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R; Trainer, Michael K; Tsai, Catalina; Veres, Patrick R; Washenfelder, Rebecca A; Warneke, Carsten; Wild, Robert J; Young, Cora J; Yuan, Bin; Zamora, Robert

    2014-10-16

    The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts

  11. Hydrogen isotope fractionation in the photolysis of formaldehyde

    NARCIS (Netherlands)

    Rhee, T.S.; Brenninkmeijer, C.A.M.; Röckmann, T.

    2007-01-01

    Experiments investigating the isotopic fractionation in the formation of H2 by the photolysis of CH2O under tropospheric conditions are reported and discussed. The deuterium (D) depletion in H2 produced is 500(±20)‰ with respect to the parent CH2O. We also observed that complete photolysis of CH2O u

  12. Flash photolysis-shock tube studies

    Energy Technology Data Exchange (ETDEWEB)

    Michael, J.V. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Even though this project in the past has concentrated on the measurement of thermal bimolecular reactions of atomic species with stable molecules by the flash or laser photolysis-shock tube (FP- or LP-ST) method using atomic resonance absorption spectrometry (ARAS) as the diagnostic technique, during the past year the authors have concentrated on studies of the thermal decompositions of selected chlorocarbon molecules. These studies are necessary if the degradation of chlorine containing organic molecules by incineration are to be understood at the molecular level. Clearly, destruction of these molecules will not only involve abstraction reactions, when possible, but also thermal decomposition followed by secondary reactions of the initially formed atoms and radicals. Studies on the thermal decomposition of CH{sub 3}Cl are complete, and the curve-of-growth for Cl-atom atomic resonance absorption has been determined. The new thermal decomposition studies are similar to those already reported for CH{sub 3}Cl.

  13. 688 AMBIENT VOLATILE ORGANIC COMPOUNDS (VOCS ...

    African Journals Online (AJOL)

    Osondu

    The VOCs were classified thus: aromatics 41%, halogenated 42%, esters 3%, ketones 8%, ... and Industrial emission were identified as sources of VOCs in the studied industrial area with ... canisters, or by dynamic or diffusive adsorption .... The GC/FID was standardized and ... with CS2 was prepared from stock standard in.

  14. DEVELOPING A NO-VOC WOOD TOPCOAT

    Science.gov (United States)

    The paper reports an evaluation of a new low-VOC (volatile organic compound) wood coating technology, its performance characteristics, and its application and emissions testing. The low-VOC wood coating selected for the project was a two-component, water-based epoxy coating. Poly...

  15. Concentration of Hydrogen Peroxide

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2006-01-01

    Methods for concentrating hydrogen peroxide solutions have been described. The methods utilize a polymeric membrane separating a hydrogen peroxide solution from a sweep gas or permeate. The membrane is selective to the permeability of water over the permeability of hydrogen peroxide, thereby facilitating the concentration of the hydrogen peroxide solution through the transport of water through the membrane to the permeate. By utilizing methods in accordance with the invention, hydrogen peroxide solutions of up to 85% by volume or higher may be generated at a point of use without storing substantial quantities of the highly concentrated solutions and without requiring temperatures that would produce explosive mixtures of hydrogen peroxide vapors.

  16. T2VOC user`s guide

    Energy Technology Data Exchange (ETDEWEB)

    Falta, R.W. [Clemson Univ., Clemson, SC (United States). Dept. of Earth Sciences; Pruess, K.; Finsterle, S. [Lawrence Berkeley Lab., CA (United States); Battistelli, A. [AQUATER S.p.A., San Lorenzo in Campo, (Italy)

    1995-03-01

    T2VOC is a numerical simulator for three-phase, three-component, non-isothermal flow of water, air, and a volatile organic compound (VOC) in multidimensional heterogeneous porous media. Developed at the Lawrence Berkeley Laboratory, T2VOC is an extension of the TOUGH2 general-purpose simulation program. This report is a self-contained guide to application of T2VOC to subsurface contamination problems involving nonaqueous phase liquids (NAPLs). It gives a technical description of the T2VOC code, including a discussion of the physical processes modeled, and the mathematical and numerical methods used. Detailed instructions for preparing input data are presented along with several illustrative sample problems.

  17. OH formation by HONO photolysis during the BERLIOZ experiment

    Science.gov (United States)

    Alicke, B.; Geyer, A.; Hofzumahaus, A.; Holland, F.; Konrad, S.; PäTz, H. W.; SchäFer, J.; Stutz, J.; Volz-Thomas, A.; Platt, U.

    2003-02-01

    The photolysis of nitrous acid (HONO) in the early morning hours is an important source of OH radicals, the most important daytime oxidizing species. Although the importance of this mechanism has been recognized for many years, no accurate quantification of this OH source is available, and the role of HONO photolysis is often underestimated. We present measurements of HONO and its precursor NO2 by Differential Optical Absorption Spectroscopy (DOAS) during the Berliner Ozonexperiment (BERLIOZ) field campaign in July/August 1998 at Pabstthum near Berlin, Germany. HONO concentrations, formation rates, and simultaneously measured HONO photolysis frequencies are used to calculate the total amount of OH formed by HONO photolysis during a full diurnal cycle. A comparison with the OH formation by photolysis of O3 and HCHO and by the reaction of alkenes with ozone shows that HONO photolysis contributed up to 20% of the total OH formed in a 24 hour period during this campaign. In the morning hours, HONO photolysis was by far the most important OH source during BERLIOZ.

  18. Degradation of water polluted with used cooking oil by solar photolysis, Fenton and solar photo Fenton.

    Science.gov (United States)

    Vergara-Sánchez, J; Silva-Martínez, S

    2010-01-01

    The degradation of used cooking safflower oil aqueous solutions by photolysis, Fenton, and photo Fenton under solar light is reported. The processes were carried out in a photochemical reactor with recirculation. Operating variables such as, pH, oil concentration and molar ratio of [H(2)O(2)]:[oil] were investigated to test their effects on the treatment efficiency of Fenton process. Also the iron catalyzed decomposition of hydrogen peroxide in the solar photo Fenton reaction was studied under different experimental conditions. The degree of oil oxidation was monitored by the measurements of chemical oxygen demand (COD) analyses. It was found that at pH 2.6 and a molar ratio of [H(2)O(2)]:[oil] of 489:1 were more efficient for COD abatement. The experimental results showed that the sole effect of the solar irradiation (photolysis) aided to decrease approximately 65% of COD at neutral pH in a reaction time period of 15 h; whereas a decrease of 47% and approximately 90% of COD was obtained by Fenton and photo Fenton treatment, respectively, after a reaction time of 50 min. It was observed a decrease in the decomposition of H(2)O(2) in the solar photo Fenton process, in subsequent additions of H(2)O(2), and H(2)O(2) + Fe(2+).

  19. PRECIPITATION OF PLUTONOUS PEROXIDE

    Science.gov (United States)

    Barrick, J.G.; Manion, J.P.

    1961-08-15

    A precipitation process for recovering plutonium values contained in an aqueous solution is described. In the process for precipitating plutonium as plutonous peroxide, hydroxylamine or hydrazine is added to the plutoniumcontaining solution prior to the addition of peroxide to precipitate plutonium. The addition of hydroxylamine or hydrazine increases the amount of plutonium precipitated as plutonous peroxide. (AEC)

  20. Photoelectron Imaging of OXIDE.VOC Clusters

    Science.gov (United States)

    Patros, Kellyn M.; Mann, Jennifer; Chick Jarrold, Caroline

    2016-06-01

    Perturbations of the bare O2- and O4- electronic structure arising from VOC (VOC = hexane, isoprene, benzene and benzene.D6) interactions are investigated using anion photoelectron imaging at 2.33 and 3.49 eV photon energies. Trends observed from comparing features in the spectra include VOC-identity-dependent electron affinities of the VOC complexes relative to the bare oxide clusters, due to enhance stability in the anion complex relative to the neutral. Autodetachment is observed in all O4-.VOC spectra and only isoprene with O2-. In addition, the intensities of transitions to states correlated with the singlet states of O2 neutral via detachment from the O2-.VOC anion complexes show dramatic VOC-identity variations. Most notably, benzene as a complex partner significantly enhances these transitions relative to O2- and O2-.hexane. A less significant enhancement is also observed in the O2-.isoprene complex. This enhancement may be due to the presence of low-lying triplet states in the complex partners.

  1. Photochemical of Polychlorinated biphenyl by the photolysis and ...

    African Journals Online (AJOL)

    Michael Horsfall

    organic pollutants (POPs) that are of international concern because of global .... analysis. For quality control, the experiments were conducted in three replicates. ... Table 2: Effect of UV intensity on PCBs degradation efficiency (%) of photolysis.

  2. Photolysis of rac-leucine with circularly polarized synchrotron radiation.

    Science.gov (United States)

    Meierhenrich, Uwe J; Filippi, Jean-Jacques; Meinert, Cornelia; Hoffmann, Søren V; Bredehöft, Jan Hendrik; Nahon, Laurent

    2010-06-01

    Amino acids that pass the RNA machinery in living organisms occur in L-configuration. The question on the evolutionary origin of this biomolecular asymmetry remains unanswered to this day. Amino acids were detected in artificially produced interstellar ices, and L-enantiomer-enriched amino acids were identified in CM-type meteorites. This hints at a possible interstellar/circumstellar origin of the amino acids themselves as well as their stereochemical asymmetry. Based upon the current knowledge about the occurrence of circularly-polarized electromagnetic radiation in interstellar environments, we subjected rac-leucine to far-UV circularly-polarized synchrotron radiation. Asymmetric photolysis was followed by an analysis in an enantioselective GC/MS system. Here, we report on an advanced photolysis rate of more than 99% for leucine. The results indicate that high photolysis rates can occur under the chosen conditions, favoring enantioselective photolysis. In 2014, the obtained results will be reexamined by cometary mission Rosetta.

  3. Formation of hydroxyl radical from the photolysis of salicylic acid.

    Science.gov (United States)

    Zhou, Can-Hua; Cheng, Shi-Bo; Yin, Hong-Ming; He, Guo-Zhong

    2011-05-26

    Photodissociation dynamics of salicylic acid (SA) in the gas phase at different photolysis wavelengths (266, 315-317 nm) is investigated by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence (LIF) technique. At all the photolysis wavelengths it is found that the nascent OH radicals are produced mostly in a vibrationally ground state (υ'' = 0) and have similar rotational state distributions. The two spin-orbit and Λ-doublet states of the OH fragment formed in the dissociation are measured to have a nonstatistical distribution at each photolysis wavelength. The LIF signal of the OH could be observed upon photolysis at 317 nm but not at 317.5 nm. The threshold of OH formation from SA photodissociation is estimated to be 98.2 ± 0.9 kcal/mol. The effect of the phenolic OH group on the dissociation of SA is discussed.

  4. Photolysis of Periodate and Periodic Acid in Aqueous Solution

    DEFF Research Database (Denmark)

    Sehested, Knud; Kläning, U. K.

    1978-01-01

    The photochemistry of periodate and periodic acid in aqueous solution was studied (i) by quantum yield measurements at low light intensity (ii) by flash photolysis, and (iii) by photolysis of glassy samples at 77 K. The photochemical studies were supplemented with pulse radiolysis studies...... of aqueous periodate solutions and with kinetic studies using stopped-flow technique. In strongly alkaline solution the photodecomposition of periodate proceeds via formation of O– and IVI. At pH

  5. Solvent Effect on the Photolysis of Riboflavin.

    Science.gov (United States)

    Ahmad, Iqbal; Anwar, Zubair; Ahmed, Sofia; Sheraz, Muhammad Ali; Bano, Raheela; Hafeez, Ambreen

    2015-10-01

    The kinetics of photolysis of riboflavin (RF) in water (pH 7.0) and in organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol, ethyl acetate) has been studied using a multicomponent spectrometric method for the assay of RF and its major photoproducts, formylmethylflavin and lumichrome. The apparent first-order rate constants (k obs) for the reaction range from 3.19 (ethyl acetate) to 4.61 × 10(-3) min(-1) (water). The values of k obs have been found to be a linear function of solvent dielectric constant implying the participation of a dipolar intermediate along the reaction pathway. The degradation of this intermediate is promoted by the polarity of the medium. This indicates a greater stabilization of the excited-triplet states of RF with an increase in solvent polarity to facilitate its reduction. The rate constants for the reaction show a linear relation with the solvent acceptor number indicating the degree of solute-solvent interaction in different solvents. It would depend on the electron-donating capacity of RF molecule in organic solvents. The values of k obs are inversely proportional to the viscosity of the medium as a result of diffusion-controlled processes.

  6. Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources

    Energy Technology Data Exchange (ETDEWEB)

    Sanches, S. [Instituto de Biologia Experimental e Tecnologica (IBET), Av. Republica, Qta. do Marques (EAN), 2784-505 Oeiras (Portugal); Instituto de Tecnologia Quimica e Biologica (ITQB) - Universidade Nova de Lisboa (UNL), Av. da Republica, Estacao Agronomica Nacional, 2780-157 Oeiras (Portugal); Leitao, C. [Instituto de Tecnologia Quimica e Biologica (ITQB) - Universidade Nova de Lisboa (UNL), Av. da Republica, Estacao Agronomica Nacional, 2780-157 Oeiras (Portugal); Penetra, A.; Cardoso, V.V.; Ferreira, E.; Benoliel, M.J. [Empresa Portuguesa das Aguas Livres, S.A., Avenida de Berlim, 15, 1800-031 Lisboa (Portugal); Crespo, M.T. Barreto [Instituto de Biologia Experimental e Tecnologica (IBET), Av. Republica, Qta. do Marques (EAN), 2784-505 Oeiras (Portugal); Instituto de Tecnologia Quimica e Biologica (ITQB) - Universidade Nova de Lisboa (UNL), Av. da Republica, Estacao Agronomica Nacional, 2780-157 Oeiras (Portugal); Pereira, V.J., E-mail: vanessap@itqb.unl.pt [Instituto de Biologia Experimental e Tecnologica (IBET), Av. Republica, Qta. do Marques (EAN), 2784-505 Oeiras (Portugal); Instituto de Tecnologia Quimica e Biologica (ITQB) - Universidade Nova de Lisboa (UNL), Av. da Republica, Estacao Agronomica Nacional, 2780-157 Oeiras (Portugal)

    2011-09-15

    Highlights: {yields} Low pressure UV photolysis can be used by drinking water utilities to degrade PAHs. {yields} Real water matrices with different compositions were tested. {yields} Photolysis kinetic parameters and by-product formation are described. {yields} The formation of photolysis by-products is highly dependent on the source waters. - Abstract: The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm{sup 2}, anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested.

  7. EVALUATION OF LOW-VOC LATEX PAINTS

    Science.gov (United States)

    The paper gives results of an evaluation of four commercially available low-VOC (volatile organic compound) latex paints as substitutes for conventional latex paints by assessing both their emission characteristics and their performance as coatings. Bulk analysis indicated that ...

  8. Locating industrial VOC sources with aircraft observations.

    Science.gov (United States)

    Toscano, P; Gioli, B; Dugheri, S; Salvini, A; Matese, A; Bonacchi, A; Zaldei, A; Cupelli, V; Miglietta, F

    2011-05-01

    Observation and characterization of environmental pollution, focussing on Volatile Organic Compounds (VOCs), in a high-risk industrial area, are particularly important in order to provide indications on a safe level of exposure, indicate eventual priorities and advise on policy interventions. The aim of this study is to use the Solid Phase Micro Extraction (SPME) method to measure VOCs, directly coupled with atmospheric measurements taken on a small aircraft environmental platform, to evaluate and locate the presence of VOC emission sources in the Marghera industrial area. Lab analysis of collected SPME fibres and subsequent analysis of mass spectrum and chromatograms in Scan Mode allowed the detection of a wide range of VOCs. The combination of this information during the monitoring campaign allowed a model (Gaussian Plume) to be implemented that estimates the localization of emission sources on the ground.

  9. Low VOC Barrier Coating for Industrial Maintenance

    Science.gov (United States)

    2012-09-01

    Technology Certification Program HAP Hazardous Air Pollutant HW hazardous waste LVBC low VOC barrier coating MEK methyl ethyl ketone MIL-DTL...peeling, blistering , tape adhesion, pull-off adhesion, film thickness, and LVBC/ZVT patch test adhesion testing in an acceptable or better manner...significant reductions in the amount of hazardous waste generated by the Navy. The ZVT technology contains less than 5 g/l of VOC and the resulting

  10. Photolysis of aromatic pollutants in clean and dirty ice

    Science.gov (United States)

    Kahan, T.; Malley, P.; Stathis, A.

    2015-12-01

    Anthropogenic aromatic pollutants such as polycyclic aromatic hydrocarbons (PAHs) and substituted benzenes often become more toxic following atmospheric oxidation. Photolysis of these pollutants in ice can be much faster than that in aqueous solution, which might lead to higher carcinogenic loadings in snow-covered regions. In this work we investigate two things. First, we investigate whether toluene, which has been detected at very elevated concentrations near hydraulic fracturing operations, can undergo photolysis at ice surfaces. Toluene in aqueous solution does not absorb sunlight, so photolysis has not been considered a potential atmospheric fate. However, benzene was recently demonstrated to undergo a significant red shift in its absorbance at ice surfaces, leading to photolysis under environmentally-relevant conditions. Here we show that toluene also undergoes photolysis at ice surfaces. In a second set of experiments, we have investigated the effects of organic matter on the photolysis kinetics ofPAHs in ice and at ice surfaces. We found that very small loadings of hydrophobic organics such as octanol can significantly suppress PAH photolysis kinetics in ice, but that the primary effect of the more soluble fulvic acid is competitive photon absorption. Our results show that photochemistry of anthropogenic pollutants can follow very different mechanisms and kinetics in ice than in aqueous solution, and that the photochemical fate of these pollutants depends strongly on the composition of the snow. These results have implications for pollutant fate and human health in a wide range of snow-covered environments including remote areas, cities, and regions near gas and oil extraction operations.

  11. Chemistry of peroxide compounds

    Science.gov (United States)

    Volnov, I. I.

    1981-01-01

    The history of Soviet research from 1866 to 1967 on peroxide compounds is reviewed. This research dealt mainly with peroxide kinetics, reactivity and characteristics, peroxide production processes, and more recently with superoxides and ozonides and emphasis on the higher oxides of group 1 and 2 elements. Solid state fluidized bed synthesis and production of high purity products based on the relative solubilities of the initial, intermediate, and final compounds and elements in liquid ammonia are discussed.

  12. POCP for individual VOC under European conditions

    Energy Technology Data Exchange (ETDEWEB)

    Altenstedt, J.; Pleijel, K.

    1998-09-01

    Ground level ozone has been recognised as one of the most important environmental threats on the regional scale in Europe. Ozone is today considered to be harmful to human health already at the relatively low concentrations present in southern Scandinavia. The fact that ozone has the potential to damage vegetation at these concentrations is already well known. Ozone also gives rise to degradation of materials and is one of the gases which adds to the greenhouse effect. Ground level ozone is formed from nitrogen oxides (NO{sub x}) and volatile organic compounds (VOC) in the presence of sunlight. The only way to reduce ozone is therefore to reduce the emissions of the precursors. Ranking individual VOC by their ozone formation potential can make emission reductions more environmentally efficient and save time and money. POCP values give a ranking of the ozone formation ability of an individual VOC relative to other VOC. A critical analysis of the POCP concept has been performed which shows that the background emissions of NO{sub x} and VOC affect the POCP values to a large extent. Based on the critical analysis, five scenarios with different background emissions of NO{sub x} and VOC were selected for calculation of POCP values. These scenarios were chosen because they reflect the variation in POCP values which arise in different environments within Europe. The range thus indicates POCP values which are intended to be applicable within Europe. POCP values for 83 different VOC are presented in the form of ranges in this report. 42 refs, 13 figs, 3 tabs

  13. VOCs in Arid soils: Technology summary

    Energy Technology Data Exchange (ETDEWEB)

    1994-02-01

    The Volatile Organic Compounds In Arid Soils Integrated Demonstration (VOC-Arid ID) focuses on technologies to clean up volatile organic compounds and associated contaminants in soil and groundwater at arid sites. The initial host site is the 200 West Area at DOE`s Hanford site in southeastern Washington state. The primary VOC contaminant is carbon tetrachloride, in association with heavy metals and radionuclides. An estimated 580--920 metric tons of carbon tetrachloride were disposed of between 1955 and 1973, resulting in extensive soil and groundwater contamination. The VOC-Arid ID schedule has been divided into three phases of implementation. The phased approach provides for: rapid transfer of technologies to the Environmental Restoration (EM-40) programs once demonstrated; logical progression in the complexity of demonstrations based on improved understanding of the VOC problem; and leveraging of the host site EM-40 activities to reduce the overall cost of the demonstrations. During FY92 and FY93, the primary technology demonstrations within the ID were leveraged with an ongoing expedited response action at the Hanford 200 West Area, which is directed at vapor extraction of VOCs from the vadose (unsaturated) zone. Demonstration efforts are underway in the areas of subsurface characterization including: drilling and access improvements, off-gas and borehole monitoring of vadose zone VOC concentrations to aid in soil vapor extraction performance evaluation, and treatment of VOC-contaminated off-gas. These current demonstration efforts constitute Phase 1 of the ID and, because of the ongoing vadose zone ERA, can result in immediate transfer of successful technologies to EM-40.

  14. Locating industrial VOC sources with aircraft observations

    Energy Technology Data Exchange (ETDEWEB)

    Toscano, P., E-mail: p.toscano@ibimet.cnr.it [Institute for Biometeorology (IBIMET - CNR), Via G. Caproni 8, 50145 Firenze (Italy); Gioli, B. [Institute for Biometeorology (IBIMET - CNR), Via G. Caproni 8, 50145 Firenze (Italy); Dugheri, S. [Careggi Hospital-University of Florence, Occupational Health Division, Largo Palagi 1, 50100 Florence (Italy); Salvini, A. [Department of Organic Chemistry, University of Florence, Via della Lastruccia 13, 50019 Sesto Fiorentino, Florence (Italy); Matese, A. [Institute for Biometeorology (IBIMET - CNR), Via G. Caproni 8, 50145 Firenze (Italy); Bonacchi, A. [Careggi Hospital-University of Florence, Occupational Health Division, Largo Palagi 1, 50100 Florence (Italy); Zaldei, A. [Institute for Biometeorology (IBIMET - CNR), Via G. Caproni 8, 50145 Firenze (Italy); Cupelli, V. [Careggi Hospital-University of Florence, Occupational Health Division, Largo Palagi 1, 50100 Florence (Italy); Miglietta, F. [Institute for Biometeorology (IBIMET - CNR), Via G. Caproni 8, 50145 Firenze (Italy); Fondazione Edmund Mach, Via Mach 1, San Michele all' Adige, Trento (Italy)

    2011-05-15

    Observation and characterization of environmental pollution, focussing on Volatile Organic Compounds (VOCs), in a high-risk industrial area, are particularly important in order to provide indications on a safe level of exposure, indicate eventual priorities and advise on policy interventions. The aim of this study is to use the Solid Phase Micro Extraction (SPME) method to measure VOCs, directly coupled with atmospheric measurements taken on a small aircraft environmental platform, to evaluate and locate the presence of VOC emission sources in the Marghera industrial area. Lab analysis of collected SPME fibres and subsequent analysis of mass spectrum and chromatograms in Scan Mode allowed the detection of a wide range of VOCs. The combination of this information during the monitoring campaign allowed a model (Gaussian Plume) to be implemented that estimates the localization of emission sources on the ground. - Highlights: > Flight plan aimed at sampling industrial area at various altitudes and locations. > SPME sampling strategy was based on plume detection by means of CO{sub 2}. > Concentrations obtained were lower than the limit values or below the detection limit. > Scan mode highlighted presence of {gamma}-butyrolactone (GBL) compound. > Gaussian dispersion modelling was used to estimate GBL source location and strength. - An integrated strategy based on atmospheric aircraft observations and dispersion modelling was developed, aimed at estimating spatial location and strength of VOC point source emissions in industrial areas.

  15. Laser photolysis-resonance fluorescence technique (LP-RF) applied to the study of reactions of atmospheric interest

    Science.gov (United States)

    Albaladejo, J.; Cuevas, C. A.; Notario, A.; Martínez, E.

    Atomic chlorine is highly reactive with a variety of organic and inorganic compounds so that relatively small concentrations can compete with the tropospheric oxidants (OH, O3 and NO3) in determining the tropospheric fate of such compounds [1]. Besides, there is a lot of evidence that bromine compounds play significant role in the ozone chemistry both in the troposphere and in the stratosphere [2]. In this work we show the laser photolysis-resonance fluorescence technique (LP-RF) applied to the study of gas phase reactions of halogen atoms with volatile organic compounds (VOCs) of interest in atmospheric chemistry [3]. By means of this technique is possible to measure the rate constants of theses reactions, and subsequently obtain the Arrhenius parameters. Halogens atoms are produced in a excess of the VOC and He, by photolyzing Cl2 at 308 nm to obtain Cl atoms, or CF2Br2 at 248 nm for Br atoms, both cases using a pulsed excimer laser. The radiation (135 nm) from a microwave-driven lamp, through which He containing a low concentrations of Cl2 or Br2 was flowed, was used to excite the resonance fluorescence from the corresponding halogen atom in the jacketed Pyrex reaction cell. Signal were obtained using photon-counting techniques in conjunction with multichannel scaling. The fluorescence signal from the PMT was processed by a preamplifier and sent to an multichannel scaler to collect the time-resolved signal. The multichannel scaler was coupled to a microcomputer for further kinetics analysis.

  16. Laboratory study of nitrate photolysis in Antarctic snow

    DEFF Research Database (Denmark)

    Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph;

    2014-01-01

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [" Laboratory study of nitrate photolysis...... in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide...... additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters...

  17. Comparison of Vanillin and Isovanillin Photolysis in Aqueous Solutions

    Science.gov (United States)

    Vusovich, O. V.; Lapin, I. N.; Svetlichnyi, V. A.; Sul'timova, N. B.; Tchaikovskaya, O. N.

    2014-03-01

    General kinetic regularities of reactions of stationary and laser photolysis of 3-methoxy-4-hydroxybenzaldehyde (vanillin) and 3-hydroxy-4-methoxybenzaldehyde (isovanillin) are investigated by the method of nanosecond laser flash-photolysis. The 4th harmonic of a Nd:YAG laser (λexc = 266 nm) with pulse duration of 7 ns, output power of 100 MW/cm2, and delay time of 30 ns was used as an excitation source. As a result of photolysis, the same photoproducts are formed in the region of absorption at 715 nm. The rate constants of vanillin and isovanillin decomposition obey the first order law and are 2.3ṡ106 and 2.5ṡ106 s-1, respectively.

  18. Hydrogen Peroxide Concentrator

    Science.gov (United States)

    Parrish, Clyde F.

    2007-01-01

    A relatively simple and economical process and apparatus for concentrating hydrogen peroxide from aqueous solution at the point of use have been invented. The heart of the apparatus is a vessel comprising an outer shell containing tubular membranes made of a polymer that is significantly more permeable by water than by hydrogen peroxide. The aqueous solution of hydrogen peroxide to be concentrated is fed through the interstitial spaces between the tubular membranes. An initially dry sweep gas is pumped through the interiors of the tubular membranes. Water diffuses through the membranes and is carried away as water vapor mixed into the sweep gas. Because of the removal of water, the hydrogen peroxide solution flowing from the vessel at the outlet end is more concentrated than that fed into the vessel at the inlet end. The sweep gas can be air, nitrogen, or any other gas that can be conveniently supplied in dry form and does not react chemically with hydrogen peroxide.

  19. Reducing VOC Press Emission from OSB Manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Gary D. McGinnis; Laura S. WIlliams; Amy E. Monte; Jagdish Rughani: Brett A. Niemi; Thomas M. Flicker

    2001-12-31

    Current regulations require industry to meet air emission standards with regard to particulates, volatile organic compounds (VOCs), hazardous air pollutants (HAPs) and other gases. One of many industries that will be affected by the new regulations is the wood composites industry. This industry generates VOCs, HAPs, and particulates mainly during the drying and pressing of wood. Current air treatment technologies for the industry are expensive to install and operate. As regulations become more stringent, treatment technologies will need to become more efficient and cost effective. The overall objective of this study is to evaluate the use of process conditions and chemical additives to reduce VOC/HAPs in air emitted from presses and dryers during the production of oriented strand board.

  20. Effect of clouds on photolysis and oxidants in the troposphere

    Science.gov (United States)

    Tie, Xuexi; Madronich, Sasha; Walters, Stacy; Zhang, Renyi; Rasch, Phil; Collins, William

    2003-10-01

    Cloud layers in the troposphere influence photolysis rates (J values) and hence concentrations of chemical species. In order to study the impact of clouds on photolysis rates and oxidants, we have developed a simplified version of the National Center for Atmospheric Research (NCAR) Tropospheric Ultraviolet-Visible (TUV) model and have coupled the simplified TUV (otherwise known as the fast TUV (FTUV)) into the NCAR/Atmospheric Chemistry Division global transport chemical model (Model for Ozone and Related Chemical Tracers (MOZART-2)). The FTUV model has the same physical processes as the TUV model, except that the wavelength bins between 121 and 750 nm are reduced from 140 to 17. As a result, FTUV is about 8 times faster than the original TUV. Differences in the calculated photolysis rates between TUV and FTUV are generally less than 5% in the troposphere. Subgrid vertical distributions of clouds are also considered in the calculation of photolysis rates in MOZART-2. The method used in this study is a mixed maximum and random overlap scheme. The subgrid method increases the computation time for photolysis rates by a factor of 3 compared to a simple method in which clouds are uniformly distributed over the MOZART-2 grids. Our calculation shows that the uniform cloud distribution method tends to significantly overestimate back scattering on the top of clouds and overestimates the impact on photochemistry in the troposphere. The results suggest that clouds have important impacts on tropospheric chemistry. Global mean OH concentration increases by about 20% due to the impact of clouds. As a result, the calculated CH4 lifetime changes to 11 years for clear sky and 9 years for cloudy sky. The latter value is closer to the methane lifetime estimated from previous studies. Calculated CO surface concentrations are compared with observed values, showing an improvement when the impact of clouds on the photolysis rates is taken into account. Clouds also have important impacts

  1. Direct photolysis of nitroaromatic compounds in aqueous solutions

    Institute of Scientific and Technical Information of China (English)

    CHEN Bing; YANG Chun; GOH Ngoh Khang

    2005-01-01

    The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated.Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroquinone, nitrosobenzene, nitrocatechol, catechol and phenol. Nitrite and nitrate ions were also detected in the irradiated solution indicating direct photolysis of nitrobenzene or nitrophenols.The degradation of nitrobenzene and nitrophenols and the formation of three nitrophenol isomers were observed to follow zero-order kinetics. The quantum yields for nitrobenzene and nitrophenols removal are about 10-3 and 10-3-10-4 respectively. The mechanism for nitrobenzene degradation was suggested to follow mainly nitro-nitrite intramolecular arrangement.

  2. Laser photolysis of ionic liquid [bmim][PF6

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafiuorophosphate ([bmim][PF6])were studied by laser photolysis at a wavelength of 266 nm. Excited triplet state 3[bmim]+* was observed, radical cation [bmim] 2+* and neutral [bmim]* radical via photoionization were also formed. Energy transfer from 3[bmim]+* to β-carotene was confirmed. Oxidation via one electron transfer from TMPD to 3[bmim]+* was also observed and the rate constant was determined to be 1.2 × 105 L. mol-1-s-1. The reaction of [bmim][PF6] with hydrated electron (eaq)was confirmed by laser photolysis in aqueous solution.

  3. VOC methods and levels in Spain

    Energy Technology Data Exchange (ETDEWEB)

    Bomboi, M.T. [Area de Contaminacion Atmosferica, Instituto de Salud Carlos III, Majadahonda (Spain)

    2004-07-01

    Ozone precursors began to be studied in the eighties in Spain, in order to know their levels and composition in areas, which had high concentrations of other atmospheric polluting agents. At the end of the eighties, VOC were incorporated into the air quality networks in urban areas in order to anticipate at the derived amendments of the entrance into force on the Directive 92/72/CEE of 1992 on air pollution by ozone. At the same time, field campaigns for VOC toxics were started in specific industrial areas and the zones with high traffic. More recently, the air quality networks have been orientated to non-urban areas, to cover the knowledge of VOC in semi-urban and rural areas. On the other hand, the role of the biogenic emissions and the role that their chemical and photochemical products play in atmospheric chemistry was becoming important in the nineties. Therefore some research projects, e.g. 'Biogenic Emissions in the Mediterranean Area (BEMA)', were developed in order to understand the vegetation emissions in the Mediterranean area in relation to anthropogenic compounds and to get information on their participation in tropospheric ozone formation. VOC have been sampled at European Monitoring and Evaluation Programme (EMEP) sites since 1999, based on recommendations from the EMEP Workshop on Measurements of Hydrocarbons/VOC in Lindau 1989. Collection of light hydrocarbons started in 1999, whereas measurements of carbonyls have just started in 2003. In this work, the most important sampling and analysis techniques to determine ozone precursors and to control VOC are shown, as well as the main results obtained in projects, networks and measurement campaigns performed with these methods.

  4. Pre-harvest UV-C irradiation triggers VOCs accumulation with alteration of antioxidant enzymes and phytohormones in strawberry leaves.

    Science.gov (United States)

    Xu, Yanqun; Luo, Zisheng; Charles, Marie Thérèse; Rolland, Daniel; Roussel, Dominique

    2017-09-08

    Recent studies have highlighted the biological and physiological effects of pre-harvest ultraviolet (UV)-C treatment on growing plants. However, little is known about the involvement of volatile organic compounds (VOCs) and their response to this treatment. In this study, strawberry plants were exposed to three different doses of UV-C radiation for seven weeks (a low dose: 9.6kJm(-2); a medium dose: 15kJm(-2); and a high-dose: 29.4kJm(-2)). Changes in VOC profiles were investigated and an attempt was made to identify factors that may be involved in the regulation of these alterations. Principle compounds analysis revealed that VOC profiles of UV-C treated samples were significantly altered with 26 VOCs being the major contributors to segregation. Among them, 18 fatty acid-derived VOCs accumulated in plants that received high and medium dose of UV-C treatments with higher lipoxygenase and alcohol dehydrogenase activities. In treated samples, the activity of the antioxidant enzymes catalase and peroxidase was inhibited, resulting in a reduced antioxidant capacity and higher lipid peroxidation. Simultaneously, jasmonic acid level was 74% higher in the high-dose group while abscisic acid content was more than 12% lower in both the medium and high-dose UV-C treated samples. These results indicated that pre-harvest UV-C treatment stimulated the biosynthesis of fatty acid-derived VOCs in strawberry leaf tissue by upregulating the activity of enzymes of the LOX biosynthetic pathway and downregulating antioxidant enzyme activities. It is further suggested that the mechanisms underlying fatty acid-derived VOCs biosynthesis in UV-C treated strawberry leaves are associated with UV-C-induced changes in phytohormone profiles. Crown Copyright © 2017. Published by Elsevier GmbH. All rights reserved.

  5. Studies on the Photodynamic Mechanism of Tetrapyrrole Compounds by Laser Flash Photolysis

    Institute of Scientific and Technical Information of China (English)

    DENG,Kui; CHEN,Zhi-Long; ZHOU,Xing-Ping; WANG,Wen-Feng; YANG,Xiao-Xia; TIAN,Juan

    2008-01-01

    Photodynamic therapy (PDT) is a promising new treatment technique which can potentially destroy unwanted and malignant tissues, such as those of cancer. The photodynamic mechanisms of three tetrapyrrole compounds:Mg-purpurin-18, tetra(meso-chlorophenyl)porphyrin (m-TCPP) and 2,7,12,18-tetramethyl-3,8-di[(1-isobutoxyl)-ethyl]-13,17-bis[3-di(2-chloroethyl)aminopropyl]porphyrin (TDBP) in acetonitrile were investigated by 355 nm laser flash photolysis. It was found that after laser flash photolysis (LFP), the excited states of TDBP and Mg-purpurin-18 could react with O2 and 1O2 was produced, which proved that TDBP and Mg-purpurin-18 took effects through type Ⅱ mechanism in PDT. This suggested that TDBP and Mg-purpurin-18 should be suitable for target tissues containing enough O2. Mg-purpurin-18 has two extra absorptions at 550 and 700 nm, which means it has broad choices of laser wavelength in PDT. It was also found that m-TCPP could be photoionized when excited with 355 nm laser under N2-saturated condition. It could also react with O2 to produce reactive oxygen species such as superoxide and the peroxide anions, but not 1O2. These were known as the Type Ⅰ mechanism. So m-TCPP could be used even at low oxygen concentration or more polar environments with good behavior in PDT. From the above studies on the three different tetrapyrrole compounds it could be concluded that the structure of porphin ring takes a main role in PDT. And there was important impact on the photodynamic mechanism for the functional group directly connecting with porphin ring, while little influence for the functional group indirectly connecting with porphin ring. These will be of great value in the discovery of new PDT drugs.

  6. Quantum Yields of OH From the Photolysis of HOOH in Ice

    Science.gov (United States)

    Chu, L.; Anastasio, C.

    2003-12-01

    Hydrogen peroxide (HOOH) is a common constituent of snow and cirrus ice clouds. Based on its behavior in aqueous solution, photolysis of HOOH on snow/ice should form hydroxyl radical (OH), a process that might be significant as a loss of HOOH as well as a source of OH. In turn, the formation of OH should lead to the oxidation of organic carbon and halides and subsequent release of these oxidation products (e.g., carbonyls, carboxylic acids, and reactive molecular halogens). Determining the importance and rate of OH generation from HOOH photolysis on snow and ice requires knowing the quantum yields for this process as a function of temperature and other environmental variables (e.g., pH and ionic strength). Since these values have not been previously measured, our goal in this work was to determine these quantum yields (i.e., Φ HOOH->OH). Our first step was to measure the molar absorptivities of HOOH between 274 K to 298 K so that we could extrapolate to ice temperatures. There was no temperature dependence of the HOOH molar absorptivity in our measurements, suggesting that the HOOH molar absorptivity is similar in the quasi-liquid layer of ice at low temperatures. Our initial experiments measuring Φ HOOH->OH as a function of temperature (243 - 268 K) show that the values roughly follow the same temperature dependence previously reported for aqueous solution (Zellner et al., 1990). In addition to these results we will also report how Φ HOOH->OH varies as a function of ionic strength and pH. The implications of our measurements for ice particle and snowpack chemistry will also be discussed. Zellner, R.; Exner, M.; Herrmann, H. J. Atmos. Chem. 1990, 10, 411.

  7. Silica deactivation of bead VOC catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Libanati, C.; Pereira, C.J. [Research Division, W. R. Grace and Co., Columbia, MD (United States); Ullenius, D.A. [Grace TEC Systems, De Pere, WI (United States)

    1998-01-15

    Catalytic oxidation is a key technology for controlling the emissions of Volatile Organic Compounds (VOCs) from industrial plants. The present paper examines the deactivation by silica of bead VOC catalysts in a flexographic printing application. Post mortem analyses of field-aged catalysts suggest that organosilicon compounds contained in the printing ink diffuse into the catalyst and deposit as silica particles in the micropores. Laboratory activity evaluation of aged catalysts suggests that silica deposition is non-selective and that silica masks the noble metal active site

  8. VOC transport in vented drums containing simulated waste sludge

    Energy Technology Data Exchange (ETDEWEB)

    Liekhus, K.J.; Gresham, G.L.; Rae, C.; Connolly, M.J.

    1994-02-01

    A model is developed to estimate the volatile organic compound (VOC) concentration in the headspace of the innermost layer of confinement in a lab-scale vented waste drum containing simulated waste sludge. The VOC transport model estimates the concentration using the measured VOC concentration beneath the drum lid and model parameters defined or estimated from process knowledge of drum contents and waste drum configuration. Model parameters include the VOC diffusion characteristic across the filter vent, VOC diffusivity in air, size of opening in the drum liner lid, the type and number of layers of polymer bags surrounding the waste, VOC permeability across the polymer, and the permeable surface area of the polymer bags. Comparison of model and experimental results indicates that the model can accurately estimate VOC concentration in the headspace of the innermost layer of confinement. The model may be useful in estimating the VOC concentration in actual waste drums.

  9. World Calibration Center for VOC (WCC-VOC), a new Facility for the WMO-GAW-Programme

    Science.gov (United States)

    Rappenglueck, B.-

    2002-12-01

    Volatile organic compounds (VOC) are recognized to be important precursors of tropospheric ozone as well as other oxidants and organic aerosols. In order to design effective control measures for the reduction of photooxidants, photochemical processes have to be understood and the sources of the precursors known. Reliable and representative measurements of VOCs are necessary to describe the anthropogenic and biogenic sources, to follow the photochemical degradation of VOCs in the troposphere. Measurement of VOCs is of key importance for the understanding of tropospheric chemistry. Tropospheric VOCs have been one of the recommended measurements to be made within the GAW programme. The purpose will be to monitor their atmospheric abundance, to characterize the various compounds with regard to anthropogenic and biogenic sources and to evaluate their role in the tropospheric ozone formation process. An international WMO/GAW panel of experts for VOC measurements developed the rational and objectives for this GAW activity and recommended the configuration and required activities of the WCC-VOC. In reflection of the complexity of VOC measurements and the current status of measurement technology, a "staged" approach was adopted. Stage 1 measurements: C2-C9 hydrocarbons, including alkanes, alkenes, alkynes, dienes and monocyclics. (The WCC-VOC operates currently under this mode). Stage 2 measurements: C10-C14 hydrocarbons, including higher homologs of the Stage 1 set as well as biogenic hydrocarbon compounds. Stage 3 measurements: Oxygenated VOCs, including alcohols, carbonyls, carboxylic acids. The Quality Assurance/Science Activity Centre (QA/SAC) Germany currently has established the World Calibration Centre for VOC (WCC-VOC). The WCC-VOC has operated in the research mode und has become operational recently. From now on, the WCC-VOC conducts one round-robin calibration audit per year at all global stations that measure VOCs and assists other stations in setting up VOC

  10. GEIGER BRICKEL BENEFITS FROM LOW -VOC COATINGS

    Science.gov (United States)

    Midwest Research Institute, under a cooperative agreement with the U.S. Environmental Protection Agency (EPA), conducted a study to identify wood furniture manufacturing facilities that had converted to low-volatile organic compound (VOC)/hazardous air pollutant (HAP) wood furnit...

  11. Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways.

    Science.gov (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldan, Gloria; Rodriguez, Elena

    2013-02-01

    The photolysis of five frequent emerging contaminants (Benzotriazole, Chlorophene, N,N-diethyl-m-toluamide or DEET, Methylindole, and Nortriptyline HCl) was investigated in ultrapure water under monochromatic ultraviolet radiation at 254 nm and by a combination of UV and hydrogen peroxide. The results revealed that the photolysis rates followed first-order kinetics, with rate constant values depending on the nature of the specific compound, the pH, and the presence or absence of the scavenger tert-butanol. Quantum yields were also determined and values in the range of 53.8 × 10⁻³ - 9.4 × 10⁻³ mol E⁻¹ for Benzotriazole, 525 × 10⁻³ - 469 × 10⁻³ mol E⁻¹ for Chlorophene, 2.8 × 10⁻³ - 0.9 × 10⁻³ mol E⁻¹ for DEET, 108 × 10⁻³ - 165 × 10⁻³ mol E⁻¹ for Methylindole, and 13.8 × 10⁻³ - 15.0 × 10⁻³ mol E⁻¹ for Nortriptyline were obtained. The study also found that the UV/H₂O₂ process enhanced the oxidation rate in comparison to direct photolysis. High-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS) technique was applied to the concentrations evaluation and further identification of the parent compounds and their by-products, which allowed the proposal of the degradation pathways for each compound. Finally, in order to assess the aquatic toxicity in the photodegradation of these compounds, the Vibrio fischeri acute toxicity test was used, and the results indicated an initial increase of this parameter in all cases, followed by a decrease in the specific case of Benzotriazole, DEET, Methylindole, and Chlorophene.

  12. CHARACTERIZATION OF LOW-VOC LATEX PAINTS: VOLATILE ORGANIC COMPOUND CONTENT, VOC AND ALDEHYDE EMISSIONS, AND PAINT PERFORMANCE

    Science.gov (United States)

    The report gives results of laboratory tests to evaluate commercially available latex paints advertised as "low-odor," "low-VOC (volatile organic compound)," or "no-VOC." Measurements were performed to quantify the total content of VOCs in the paints...

  13. [VOCs tax policy on China's economy development].

    Science.gov (United States)

    Liu, Chang-Xin; Wang, Yu-Fei; Wang, Hai-Lin; Hao, Zheng-Ping; Wang, Zheng

    2011-12-01

    In this paper, environmental tax was designed to control volatile organic compounds (VOCs) emissions. Computable general equilibrium (CGE) model was used to explore the impacts of environmental tax (in forms of indirect tax) on the macro-economy development at both national and sector levels. Different levels of tax were simulated to find out the proper tax rate. It is found out that imposing environmental tax on high emission sectors can cause the emission decreased immediately and can lead to negative impacts on macro-economy indicators, such as GDP (gross domestic products), total investment, total product and the whole consumption etc. However, only the government income increased. In addition, the higher the tax rate is, the more pollutants can be reduced and the worse economic effects can be caused. Consequently, it is suggested that, the main controlling policies of VOCs abatement should be mandatory orders, and low environmental tax can be implemented as a supplementary.

  14. Potential energy surface of the photolysis of isocyanic acid HNCO

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The dissociation curves of the photolysis of the isocyanic acidHNCOHN+CO corresponding to the ground state (S0), the first triplet excited state (T1) and the first singlet excited state (S1) have been studied respectively at the UHF/6-311G** and CIS/6-311G** levels using ab initio method. The energy surface crossing points, S1/T1, T1/S0 and S1/S0, have been found and the characteristics of the energy minimum crossing point were given, based on which, the changes of the crossing points' geometries along the lower electronic energy surface and its end-result have been located according to the steepest descent principle. The computational result indicates that the photolysis of the isocyanic acid HNCOHN+CO has three competitive reaction channels ((A)-(C)), and from the kinetic piont of view, channel (A) is the most advantageous.

  15. Solar Photolysis and Photocatalytic Decolorization of Thymol Blue

    Directory of Open Access Journals (Sweden)

    Falah H. Hussein

    2008-01-01

    Full Text Available The photolysis and photocatalytic decolorization of an aqueous propane-2-ol solution of thymol blue(TB (Phenol, 4,4'-(3H-2,1-benzoxathiol-3-ylidenebis(5-methyl-2-(1-methylethyl-,S,S-dioxide; Thymolsulfonpthalein (C27H30O5S,were carried out under natural weathering conditions. Direct photolysis of TB solution of concentration 4.3X10−3 M degraded 37.1% of the colored solution after two hours of solar irradiation, however, the solar photocatalytic decolorization percentage reached 79.04% and 86.21% after the addition of zinc oxide and titanium dioxide, respectively, for the same period. The degradation percentages were investigated by monitoring the dye decolorization spectrophotometrically. The decolorization rates of TB are markedly related with amount of hydroxyl radical formed. A suitable mechanism for the mineralization of TB has been proposed.

  16. Direct photolysis and photocatalytic degradation of 2-amino-5-chloropyridine

    Directory of Open Access Journals (Sweden)

    BILJANA F. ABRAMOVIC

    2003-12-01

    Full Text Available The direct photolysis and photocatalytic degradation of a pyridine pesticide analogue, 2-amino-5-chloropyridine, were investigated employing different analytical techniques – potentiometry, for monitoring the pH and chloride generation, spectrophotometry, for studying the degradation of the pyridine moiety, ion chromatography, for monitoring nitrate formation, and total organic carbon analysis for investigating the efficiency of the process. The photocatalytic degradation was studied in aqueous suspensions of titanium dioxide under illumination by UV light. It was found that chloride evolution was a zero-order reaction which takes place by direct photolysis, in that way differing from the degradation of the pyridine moiety, which takes place in the presence of titanium dioxide. Changes in pH during degradation indicate the formation of acidic intermediates and nitrate in addition to chloride. The effect of the initial substrate concentration was also investigated by monitoring the reaction of chloride generation as well as the degradation reaction of the pyridine moiety. It was found that degradation of the parent compound (2.5 mmol/dm3 by direct photolysis is completed in about 20 minutes, and of the pyridine moety by photocatalytic degradation in about nine hours. Based on the obtained data a possible reaction mechanism is proposed.

  17. Deuterium fractionation in formaldehyde photolysis: chamber experiments and RRKM theory

    Directory of Open Access Journals (Sweden)

    E. J. K. Nilsson

    2013-04-01

    Full Text Available While isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions with the δD of atmospheric in situ hydrogen production, the mechanism and the extent of their pressure dependencies is not adequately described. The pressure dependence of the photolysis rates of the mono- and di-deuterated formaldehyde isotopologues HDCO and D2CO relative to the parent isotopologue H2CO was investigated using RRKM theory and experiment. D2CO and H2CO were photolysed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our earlier work with HDCO vs. H2CO. The UV lamps used for photolysis emit light at wavelengths that mainly dissociate formaldehyde into molecular products, CO and H2 or D2. A model was constructed using RRKM theory to calculate the lifetime of excited formaldehyde on the S0 surface to describe the observed pressure dependent photolytic fractionation of deuterium. The effect of deuteration on the RRKM lifetime of the S0 state is not the main cause of the experimentally observed isotope effect. We propose that there is an additional previously unrecognised isotopic fractionation in the rate of transfer of population from the initially excited S1 state onto the S0 surface.

  18. Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanone.

    Science.gov (United States)

    Liu, Qifan; Li, Hongmin; Wu, Zhuang; Li, Dingqing; Beckers, Helmut; Rauhut, Guntram; Zeng, Xiaoqing

    2016-10-20

    The stepwise decomposition of carbonyl diisocyanate, OC(NCO)2 , has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser (λ=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO)2 (62 % syn-syn and 38 % syn-anti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light (λ>395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N2 and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF-laser photolysis of the closely related NNNNCO and cyclo-N2 CO in solid argon matrices were also studied. The observations of NOCN and in situ CO-trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo-N2 CO. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Inhibition of Neutral red photolysis with different antioxidants.

    Science.gov (United States)

    Rimpapa, Zlatan; Sofić, Emin; Sapcanin, Aida; Toromanović, Jasmin; Tahirović, Ismet

    2007-02-01

    Neutral red is a dye the azine structure which has been used as an acido-base indicator and a dye in histochemistry. In 1960 Goldhaber introduced Neutral red into the medium of resorbing bone cultures to localize the osteoclast in the living cultures. Using time-lapse microcinematography in order to follow the osteoclasts, he reported excellent contrast could be obtained with Neutral red due to the avidity of osteoclasts for this dye. Unfortunately, however, the photodynamic effect resulting from subsequent exposure of these cultures to light precluded this approach, and again in 1963. it was observed that the death of the osteoclasts was probably due to a photodynamic effect related to the dye in the cell, the presence of oxygen and the frequent exposure of light by our time-lapse photography. VIS and UV irradiation induced photolysis of Neutral red, and from Neutral red cation produced with photons a Neutral red radical. This Neutral red radical can be inhibited with action of an antioxidant, such as melatonin, glutathione, ascorbic acid, E vitamin, etc. We developed an assay with Neutral red photolysis which utilizes a VIS and UV irradiation technique for quantification the inhibition of photolysis with action of an antioxidant. In this method Neutral red acts double, as a free radical generator and as a photosensitizer.

  20. EMERGING TECHNOLOGY REPORT: BENCH-SCALE TESTING OF PHOTOLYSIS, CHEMICAL OXIDATION AND BIODEGRADATION OF PCB CONTAMINATED SOILS AND PHOTOLYSIS OF TCDD CONTAMINATED SOILS

    Science.gov (United States)

    This report presents the results of bench-scale testing on degradation of 2,3,7,8-TCDD using W photolysis, and PCB degradation using UV photolysis, chemical oxidation and biological treatment. Bench-scale tests were conducted to investigate the feasibility of a two-phase detoxifi...

  1. Hydrogen peroxide catalytic decomposition

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  2. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    Science.gov (United States)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

    2016-09-01

    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  3. Electrochemical Hydrogen Peroxide Generator

    Science.gov (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

    2010-01-01

    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  4. Wavelength dependence of isotope fractionation in N2O photolysis

    Directory of Open Access Journals (Sweden)

    P. J. Crutzen

    2002-10-01

    Full Text Available In previous reports on isotopic fractionation in the ultraviolet photolysis of nitrous oxide (N2O only enrichments of heavy isotopes in the remaining N2O fraction have been found. However, most direct photolysis experiments have been performed at wavelengths far from the absorption maximum at 182 nm. Here we present high-precision measurements of the 15N and 18O fractionation constants (e in photolysis at 185 nm. Small, but statistically robust depletions of heavy isotopes for the terminal atoms in the linear N2O molecule are found. This means that the absorption cross sections s(15N14N16O and s(14N218O are larger than s(14N216O at this specific wavelength. In contrast, the central N atom becomes enriched in 15N. The corresponding fractionation constants (±1 standard deviation are 15e1 = s(15N14N16O/s(14N216O - 1 = (3.7 ± 0.2%o 18e = s(14N218O/s(14N216O - 1 = (4.5 ± 0.2%o  and   15e2 = s(chem{14N15N16O/s(14N216O - 1 = (-18.6 ± 0.5 %o To our knowledge, this is the first documented case of such a heavy isotope depletion in the photolysis of N2O which supports theoretical models and pioneering vacuum ultraviolet spectroscopic measurements of 15N substituted N2O species that predict fluctuations of e around zero in this spectral region (Selwyn and Johnston, 1981. Such a variability in isotopic fractionation could have consequences for atmospheric models of N2O isotopes since actinic flux varies also strongly over narrow wavelength regions between 175 and 200 nm due to the Schumann-Runge bands of oxygen. However, the spacing between maxima and minima of the fractionation constants and of the actinic flux differ by two orders of magnitude in the wavelength  domain. The wavelength dependence of fractionation constants in N2O photolysis can thus be approximated by a linear fit with negligible consequences on the actual value of the spectrally averaged fractionation constant. In order to establish this linear fit, additional measurements at

  5. Erythromycin and Benzoyl Peroxide Topical

    Science.gov (United States)

    The combination of erythromycin and benzoyl peroxide is used to treat acne. Erythromycin and benzoyl peroxide are in a class of medications called topical antibiotics. The combination of erythromycin ...

  6. Clindamycin and Benzoyl Peroxide Topical

    Science.gov (United States)

    The combination of clindamycin and benzoyl peroxide is used to treat acne. Clindamycin and benzoyl peroxide are in a class of medications called topical antibiotics. The combination of clindamycin ...

  7. Reducing odorous VOC emissions from swine manure using soybean peroxidase and peroxides

    Science.gov (United States)

    Air emissions from swine production facilities can cause odor nuisance issues. Peroxidase enzymes have been used to treat phenolic compounds in industrial wastewaters, but little is known about their efficacy for treating swine manure. The objective of the research was to determine the optimum app...

  8. Pulsed Corona Discharges and Their Applications in Toxic VOCs Abatement

    Institute of Scientific and Technical Information of China (English)

    MuhammadArifMalik; SalmanAkbarMalik

    1999-01-01

    plasma processes are among the emerging technologies for volatile organic compounds (VOCs) sbatoment. Both thermal plasmas and non-equil[brimn plasmas (cold plasmas) are being developed for VOCs clesnup. Particularly, pulsed corona discharges offer several edvantages over conventional VOCs abatement tochniqvee, To optimize the existing technology and to developit further, there is need to understand the mechanlsms involved in plasma chemical reacticms, Furthermore, it is strongly desirable to be able to predict the behavior of new VOCs in non-equillbrlum plasma enviromuent from the data known for a few representative oompounds, Pulsed corona discharge technique is introduced here with dtafion of refevant literature, Fundamental principfes,useful for predicting the VOCs' decomposition behavior, have been worked out from the published literature. Latest developments in the area, targeted to minimize the enersy losses, improve the VOCs destruction efficiency and reduce the generation of unwanted organic and inorganic by-products, are presented.

  9. Photolysis of polycyclic aromatic hydrocarbons on soil surfaces under UV irradiation

    Institute of Scientific and Technical Information of China (English)

    Chengbin Xu; Dianbo Dong; Xuelian Meng; Xin Su; Xu Zheng; Yaoyao Li

    2013-01-01

    Photolysis of some polycyclic aromatic hydrocarbons (PAHs) on soil surfaces may play an important role in the fate of PAHs in the environment.Photolysis of PAHs on soil surfaces under UV irradiation was investigated.The effects of oxygen,irradiation intensity and soil moisture on the degradation of the three PAHs were observed.The results showed that oxygen,soil moisture and irradiation intensity enhanced the photolysis of the three PAHs on soil surfaces.The degradation of the three PAHs on soil surfaces is related to their absorption spectra and the oxidation-half-wave potential.The photolysis of PAHs on soil surfaces in the presence of oxygen followed pseudo first-order kinetics.The photolysis half-lives ranged from 37.87 days for benzo[a]pyrene to 58.73 days for phenanthrene.The results indicate that photolysis is a successful way to remediate PAHs-contaminated soils.

  10. Are Some Fungal Volatile Organic Compounds (VOCs) Mycotoxins?

    OpenAIRE

    Bennett, Joan W.; Arati A. Inamdar

    2015-01-01

    Volatile organic compounds (VOCs) are carbon-compounds that easily evaporate at room temperature. Toxins are biologically produced poisons; mycotoxins are those toxins produced by microscopic fungi. All fungi emit blends of VOCs; the qualitative and quantitative composition of these volatile blends varies with the species of fungus and the environmental situation in which the fungus is grown. These fungal VOCs, produced as mixtures of alcohols, aldehydes, acids, ethers, esters, ketones, terpe...

  11. Outdoor, indoor, and personal exposure to VOCs in children.

    Science.gov (United States)

    Adgate, John L; Church, Timothy R; Ryan, Andrew D; Ramachandran, Gurumurthy; Fredrickson, Ann L; Stock, Thomas H; Morandi, Maria T; Sexton, Ken

    2004-10-01

    We measured volatile organic compound (VOC) exposures in multiple locations for a diverse population of children who attended two inner-city schools in Minneapolis, Minnesota. Fifteen common VOCs were measured at four locations: outdoors (O), indoors at school (S), indoors at home (H), and in personal samples (P). Concentrations of most VOCs followed the general pattern O approximately equal to S long-term health risks from children's exposure to these compounds.

  12. Ozone Formation in Laser Flash Photolysis of Oxoacids and Oxoanions of Chlorine and Bromine

    DEFF Research Database (Denmark)

    Kläning, Ulrik; Sehested, Knud; Wolff, Thomas

    1984-01-01

    The kinetics of ozone formation in the photolysis of oxygen-containing solutions of HClO, ClO–, ClO–2, ClO–3, HBrO, BrO– and BrO–3 has been studied by laser flash photolysis and conventional flash photolysis. The usual assumption, that ozone only forms in the reaction of oxygen atoms in the spin-...

  13. Temperature-dependent absorption cross sections for hydrogen peroxide vapor

    Science.gov (United States)

    Nicovich, J. M.; Wine, P. H.

    1988-03-01

    Relative absorption cross sections for hydrogen peroxide vapor were measured over the temperature ranges 285-381 K for lambda = 230 nm-295 nm and 300-381 K for lambda = 193 nm-350 nm. The well established 298 K cross sections at 202.6 and 228.8 nm were used as an absolute calibration. A significant temperature dependence was observed at the important tropospheric photolysis wavelengths lambda over 300 nm. Measured cross sections were extrapolated to lower temperatures, using a simple model which attributes the observed temperature dependence to enhanced absorption by molecules possessing one quantum of O-O stretch vibrational excitation. Upper tropospheric photodissociation rates calculated using the extrapolated cross sections are about 25 percent lower than those calculated using currently recommended 298 K cross sections.

  14. Remove volatile organic compounds (VOCs) with membrane separation techniques

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Membrane separation, a new technology for removing VOCs including pervaporation, vapor permeation, membrane contactor, and membrane bioreactor was presented. Comparing with traditional techniques, these special techniques are an efficient and energy-saving technology. Vapor permeation can be applied to recovery of organic solvents from exhaust streams. Membrane contactor could be used for removing or recovering VOCs from air or wastewater. Pervaporation and vapor permeation are viable methods for removing VOCs from wastewater to yield a VOC concentrate which could either be destroyed by conventional means, or be recycled for reuse.

  15. Use of mass spectrometric methods for field screening of VOC`s

    Energy Technology Data Exchange (ETDEWEB)

    Evans, J.C.

    1994-11-01

    While mass spectrometric (MS) methods of chemical analysis, particularly gas chromatography-mass spectrometry (GC/MS), have been the mainstay of environmental organic analytical techniques in the laboratory through the use of EPA and other standard methods, field implementation is relatively rare. Instrumentation and methods now exist for utilizing MS and GC/MS techniques in the field for analysis of VOC`s in gas phase, aqueous, and soil media. Examples of field investigations utilizing HP 5971A and Viking SpectraTrak systems for analysis of VOC`s in all three media will be presented. Mass spectral methods were found to offer significant advantages in terms of speed of analysis and reliability of compound identification over field gas chromatography (GC) methods while preserving adequate levels of detection sensitivity. The soil method in particular provides a method for rapid in-field analysis of methanol preserved samples thus minimizing the problem of volatiles loss which typically occurs with routine use of the EPA methods and remote analysis. The high cost of MS instrumentation remains a major obstacle to more widespread use.

  16. Effects of Chromophoric Dissolved Organic Matter on Anthracene Photolysis Kinetics in Aqueous Solution and Ice.

    Science.gov (United States)

    Malley, Philip P A; Grossman, Jarod N; Kahan, Tara F

    2017-09-27

    We measured photolysis kinetics of the PAH anthracene in aqueous solution, in bulk ice, and at ice surfaces in the presence and absence of chromophoric dissolved organic matter (CDOM). Self-association, which occurs readily at ice surfaces, may be responsible for the faster anthracene photolysis observed there. Photolysis rate constants in liquid water increased under conditions where anthracene self-association was observed. Concomitantly, kinetics changed from first-order to second-order, indicating that the photolysis mechanism at ice surfaces might be different than that in aqueous solution. Other factors that could lead to faster photolysis at ice surfaces were also investigated. Increased photon fluxes due to scattering in the ice samples can account for at most 20% of the observed rate increase, and other factors including singlet oxygen ((1)O2*) production and changes in pH and polarity were determined not to be responsible for the faster photolysis. CDOM (in the form of fulvic acid (FA)) did not affect anthracene photolysis kinetics in aqueous solution but suppressed photolysis in ice cubes and ice granules (by 30% and 56%, respectively). This was primarily due to competitive photon absorption (the inner filter effect). Freeze-concentration (or "salting out") appears to slightly increase the suppressing effects of FA on anthracene photolysis. This may be due to increased competitive photon absorption or to physical interactions between anthracene and FA.

  17. Ecotoxicity of ketoprofen, diclofenac, atenolol and their photolysis byproducts in zebrafish (Danio rerio).

    Science.gov (United States)

    Diniz, M S; Salgado, R; Pereira, V J; Carvalho, G; Oehmen, A; Reis, M A M; Noronha, J P

    2015-02-01

    The occurrence of pharmaceutical compounds in wastewater treatment plants and surface waters has been detected worldwide, constituting a potential risk for aquatic ecosystems. Adult zebrafish, of both sexes, were exposed to three common pharmaceutical compounds (atenolol, ketoprofen and diclofenac) and their UV photolysis by-products over seven days. The results show that diclofenac was removed to concentrationsketoprofen was reduced after the parent compounds were transformed by photolysis, whereas the toxicity increased significantly from the by-products generated through diclofenac photolysis. Therefore, diclofenac photolysis would possibly necessitate higher irradiation time to ensure that the associated by-products are completely degraded to harmless form(s).

  18. LIPID PEROXIDATION IN PREECLAMPSIA

    Directory of Open Access Journals (Sweden)

    T.Sharmila Krishna

    2015-03-01

    Full Text Available Hypertension in pregnancy is a leading cause of both maternal and fetal mortality and morbidity. Preeclampsia is characterised by hypertension and proteinuria. Lipid peroxidation is an important factor in the pathophysiology of Preeclampsia. The present study was undertaken to determine Serum Malondialdehyde (MDA levels , a product of lipid peroxidation , in clinically diagnosed Preeclamptic women(n=30 and the values were compared with that of Normotensive pregnant women (n=30 aged between 18-30yrs. All of them were in their third trimester and were primigravida. Serum MDA was estimated by TBARS (thiobarbituric acid reactive substances method. We observed that Serum MDA levels were significantly increased in Preeclamptic women (p <0.000 as compared to that of Normotensive pregnant women . Increased levels of lipid peroxiation product - MDA may contribute to the pathophysiology of Preeclampsia.

  19. HYDROGEN AND VOC RETENTION IN WASTE BOXES

    Energy Technology Data Exchange (ETDEWEB)

    PACE ME; MARUSICH RM

    2008-11-21

    The Hanford Waste Management Project Master Documented Safety Analysis (MDSA) (HNF-14741, 2003) identifies derived safety controls to prevent or mitigate the risks of a single-container deflagration during operations requiring moving, venting or opening transuranic (TRU)-waste containers. The issue is whether these safety controls are necessary for operations involving TRU-waste boxes that are being retrieved from burial at the Hanford Site. This paper investigates the potential for a deflagration hazard within these boxes and whether safety controls identified for drum deflagration hazards should be applied to operations involving these boxes. The study evaluates the accumulation of hydrogen and VOCs within the waste box and the transport of these gases and vapors out of the waste box. To perform the analysis, there were numerous and major assumptions made regarding the generation rate and the transport pathway dimensions and their number. Since there is little actual data with regards to these assumptions, analyses of three potential configurations were performed to obtain some indication of the bounds of the issue (the concentration of hydrogen or flammable VOCs within a waste box). A brief description of each of the three cases along with the results of the analysis is summarized.

  20. Analysis of Sidestream Smoke VOCs and Characterization of their Odor Profiles by VOC Preconcentrator-GC-O Techniques

    Directory of Open Access Journals (Sweden)

    Higashi N

    2014-12-01

    Full Text Available Various techniques have been employed in the analysis of volatile organic compounds (VOCs. However, these techniques are insufficient for the precise analysis of tobacco smoke VOCs because of the complexity of the operating system, system instability, or poor sensitivity. To overcome these problems, a combined system of VOC preconcentrator, gas chromatograph, and olfactometer has been developed. The performance of this new system was evaluated in the analysis of VOCs in tobacco smoke and applied to the odor profiling of sidestream smoke (SSS that has not been sufficiently investigated in the past.

  1. Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Meusinger, Carl; Johnson, Matthew S. [Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joel, E-mail: jsavarino@lgge.obs.ujf-grenoble.fr [Univ. Grenoble Alpes, LGGE, F-38000 Grenoble (France); CNRS, LGGE, F-38000 Grenoble (France)

    2014-06-28

    Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.

  2. Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry.

    Science.gov (United States)

    Meusinger, Carl; Berhanu, Tesfaye A; Erbland, Joseph; Savarino, Joel; Johnson, Matthew S

    2014-06-28

    Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude - apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix - constituting the largest uncertainty in models of snowpack NOx emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NOx emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.

  3. NEW SOIL VOC SAMPLERS: EN CORE AND ACCU CORE SAMPLING/STORAGE DEVICES FOR VOC ANALYSIS

    Energy Technology Data Exchange (ETDEWEB)

    Susan S. Sorini; John F. Schabron; Joseph F. Rovani Jr

    2006-06-01

    Soil sampling and storage practices for volatile organic analysis must be designed to minimize loss of volatile organic compounds (VOCs) from samples. The En Core{reg_sign} sampler is designed to collect and store soil samples in a manner that minimizes loss of contaminants due to volatilization and/or biodegradation. An ASTM International (ASTM) standard practice, D 6418, Standard Practice for Using the Disposable En Core Sampler for Sampling and Storing Soil for Volatile Organic Analysis, describes use of the En Core sampler to collect and store a soil sample of approximately 5 grams or 25 grams for volatile organic analysis and specifies sample storage in the En Core sampler at 4 {+-} 2 C for up to 48 hours; -7 to -21 C for up to 14 days; or 4 {+-} 2 C for up to 48 hours followed by storage at -7 to -21 C for up to five days. This report discusses activities performed during the past year to promote and continue acceptance of the En Core samplers based on their performance to store soil samples for VOC analysis. The En Core sampler is designed to collect soil samples for VOC analysis at the soil surface. To date, a sampling tool for collecting and storing subsurface soil samples for VOC analysis is not available. Development of a subsurface VOC sampling/storage device was initiated in 1999. This device, which is called the Accu Core{trademark} sampler, is designed so that a soil sample can be collected below the surface using a dual-tube penetrometer and transported to the laboratory for analysis in the same container. Laboratory testing of the current Accu Core design shows that the device holds low-level concentrations of VOCs in soil samples during 48-hour storage at 4 {+-} 2 C and that the device is ready for field evaluation to generate additional performance data. This report discusses a field validation exercise that was attempted in Pennsylvania in 2004 and activities being performed to plan and conduct a field validation study in 2006. A draft ASTM

  4. SUBSTRATE EFFECTS ON VOC EMISSIONS FROM A LATEX PAINT

    Science.gov (United States)

    The effects of two substrates -- a stainless steel plate and a gypsum board -- on the volatile organic compound (VOC) emissions from a latex paint were evaluated by environmental chamber tests. It was found that the amount of VOCs emitted from the painted stainless steel was 2 to...

  5. FORMULATING ULTRA-LOW-VOC WOOD FURNITURE COATINGS

    Science.gov (United States)

    The article discusses the formulation of ultra-low volatile organic compound (VOC) wood furniture coatings. The annual U.S. market for wood coatings is about 240, 000 cu m (63 million gal). In this basis, between 57 and 91 million kg (125 and 200 million lb) of VOCs are emitted i...

  6. Direct measurement of VOC diffusivities in tree tissues

    DEFF Research Database (Denmark)

    Baduru, K.K.; Trapp, Stefan; Burken, Joel G.

    2008-01-01

    fundamental terminal fate processes for VOCs that have been translocated from contaminated soil or groundwater, and diffusion constitutes the mass transfer mechanism to the plant−atmosphere interface. Therefore, VOC diffusion through woody plant tissues, that is, xylem, has a direct impact on contaminant fate...

  7. Are Some Fungal Volatile Organic Compounds (VOCs) Mycotoxins?

    Science.gov (United States)

    Bennett, Joan W; Inamdar, Arati A

    2015-09-22

    Volatile organic compounds (VOCs) are carbon-compounds that easily evaporate at room temperature. Toxins are biologically produced poisons; mycotoxins are those toxins produced by microscopic fungi. All fungi emit blends of VOCs; the qualitative and quantitative composition of these volatile blends varies with the species of fungus and the environmental situation in which the fungus is grown. These fungal VOCs, produced as mixtures of alcohols, aldehydes, acids, ethers, esters, ketones, terpenes, thiols and their derivatives, are responsible for the characteristic moldy odors associated with damp indoor spaces. There is increasing experimental evidence that some of these VOCs have toxic properties. Laboratory tests in mammalian tissue culture and Drosophila melanogaster have shown that many single VOCs, as well as mixtures of VOCs emitted by growing fungi, have toxic effects. This paper describes the pros and cons of categorizing toxigenic fungal VOCs as mycotoxins, uses genomic data to expand on the definition of mycotoxin, and summarizes some of the linguistic and other conventions that can create barriers to communication between the scientists who study VOCs and those who study toxins. We propose that "volatoxin" might be a useful term to describe biogenic volatile compounds with toxigenic properties.

  8. Are Some Fungal Volatile Organic Compounds (VOCs Mycotoxins?

    Directory of Open Access Journals (Sweden)

    Joan W. Bennett

    2015-09-01

    Full Text Available Volatile organic compounds (VOCs are carbon-compounds that easily evaporate at room temperature. Toxins are biologically produced poisons; mycotoxins are those toxins produced by microscopic fungi. All fungi emit blends of VOCs; the qualitative and quantitative composition of these volatile blends varies with the species of fungus and the environmental situation in which the fungus is grown. These fungal VOCs, produced as mixtures of alcohols, aldehydes, acids, ethers, esters, ketones, terpenes, thiols and their derivatives, are responsible for the characteristic moldy odors associated with damp indoor spaces. There is increasing experimental evidence that some of these VOCs have toxic properties. Laboratory tests in mammalian tissue culture and Drosophila melanogaster have shown that many single VOCs, as well as mixtures of VOCs emitted by growing fungi, have toxic effects. This paper describes the pros and cons of categorizing toxigenic fungal VOCs as mycotoxins, uses genomic data to expand on the definition of mycotoxin, and summarizes some of the linguistic and other conventions that can create barriers to communication between the scientists who study VOCs and those who study toxins. We propose that “volatoxin” might be a useful term to describe biogenic volatile compounds with toxigenic properties.

  9. An experimental study on bioremediation and photolysis of enrofloxacin.

    Science.gov (United States)

    Zamanpour, Ghasem; Mehrabani-Zeinabad, Arjomand

    2014-01-01

    Recent studies have identified the occurrence of a vast number of pharmaceuticals into the municipal wastewater through excreted urine and feces. Some of these pharmaceutical compounds are degraded in the environment. However, there have been reports on the presence of pharmaceutical active compounds in drinking water. Concerns have been raised over the potential adverse effects of these pharmaceuticals on public health and the aquatic environment. In order to investigate the removal process of pharmaceutical enrofloxacin, a unit consisting of a structured packing rotating biological contactor (spRBC) was designed and constructed as a biological treatment unit. The removal rate reached a maximum of 70% in this biological unit. In the meantime, the effect of photolysis process on the effluent of the biological unit was also studied. In the direct photolysis, the removal performance reached 51% and by adding H2O2 the removal efficiency was increased to 87%. The removal efficiency for the entire system including spRBC and an ultraviolet radiation unit was 94%.

  10. Relative tropospheric photolysis rates of acetaldehyde and formaldehyde measured at the European Photoreactor Facility

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Bache-Andreassen, Lihn; Johnson, Matthew Stanley;

    2009-01-01

    The photolysis rates of HCHO, DCDO, CH3CHO, and CH3CDO are studied by long-path FTIR spectroscopy in natural tropospheric conditions at the European Photoreactor Facility (EUPHORE) in Valencia, Spain. Average relative photolysis rates jHCHO/jDCDO ) 3.15 ( 0.08 and jCH3CHO/jCH3CDO ) 1.26 ( 0...

  11. Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation.

    Science.gov (United States)

    Chen, Pei-Jen; Linden, Karl G; Hinton, David E; Kashiwada, Shosaku; Rosenfeldt, Erik J; Kullman, Seth W

    2006-11-01

    Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.

  12. ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

    Directory of Open Access Journals (Sweden)

    O. Sumińska-Ebersoldt

    2011-07-01

    Full Text Available The photolysis frequency of dichlorine peroxide (ClOOCl JClOOCl is a critical parameter in catalytic cycles destroying ozone in the polar stratosphere. In the atmospherically relevant wavelength region, published laboratory measurements of ClOOCl absorption cross sections and spectra are not in good agreement, resulting in significant discrepancies in JClOOCl. Previous investigations of the consistency with atmospheric observations of ClO and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the rate constant of the ClO recombination reaction krec. Here, we constrain the atmospherically effective JClOOCl independent of krec using ClO data sampled in the same air masses before and directly after sunrise. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the rise in ClO concentration is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007, but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009. In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm, is effectively ruled out by our observations. Additionally, the night-time ClO observations show that the ClO/ClOOCl thermal equilibrium constant can not be significantly higher than the one proposed by Plenge et al. (2005.

  13. Nieuwsgaring in Batavia tijdens de VOC

    Directory of Open Access Journals (Sweden)

    Adrienne Zuiderweg

    2010-12-01

    Full Text Available  The board members of the Dutch East India Company (1602-1795, the Heren Zeventien, promulgated various decrees in which they forbade to bring out information regarding their colonies in the Dutch East Indies and Batavia in letters, manuscripts and printed matter. But in Batavia some inventive Company servants and even staff members got around these regulations, as did some printers in Holland. They published newspapers like Bataviase Nouvelles and Vendu-Nieuws, and also the specialized journal Verhandelingen van het Bataviaasch Genootschap. The initiators of this journal joined hands with the Dutch world of learning and its journals. This article provides an overview of early journalism in the Dutch East Indies and thus contributes to the reconstruction of the literary and cultural climate in Batavia at the time of the VOC.

  14. Protein oxidation and peroxidation

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2016-01-01

    and chain reactions with alcohols and carbonyls as major products; the latter are commonly used markers of protein damage. Direct oxidation of cysteine (and less commonly) methionine residues is a major reaction; this is typically faster than with H2O2, and results in altered protein activity and function....... Unlike H2O2, which is rapidly removed by protective enzymes, protein peroxides are only slowly removed, and catabolism is a major fate. Although turnover of modified proteins by proteasomal and lysosomal enzymes, and other proteases (e.g. mitochondrial Lon), can be efficient, protein hydroperoxides...

  15. Millimeter/submillimeter Spectroscopy to Measure the Branching Ratios for Methanol Photolysis

    Science.gov (United States)

    McCabe, Morgan N.; Powers, Carson Reed; Zinga, Samuel; Widicus Weaver, Susanna L.

    2016-06-01

    Methanol is one of the most abundant and important molecules in the interstellar medium, playing a key role in driving more complex organic chemistry both on grain surfaces and through gas-phase ion-molecule reactions. Methanol photolysis produces many radicals such as hydroxyl, methoxy, hydroxymethyl, and methyl that may serve as the building blocks for more complex organic chemistry in star-forming regions. The branching ratios for methanol photolysis may govern the relative abundances of many of the more complex species already detected in these environments. However, no direct, comprehensive, quantitative measurement of methanol photolysis branching ratios is available. Using a 193 nm excimer laser, the gas phase photolysis of methanol was studied in the (sub)millimeter range, where the rotational spectroscopic signatures of the photolysis products were probed. Here we present preliminary results from this experiment.

  16. VOCs and odors: key factors in selecting `green` building materials?

    Energy Technology Data Exchange (ETDEWEB)

    Coombs, C. [Steven Winter Associates Inc., Norwalk, CT and Washington DC (United States)

    1998-12-01

    The current state of knowledge available for selecting building materials on the basis of emissions of volatile organic compounds (VOCs) and odors is reviewed. The significance of VOCs and odors in building materials is related to their role in influencing indoor air quality. As far as toxicity is concerned, many of the VOCs detected in indoor air are relatively inert when considered singly. They are not however, unimportant because in actual fact they are invariably found in mixtures some of which can be toxic. Although knowledge of VOCs is incomplete, it is important to specify ozone-resistant polymeric building products, i.e. those that are chemically stable and inert to oxidation. In addition to VOCs, attention should also be focused on semi-volatile organic compounds (SVOCs) since they are even more persistent than VOCs and tend to offgas for prolonged periods of time. Similarly, it is reasonable to specify low-odor materials. Inclusion of issues related to complex indoor chemistry, less volatile emissions, in addition to VOCs and odor, should in time result in expanded choices of building materials that promote indoor air quality. 16 refs.,2 tabs.

  17. The examination of berberine excited state by laser flash photolysis

    Science.gov (United States)

    Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

    2009-07-01

    The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

  18. Hydrogen isotope fractionation in the photolysis of formaldehyde

    Directory of Open Access Journals (Sweden)

    T. S. Rhee

    2007-08-01

    Full Text Available Experiments investigating the isotopic fractionation in the formation of H2 by the photolysis of CH2O under tropospheric conditions are reported and discussed. The deuterium (D depletion in H2 produced is 500(±20‰ with respect to the parent CH2O. We also observed that complete photolysis of CH2O under atmospheric conditions produces H2 that has virtually the same isotopic ratio as that of the parent CH2O. These findings imply that there must be a very strong concomitant isotopic enrichment in the radical channel (CH2O + → CHO + H as compared to the molecular channel (CH2O + → H2 + CO of the photolysis of CH2O in order to balance the relatively small isotopic fractionation in the competing reaction of CH2O with OH. Using a 1-box photochemistry model we calculated the isotopic fractionation factor for the radical channel to be 0.22(±0.08, which is equivalent to a 780(±80‰ enrichment in D of the remaining CH2O. When CH2O is in photochemical steady state, the isotopic ratio of the H2 produced is determined not only by the isotopic fractionation occurring during the photolytical production of H2m but also by overall fractionation for the removal processes of CH2O (αf, and is represented by the ratio of αmf. Applying the isotopic fractionation factors relevant to CH2O photolysis obtained in the present study to the troposphere, the ratio of αmf varies from ~0.8 to ~1.2 depending on the fraction of CH2O that reacts with OH and that produces H2. This range of αmf can render the H2 produced from the photochemical oxidation of CH4 to be enriched in D (with respect to the original CH

  19. Hydrogen isotope fractionation in the photolysis of formaldehyde

    Directory of Open Access Journals (Sweden)

    T. S. Rhee

    2008-03-01

    Full Text Available Experiments investigating the isotopic fractionation in the formation of H2 by the photolysis of CH2O under tropospheric conditions are reported and discussed. The deuterium (D depletion in the H2 produced is 500(±20‰ with respect to the parent CH2O. We also observed that complete photolysis of CH2O under atmospheric conditions produces H2 that has virtually the same isotope ratio as that of the parent CH2O. These findings imply that there must be a very strong concomitant isotopic enrichment in the radical channel (CH2O+hν → CHO+H as compared to the molecular channel (CH2O+hν → H2+CO of the photolysis of CH2O in order to balance the relatively small isotopic fractionation in the competing reaction of CH2O with OH. Using a 1-box photochemistry model we calculated the isotopic fractionation factor for the radical channel to be 0.22(±0.08, which is equivalent to a 780(±80‰ enrichment in D of the remaining CH2O. When CH2O is in photochemical steady state, the isotope ratio of the H2 produced is determined not only by the isotopic fractionation occurring during the photolytical production of H2m but also by overall fractionation for the removal processes of CH2O (αf, and is represented by the ratio of αmf. Applying the isotopic fractionation factors relevant to CH2O photolysis obtained in the present study to the troposphere, the ratio of αmf varies from ~0.8 to ~1.2 depending on the fraction of CH2O that reacts with OH and that produces H2. This range of αmf can render the H2 produced from the photochemical oxidation of CH4 to

  20. Carbamazepine degradation by photolysis and titanium dioxide photocatalysis.

    Science.gov (United States)

    Im, Jong-Kwon; Son, Hyun-Seok; Kang, Young-Min; Zoh, Kyung-Duk

    2012-07-01

    We investigated the degradation of carbamazepine by photolysis/ultraviolet (UV)-C only and titanium dioxide photocatalysis. The degradation of carbamazepine by UV-only and titanium-dioxide-only (adsorption) reactions were inefficient, however, complete degradation of carbamazepine was observed by titanium dioxide photocatalysis within 30 min. The rate of degradation increased as initial carbamazepine concentration decreased, and the removal kinetics fit well with the Langmuir-Hinshelwood model. The addition of methanol, a radical scavenger, decreased carbamazepine removal, suggesting that the hydroxide radical played an important role during carbamazepine degradation. The addition of oxygen during titanium dioxide photocatalysis accelerated hydroxide radical production, thus improving mineralization activity. The photocatalytic degradation was more efficient at a higher pH, whereas the removal of carbamazepine and acridine (a major intermediate) were more efficient under aerobic conditions. The mineralization of carbamazepine during photocatalysis produced various ionic by-products such as ammonium and nitrate by way of nitrogen dioxide.

  1. Photolysis of incorporated benzophenone derivatives inside compressed lipid monolayers

    Directory of Open Access Journals (Sweden)

    DEJAN Z. MARKOVIC

    2001-05-01

    Full Text Available The goal of this work was to study the possibility of the occurrence of radical-type lipid peroxidation of the lipid constituents on biomembranes, in compressed monolayers, having lipoidal benzophenone photosensitizers incorporated. The triplets of the photosensitizer abstract allylic and doubly-allylic hydrogen atoms from anticonjugated moities of the lipid molecules. The results simultaneously confirmed the occurrence of H-abstraction (and so the initiation of the peroxidizing chain mechanism, and the absence of the formation of lipid peroxides. The reason lies in "cage effect": the highly restricted spacial area of compressed lipid monolayers limits the mobility of the created radicals (lipid radicals and ketyl radicals and leads to their recombination, thus preventing the propagation step of the chain mechanism. With certain reservations it may be concluded that these results have a clear implication on real biomembranes: the structure of which is one of themain factors preventing the spread of the chain reaction, and the formation of lipid peroxides.

  2. VOC and HAP recovery using ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy

  3. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-09-01

    Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will (or will not) have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  4. Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-04-01

    Gas phase photolysis is an important tropospheric sink for many carbonyl compounds, however the significance of direct photolysis of carbonyl compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived Henry's law parameters, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations of atmospherically relevant carbonyl compounds designed to estimate gas and aqueous phase extinction coefficients. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only three out of the 92 carbonyl compounds investigated, pyruvic acid, 3-oxobutanoic acid, and 3-oxopropanoic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α, β conjugation, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected.

  5. Evaluation of simulated photolysis rates and their response to solar irradiance variability

    Science.gov (United States)

    Sukhodolov, Timofei; Rozanov, Eugene; Ball, William T.; Bais, Alkiviadis; Tourpali, Kleareti; Shapiro, Alexander I.; Telford, Paul; Smyshlyaev, Sergey; Fomin, Boris; Sander, Rolf; Bossay, Sébastien; Bekki, Slimane; Marchand, Marion; Chipperfield, Martyn P.; Dhomse, Sandip; Haigh, Joanna D.; Peter, Thomas; Schmutz, Werner

    2016-05-01

    The state of the stratospheric ozone layer and the temperature structure of the atmosphere are largely controlled by the solar spectral irradiance (SSI) through its influence on heating and photolysis rates. This study focuses on the uncertainties in the photolysis rate response to solar irradiance variability related to the choice of SSI data set and to the performance of the photolysis codes used in global chemistry-climate models. To estimate the impact of SSI uncertainties, we compared several photolysis rates calculated with the radiative transfer model libRadtran, using SSI calculated with two models and observed during the Solar Radiation and Climate Experiment (SORCE) satellite mission. The importance of the calculated differences in the photolysis rate response for ozone and temperature changes has been estimated using 1-D a radiative-convective-photochemical model. We demonstrate that the main photolysis reactions, responsible for the solar signal in the stratosphere, are highly sensitive to the spectral distribution of SSI variations. Accordingly, the ozone changes and related ozone-temperature feedback are shown to depend substantially on the SSI data set being used, which highlights the necessity of obtaining accurate SSI variations. To evaluate the performance of photolysis codes, we compared the results of eight, widely used, photolysis codes against two reference schemes. We show that, in most cases, absolute values of the photolysis rates and their response to applied SSI changes agree within 30%. However, larger errors may appear in specific atmospheric regions because of differences, for instance, in the treatment of Rayleigh scattering, quantum yields, or absorption cross sections.

  6. Measurement of VOCs in vehicle exhaust by extractive FTIR spectroscopy

    Science.gov (United States)

    Lechner, Bernhard; Paar, H.; Sturm, Peter J.

    2001-02-01

    12 The detection of benzene and other organic compounds in vehicle exhaust by FT-IR-spectroscopy is seriously limited by the strong interference of carbon dioxide and the rather weak absorption coefficient of the gases. Therefore, a measurement device was developed which separates the components of interest (mostly VOCs) from carbon dioxide, water and nitric oxide. In addition the VOCs have to be pre- concentrated. To avoid condensation of VOCs the measurements have to take place at higher temperatures. The vehicle exhaust was led through an activated charcoal tube where the organic compounds were adsorbed. Afterwards, the charcoal tube was heated in a furnace, the VOCs were desorbed thermically and were carried by (heated) nitrogen into a gas cell with a path-length of 10 m where the concentration of the different species was measured. With the help of this measurement device a lot of VOC- components like benzene, toluene, and xylene were detected successfully. Measurements were performed on an engine test bed and a chassis dynamometer for heavy duty vehicles. The detection limit of most of the VOCs was about 2 to 3 ppb for a sampling time of 20 min. Calibration measurements showed an accuracy of 15%.

  7. Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration.

    Science.gov (United States)

    Tian, Guoxun; Moosmüller, Hans; Arnott, W Patrick

    2013-09-01

    Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO2) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO2 concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO2.

  8. Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis

    CSIR Research Space (South Africa)

    Nkosi, SS

    2013-06-01

    Full Text Available , and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron...

  9. The role of electron donors generated from UV photolysis for accelerating pyridine biodegradation.

    Science.gov (United States)

    Tang, Yingxia; Zhang, Yongming; Yan, Ning; Liu, Rui; Rittmann, Bruce E

    2015-09-01

    Employing an internal circulation baffled biofilm reactor (ICBBR), we evaluated the mechanisms by which photolysis accelerated the biodegradation and mineralization of pyridine (C5 H5 N), a nitrogen-containing heterocyclic compound. We tested the hypothesis that pyridine oxidation is accelerated because a key photolysis intermediate, succinate, is as electron donor that promotes the initial mono-oxygenation of pyridine. Experimentally, longer photolysis time generated more electron-donor products (succinate), which stimulated faster pyridine biodegradation. This pattern was confirmed by directly adding succinate, and the stimulation effect occurred similarly with addition of the same equivalents of acetate and formate. Succinate, whether generated by UV photolysis or added directly, also accelerated mono-oxygenation of the first biodegradation intermediate, 2-hydroxyl pyridine (2HP). 2HP and pyridine were mutually inhibitory in that their mono-oxygenations competed for internal electron donor; thus, the addition of any readily biodegradable donor accelerated both mono-oxygenation steps, as well as mineralization.

  10. A Novel Methodology to Evaluate Health Impacts Caused by VOC Exposures Using Real-Time VOC and Holter Monitors

    Directory of Open Access Journals (Sweden)

    Hiroaki Kumano

    2010-11-01

    Full Text Available While various volatile organic compounds (VOCs are known to show neurotoxic effects, the detailed mechanisms of the action of VOCs on the autonomic nervous system are not fully understood, partially because objective and quantitative measures to indicate neural abnormalities are still under development. Nevertheless, heart rate variability (HRV has been recently proposed as an indicative measure of the autonomic effects. In this study, we used HRV as an indicative measure of the autonomic effrects to relate their values to the personal concentrations of VOCs measured by a real-time VOC monitor. The measurements were conducted for 24 hours on seven healthy subjects under usual daily life conditions. The results showed HF powers were significantly decreased for six subjects when the changes of total volatile organic compound (TVOC concentrations were large, indicating a suppression of parasympathetic nervous activity induced by the exposure to VOCs. The present study indicated these real-time monitoring was useful to characterize the trends of VOC exposures and their effects on autonomic nervous system.

  11. Towards a quantitative study of the VUV photolysis of methane: preliminary experiment on trichloromethane

    Science.gov (United States)

    Gans, B.; Boyé-Péronne, S.; Douin, S.; Gauyacq, D.

    2010-01-01

    Photolysis of methane in Titan's stratosphere is the starting point of gas phase carbon chemistry. Quantitative studies of methane photolytic products are of utmost importance for Titan atmosphere models. With this aim, two experimental strategies are presented in this article. Preliminary results demonstrate the possibility of using CRDS absorption coupled with pulsed photolysis on the example of a halogenated derivative of methane: Trichloromethane (CHCl_3).

  12. Intimately coupling of photolysis accelerates nitrobenzene biodegradation, but sequential coupling slows biodegradation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lihui [Department of Environmental Science and Engineering, College of Life and Environmental Science, Shanghai Normal University, Shanghai 200234 (China); Zhang, Yongming, E-mail: zhym@shnu.edu.cn [Department of Environmental Science and Engineering, College of Life and Environmental Science, Shanghai Normal University, Shanghai 200234 (China); Bai, Qi; Yan, Ning; Xu, Hua [Department of Environmental Science and Engineering, College of Life and Environmental Science, Shanghai Normal University, Shanghai 200234 (China); Rittmann, Bruce E. [Swette Center for Environmental Biotechnology, Biodesign Institute, Arizona State University, Tempe, AZ 85287-5701 (United States)

    2015-04-28

    Highlights: • Intimately coupled UV photolysis accelerated nitrobenzene biodegradation. • NB biodegradation was slowed by accumulation of nitrophenol. • Oxalic acid was a key product of UV photolysis. • Oxalic acid accelerated biodegradation of nitrobenzene and nitrophenol by a co-substrate effect. • Intimate coupling of UV and biodegradation accentuated the benefits of oxalic acid. - Abstract: Photo(cata)lysis coupled with biodegradation is superior to photo(cata)lysis or biodegradation alone for removal of recalcitrant organic compounds. The two steps can be carried out sequentially or simultaneously via intimate coupling. We studied nitrobenzene (NB) removal and mineralization to evaluate why intimate coupling of photolysis with biodegradation was superior to sequential coupling. Employing an internal circulation baffled biofilm reactor, we compared direct biodegradation (B), biodegradation after photolysis (P + B), simultaneous photolysis and biodegradation (P&B), and biodegradation with nitrophenol (NP) and oxalic acid (OA) added individually and simultaneously (B + NP, B + OA, and B + NP + OA); NP and OA were NB’s main UV-photolysis products. Compared with B, the biodegradation rate P + B was lower by 13–29%, but intimately coupling (P&B) had a removal rate that was 10–13% higher; mineralization showed similar trends. B + OA gave results similar to P&B, B + NP gave results similar to P + B, and B + OA + NP gave results between P + B and P&B, depending on the amount of OA and NP added. The photolysis product OA accelerated NB biodegradation through a co-substrate effect, but NP was inhibitory. Although decreasing the UV photolysis time could minimize the inhibition impact of NP in P + B, P&B gave the fastest removal of NB by accentuating the co-substrate effect of OA.

  13. Photolysis of oxygen saturated ethers in the presence of Sn (Ⅱ) or Cu (Ⅱ) salts

    Institute of Scientific and Technical Information of China (English)

    施敏

    2000-01-01

    Photolysis of diethyl ether-oxygen charge transfer complex the presence of Sn(Ⅱ) or Cu(Ⅱ) salts gave higher yields of the oxiation products, ethyl acetate, acetaldehyde, ethanol,ethyl formate and methanol compared with those without the salts. In addition, the photolysis of an oxygen saturated tetrahydrofuran (THF) or dibutyl lether solution gave γ-butyro-Their yields were also affected by the addition of Cu(Ⅱ) or Sn(Ⅱ) salts.

  14. Kinetics of Hydrolysis and Products of Hydrolysis and Photolysis of Tetryl.

    Science.gov (United States)

    1984-10-22

    NSWC TR 84-88 Lfl KINETICS OF HYDROLYSIS AND PRODUCTS OF HYDROLYSIS AND PHOTOLYSIS OF TETRYL BY ELEONORE G. KAYSER NICHOLAS E. BURLINSON DAVID H...PHOTOLYSIS OF TETRYL Feb 1980 to Dec 1981 S.PERFORMING ORG. REPORT NUMBER 7. AU THOR(s) SCONTRACT OR GRANT NUMUER11110 Eleonore G. Kayser, NLchcolas E...Library 1 Monitoring Techniques Division Dr. Ron Spanggord I Attn: RD680 (Robert B. Medz) 1 333 Rcvenswood Avenue Washington, DC 20460 Menlo Park

  15. Pesticide photolysis in prairie potholes: probing photosensitized processes.

    Science.gov (United States)

    Zeng, Teng; Arnold, William A

    2013-07-02

    Prairie pothole lakes (PPLs) are glacially derived, ecologically important water bodies found in central North America and represent a unique setting in which extensive agriculture occurs within wetland ecosystems. In the Prairie Pothole Region (PPR), elevated pesticide use and increasing hydrologic connectivity have raised concerns about the impact of nonpoint source agricultural pollution on the water quality of PPLs and downstream aquatic systems. Despite containing high dissolved organic matter (DOM) levels, the photoreactivity of the PPL water and the photochemical fate of pesticides entering PPLs are largely unknown. In this study, the photodegradation of sixteen pesticides was investigated in PPL waters sampled from North Dakota, under simulated and natural sunlight. Enhanced pesticide removal rates in the irradiated PPL water relative to the control buffer pointed to the importance of indirect photolysis pathways involving photochemically produced reactive intermediates (PPRIs). The steady-state concentrations of carbonate radical, hydroxyl radical, singlet oxygen, and triplet-excited state DOM were measured and second-order rate constants for reactions of pesticides with these PPRIs were calculated. Results from this study underscore the role of DOM as photosensitizer in limiting the persistence of pesticides in prairie wetlands through photochemical reactions.

  16. Study of carboxyhemoglobin photodissociation with laser flash-photolysis

    Science.gov (United States)

    Kuzmin, Vasiliy V.; Salmin, Vladimir V.; Salmina, A. B.; Provorov, Alexander S.

    2004-08-01

    Assessment of the carboxyhemoglobin photodissociation has been performed under the native conditions. This investigation has a great importance for the development and creation of completely new approach for the treatment of carbon monoxide poisoning based on the photoinduced dissociation of carboxyhemoglobin. Photodissociation was registered on the experimental setup with crossing laser beams were pulsed Nd:YAG laser at the second harmonics wavelength (λ=532 nm) was used as a source of photolyzing radiation. Buffered solutions of whole human peripheral blood (PBS, pH=7.4) and diluted hemolized human peripheral blood were used. We found optimal parameters for the registration of the photodissociation such as using of buffered solutions of the whole human peripheral blood with the concentration of carboxyhemoglobin around 50% detection of dissociation of carboxyhemoglobin at the maximum of absorption within the Soret's band (435 nm). Dependence of photodissociation efficiency on the concentration of the complex in the tested solutions, as well as on the photolysis radiation intensity in both types of solutions was proved.

  17. Four-dimensional multi-site photolysis of caged neurotransmitters

    Directory of Open Access Journals (Sweden)

    Mary Ann eGo

    2013-12-01

    Full Text Available Neurons receive thousands of synaptic inputs that are distributed in space and time. The systematic study of how neurons process these inputs requires a technique to stimulate multiple yet highly targeted points of interest along the neuron's dendritic tree. Three-dimensional multi-focal patterns produced via holographic projection combined with two-photon photolysis of caged compounds can provide for highly localized release of neurotransmitters within each diffraction-limited focus, and in this way emulate simultaneous synaptic inputs to the neuron. However, this technique so far cannot achieve time-dependent stimulation patterns due to fundamental limitations of the hologram-encoding device and other factors that affect the consistency of controlled synaptic stimulation. Here, we report an advanced technique that enables the design and application of arbitrary spatio-temporal photostimulation patterns that resemble physiological synaptic inputs. By combining holographic projection with a programmable high-speed light-switching array, we have overcome temporal limitations with holographic projection, allowing us to mimic distributed activation of synaptic inputs leading to action potential generation. Our experiments uniquely demonstrate multi-site two-photon glutamate uncaging in three dimensions with submillisecond temporal resolution. Implementing this approach opens up new prospects for studying neuronal synaptic integration in four dimensions.

  18. Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions.

    Science.gov (United States)

    Cao, Guiping; Lu, Jilai; Wang, Gongying

    2012-01-01

    The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics: the rate was gamma = 0.0161C(BPS) under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.

  19. Photolysis of three antiviral drugs acyclovir, zidovudine and lamivudine in surface freshwater and seawater.

    Science.gov (United States)

    Zhou, Chengzhi; Chen, Jingwen; Xie, Qing; Wei, Xiaoxuan; Zhang, Ya-nan; Fu, Zhiqiang

    2015-11-01

    Photodegradation is an important elimination process for many pharmaceuticals in surface waters. In this study, photodegradation of three antiviral drugs, acyclovir, zidovudine, and lamivudine, was investigated in pure water, freshwater, and seawater under the irradiation of simulated sunlight. Results showed that zidovudine was easily transformed via direct photolysis, while acyclovir and lamivudine were mainly transformed via indirect photolysis. We found that in freshwater, nitrate enhanced the photodegradation of the three antiviral drugs, bicarbonate promoted the photodegradation of acyclovir, and dissolved organic matter (DOM) accelerated the photolysis of acyclovir and lamivudine. In seawater, the photolysis of acyclovir was not susceptible to Cl(-), Br(-) and ionic strength; however, the photolysis of zidovudine was inhibited by Cl(-) and Br(-), and the photolysis of lamivudine was enhanced by Cl(-), Br(-) and ionic strength. Second-order reaction rate constants for the three antiviral drugs with (1)O2 (k1O2) and OH (kOH) were also measured. These results are important for fate and ecological risk assessment of the antiviral drugs in natural waters.

  20. Photolysis of metal oxides as a source of atoms in planetary exospheres

    Science.gov (United States)

    Valiev, R. R.; Berezhnoy, A. A.; Sidorenko, A. D.; Merzlikin, B. S.; Cherepanov, V. N.

    2017-10-01

    The cross sections of photolysis of LiO, NaO, KO, MgO, and CaO molecules have been calculated by the use of quantum chemistry methods. The maximal values for photolysis cross sections of alkali metal monoxides have the order of 10-17 cm2, and for alkaline earth metal monoxides these values are less on 1-2 orders of the magnitude. The lifetimes of photolysis at 1 astronomical unit are estimated as 5, 3, 60, 70, and 3,000 s for LiO, NaO, KO, MgO, and CaO, respectively. Typical kinetic energies of main peaks of photolysis-generated metal atoms are determined. Impact-produced LiO, NaO, KO, and MgO molecules are destroyed in the lunar and Hermean exospheres almost completely during the first ballistic flight while CaO molecule is more stable against destruction by photolysis. Photolysis-generated metal atoms in planetary exospheres can be detected by performing high-resolution spectral observations of velocity distribution of exospheric metal atoms.

  1. Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions

    Institute of Scientific and Technical Information of China (English)

    Guiping Cao; Jilai Lu; Gongying Wang

    2012-01-01

    The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions.Photolysis and kinetics were investigated,as were the photolysis mechanism and the influences of initial pH value,light source,and environmental substances in water.The results showed that the photolysis of BPS occurred under UV light,and the rate increased with light source intensity.The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics:the rate was Υ =0.0161Caps under a 40-W UV-lamp,and the degradation half-life was 43.1 min.Due to its absorption of light,direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species.The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS.The photodegradation rate of BPS increased in the presence of chloride and ferric ions,while the rate was inhibited by nitrate and phosphate in aqueous solution.

  2. Inner-shell excitation spectroscopy of peroxides

    NARCIS (Netherlands)

    Harding, K. L.; Kalirai, S.; Hayes, R.; Ju, V.; Cooper, G.; Hitchcock, A. P.; Thompson, M. R.

    2015-01-01

    O 1s inner-shell excitation spectra of a number of vapor phase molecules containing peroxide bonds - hydrogen peroxide (H2O2), di-t-butylperoxide ((BuOBu)-Bu-t-Bu-t), benzoyl peroxide, ((C6H5(CO)O)(2)), luperox-F [1,3(4)-bis(tertbutylperoxyisopropyl)benzene], and analogous, non-peroxide compounds -

  3. TO PURGE OR NOT TO PURGE? VOC CONCENTRATION ...

    Science.gov (United States)

    Soil vapor surveys are commonly used as a screening technique to delineate volatile organic compound (VOC) contaminant plumes and provide information for soil sampling plans. Traditionally, three purge volumes of vapor are removed before a sample is collected. One facet of this study was to evaluate the VOC concentrations lost during purging and explore the potential implications of those losses. The vapor data was compared to collocated soil data to determine if any correlation existed between the VOC concentrations. Two different methods for soil vapor collection were compared: 1) active/micro-volume; and 2) active/macro-volume. The active/micro-volume vapor sample had total line purge volume of 1.25 mL and the active/macro-volume vapor sample had a total line purge volume of 15 mL. Six line purge volumes were collected for each vapor sampling technique, with the fourth purge volume representing the traditional sample used for site screening data. Each sample was collected by gas tight syringe and transferred to a thermal de sorption tube for sorption, transport, and analysis. Following the removal of the soil vapor samples, collocated soil samples were taken. For both active vapor sampling techniques, the VOC concentrations in the first three purge volumes exceeded the VOC concentrations in the last three purge volumes. This implies that the general rule of removal of three purge volumes prior to taking a sample for analysis could lead to underestimating the

  4. An Evaluation of the FAST-J Photolysis algorithm for predicting nitrogen dioxide photolysis rates under clear and cloudy sky conditions

    Energy Technology Data Exchange (ETDEWEB)

    Barnard, James C.; Chapman, Elaine G.; Fast, Jerome D.; Schmelzer, John R.; Schlusser, James R.; Shetter, Richard E.

    2004-07-04

    The FAST-J model was developed to quickly calculate photolysis rates under both clear and cloudy sky conditions. In this paper, photolysis rates of nitrogen dioxide (NO2) were calculated using FAST-J and compared with measurements taken at two sites in the United States: Phoenix, Arizona, and Houston, Texas. The measurements were derived from either an actinic flux filter radiometer (Phoenix) or a spectroradiometer (Houston). A sun photometer, sited nearby these radiometers, provided irradiances measurements from which aerosol and cloud optical thicknesses were obtained. Aerosol single scattering albedo was not known, but was taken to be either 0.79 or 0.94, representative of either soot-like aerosols or sulfate-like aerosols, respectively. These optical properties served as input to the FAST-J model, which in turn was used to calculate photolysis rates. For both clear and cloudy sky cases, the modeled and measured photolysis rates agree within the uncertainties of the measurements for a single scattering albedo of 0.94. For a single scattering albedo of 0.79, the agreement is again within the uncertainty limits except for the cloudy sky case in Houston.

  5. Dissolved organic matter photolysis in Canadian arctic thaw ponds

    Science.gov (United States)

    Laurion, Isabelle; Mladenov, Natalie

    2013-09-01

    The abundant thaw lakes and ponds in the circumarctic receive a new pool of organic carbon as permafrost peat soils degrade, which can be exposed to significant irradiance that potentially increases as climate warms and ice cover shortens. Exposure to sunlight is known to accelerate the transformation of dissolved organic matter (DOM) into molecules that can be more readily used by microbes. We sampled the water from two common classes of ponds found in the ice-wedge system of continuous permafrost regions of Canada, polygonal and runnel ponds, and followed the transformation of DOM over 12 days by looking at dissolved organic carbon (DOC) concentration and DOM absorption and fluorescence properties. The results indicate a relatively fast decay of color (3.4 and 1.6% loss d-1 of absorption at 320 nm for the polygonal and runnel pond, respectively) and fluorescence (6.1 and 8.3% loss d-1 of total fluorescent components, respectively) at the pond surface, faster in the case of humic-like components, but insignificant losses of DOC over the observed period. This result indicates that direct DOM mineralization (photochemical production of CO2) is apparently minor in thaw ponds compared to the photochemical transformation of DOM into less chromophoric and likely more labile molecules with a greater potential for microbial mineralization. Therefore, DOM photolysis in arctic thaw ponds can be considered as a catalytic mechanism, accelerating the microbial turnover of mobilized organic matter from thawing permafrost and the production of greenhouse gases, especially in the most shallow ponds. Under a warming climate, this mechanism will intensify as summers lengthen.

  6. ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

    Directory of Open Access Journals (Sweden)

    O. Sumińska-Ebersoldt

    2012-02-01

    Full Text Available The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3 in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm, significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007, but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009. In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm is not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005.

  7. Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

    Institute of Scientific and Technical Information of China (English)

    Chen Liang; Huimin Zhao; Minjie Deng; Xie Quan; Shuo Chen; Hua Wang

    2015-01-01

    Norfloxacin (NOR),an ionizable antibiotic frequently used in the aquaculture industry,has aroused public concern due to its persistence,bacterial resistance,and environmental ubiquity.Therefore,we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water-dissolved organic matter (DOM),which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore,scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water.The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (1O2) based on the scavenging experiments.In addition,DOM was found to influence the photolysis of different NOR species,and its impact was related to the concentration of DOM and type of NOR species.Photolysis of cationic NOR was photosensitized by DOM at low concentration,while zwitterionic and anionic NOR were photoinhibited by DOM,where quenching of ·OH predominated according to EPR experiments,accompanied by possible participation of excited triplet-state NOR and 1O2.Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination,cleavage of the piperazine side chain and photooxidation,and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates.The results implied that for accurate ecological risk assessment of emerging ionizable pollutants,the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.

  8. Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin.

    Science.gov (United States)

    Liang, Chen; Zhao, Huimin; Deng, Minjie; Quan, Xie; Chen, Shuo; Wang, Hua

    2015-01-01

    Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water - dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (OH) and singlet oxygen ((1)O2) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of OH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and (1)O2. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored. Copyright © 2014. Published by Elsevier B.V.

  9. Arabidopsis thaliana as Bioindicator of Fungal VOCs in Indoor Air

    Science.gov (United States)

    Hung, Richard; Yin, Guohua; Klich, Maren A.; Grimm, Casey; Bennett, Joan W.

    2016-01-01

    In this paper, we demonstrate the ability of Arabidopsis thaliana to detect different mixtures of volatile organic compounds (VOCs) emitted by the common indoor fungus, Aspergillus versicolor, and demonstrate the potential usage of the plant as a bioindicator to monitor fungal VOCs in indoor air. We evaluated the volatile production of Aspergillus versicolor strains SRRC 108 (NRRL 3449) and SRRC 2559 (ATCC 32662) grown on nutrient rich fungal medium, and grown under conditions to mimic the substrate encountered in the built environment where fungi would typically grow indoors (moist wallboard and ceiling tiles). Using headspace solid phase microextraction/gas chromatography-mass spectrometry, we analyzed VOC profiles of the two strains. The most abundant compound produced by both strains on all three media was 1-octen-3-ol. Strain SRRC 2559 made several terpenes not detected from strain SRRC 108. Using a split-plate bioassay, we grew Arabidopsis thaliana in a shared atmosphere with VOCs from the two strains of Aspergillus versicolor grown on yeast extract sucrose medium. The VOCs emitted by SRRC 2559 had an adverse impact on seed germination and plant growth. Chemical standards of individual VOCs from the Aspergillus versicolor mixture (2-methyl-1-butanol, 3-methyl-1-butanol, 1-octen-3-ol, limonene, and β-farnesene), and β-caryophyllene were tested one by one in seed germination and vegetative plant growth assays. The most inhibitory compound to both seed germination and plant growth was 1-octen-3-ol. Our data suggest that Arabidopsis is a useful model for monitoring indoor air quality as it is sensitive to naturally emitted fungal volatile mixtures as well as to chemical standards of individual compounds, and it exhibits relatively quick concentration- and duration-dependent responses.

  10. Distributions of personal VOC exposures: a population-based analysis.

    Science.gov (United States)

    Jia, Chunrong; D'Souza, Jennifer; Batterman, Stuart

    2008-10-01

    Information regarding the distribution of volatile organic compound (VOC) concentrations and exposures is scarce, and there have been few, if any, studies using population-based samples from which representative estimates can be derived. This study characterizes distributions of personal exposures to ten different VOCs in the U.S. measured in the 1999--2000 National Health and Nutrition Examination Survey (NHANES). Personal VOC exposures were collected for 669 individuals over 2-3 days, and measurements were weighted to derive national-level statistics. Four common exposure sources were identified using factor analyses: gasoline vapor and vehicle exhaust, methyl tert-butyl ether (MBTE) as a gasoline additive, tap water disinfection products, and household cleaning products. Benzene, toluene, ethyl benzene, xylenes chloroform, and tetrachloroethene were fit to log-normal distributions with reasonably good agreement to observations. 1,4-Dichlorobenzene and trichloroethene were fit to Pareto distributions, and MTBE to Weibull distribution, but agreement was poor. However, distributions that attempt to match all of the VOC exposure data can lead to incorrect conclusions regarding the level and frequency of the higher exposures. Maximum Gumbel distributions gave generally good fits to extrema, however, they could not fully represent the highest exposures of the NHANES measurements. The analysis suggests that complete models for the distribution of VOC exposures require an approach that combines standard and extreme value distributions, and that carefully identifies outliers. This is the first study to provide national-level and representative statistics regarding the VOC exposures, and its results have important implications for risk assessment and probabilistic analyses.

  11. Volatile organic compound (VOC) emissions during malting and beer manufacture

    Science.gov (United States)

    Gibson, Nigel B.; Costigan, Gavin T.; Swannell, Richard P. J.; Woodfield, Michael J.

    Estimates have been made of the amounts of volatile organic compounds (VOCs) released during different stages of beer manufacture. The estimates are based on recent measurements and plant specification data supplied by manufacturers. Data were obtained for three main manufacturing processes (malting, wort processing and fermentation) for three commercial beer types. Some data on the speciation of emitted compounds have been obtained. Based on these measurements, an estimate of the total unabated VOC emission. from the U.K. brewing industry was calculated as 3.5 kta -1, over 95% of which was generated during barley malting. This value does not include any correction for air pollution control.

  12. Effect of colloids on the occurrence, distribution and photolysis of emerging organic contaminants in wastewaters.

    Science.gov (United States)

    Yan, Caixia; Nie, Minghua; Yang, Yi; Zhou, Junliang; Liu, Min; Baalousha, Mohammed; Lead, Jamie R

    2015-12-15

    The effect of colloids on the occurrence, phase distribution and photolysis of twenty-seven emerging organic contaminants (EOCs) was studied in domestic and livestock wastewaters (DW and LW), respectively. Filtered water (colloids was 13.5% and 14.4% in DW and LW. Most of the EOCs exhibited pseudo-first-order degradation kinetics in all water samples. Control experiments using glass and quartz reactors showed that UV light was more effective on the photolysis of most EOCs. The EOCs photolysis in the three fractions of DW and LW could be accelerated or inhibited compared to ultrapure water with the enhancement factor ranging from -0.94 to 7.33. The impact of colloids on the photolysis of EOCs depended on the compound and the source of water. The photolysis of most EOCs in permeates and filtrates was generally accelerated, while inhibited in the retentates, which could be attributed to the relatively high dissolved organic carbon contents in retentates. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases

    Science.gov (United States)

    Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.

    2016-03-01

    Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

  14. Combined Application of UV Photolysis and Ozonation with Biological Aerating Filter in Tertiary Wastewater Treatment

    Directory of Open Access Journals (Sweden)

    Zhaoqian Jing

    2012-01-01

    Full Text Available To enhance the biodegradability of residual organic pollutants in secondary effluent of wastewater treatment plants, UV photolysis and ozonation were used in combination as pretreatment before a biological aerating filter (BAF. The results indicated that UV photolysis could not remove much COD (chemical oxygen demand, and the performance of ozonation was better than the former. With UV photolysis combined with ozonation (UV/O3, COD removal was much higher than the sum of that with UV photolysis and ozonation alone, which indicated that UV photolysis could efficiently promote COD removal during ozonation. This pretreatment also improved molecular weight distribution (MWD and biodegradability greatly. Proportion of organic compounds with molecular weight (MW <3 kDalton was increased from 51.9% to 85.9%. COD removal rates with BAF and O3/BAF were only about 25% and 38%, respectively. When UV/O3 oxidation was combined with BAF, the average COD removal rate reached above 61%, which was about 2.5 times of that with BAF alone. With influent COD ranging from 65 to 84 mg/L, the effluent COD was stably in the scope of 23–31 mg/L. The combination of UV/O3 oxidation with BAF was quite efficient in organic pollutants removal for tertiary wastewater treatment.

  15. Product study of the photolysis of ketene and ethyl ethynyl ether at 193.3 nm.

    Science.gov (United States)

    Fockenberg, Christopher

    2005-08-18

    The product distributions of the excimer laser photolysis of ketene (CH2CO) and ethyl ethynyl ether (C2H5OCCH) at lambda = 193.3 nm (ArF) were studied using a time-of-flight mass spectrometer (TOFMS) as an analytical tool. Ketene was photolyzed in bath gases consisting of mixtures of He and H2/D2 at various mixing ratios at constant total pressures of 4 Torr and temperature of about 300 K. Singlet methylene (1CH2) produced in the photolysis of ketene was almost instantaneously converted either to triplet methylene (3CH2) or to methyl radicals in collisions with He and H2 or D2. By extrapolating the methyl and methylene signals to zero time after photolysis, initial concentrations of these radicals were obtained. Analyzing the initial 3CH2 and CH3 concentrations as functions of hydrogen-to-helium ratios as well as simulating the observed traces of reactant and product species resulted in 1CH2 + CO (66 +/- 8)%, as the main product channel of the ketene photolysis with smaller contributions from HCCO + H (17 +/- 7)% and 3CH2 + CO (6 +/- 9)%. Hydrogen atoms, acetylene, ethylene, ethyl, and ketenyl radicals, and small amounts of ketene were observed as primary products of the ethyl ethynyl ether photolysis. Quantification of C2H2, C2H4, C2H5, and CH2CO product leads to a HCCO yield of (91 +/- 14)%.

  16. Progress toward hydrogen peroxide micropulsion

    Energy Technology Data Exchange (ETDEWEB)

    Whitehead, J C; Dittman, M D; Ledebuhr, A G

    1999-07-08

    A new self-pressurizing propulsion system has liquid thrusters and gas jet attitude control without heavy gas storage vessels. A pump boosts the pressure of a small fraction of the hydrogen peroxide, so that reacted propellant can controllably pressurize its own source tank. The warm decomposition gas also powers the pump and is supplied to the attitude control jets. The system has been incorporated into a prototype microsatellite for terrestrial maneuvering tests. Additional progress includes preliminary testing of a bipropellant thruster, and storage of unstabilized hydrogen peroxide in small sealed tanks.

  17. Low VOC drying of lumber and wood panel products. Progress report No. 8

    Energy Technology Data Exchange (ETDEWEB)

    Su, W.; Yan, H.; Hooda, U.; Wild, M.P.; Banerjee, S. [Inst. of Paper Science and Technology, Atlanta, GA (United States); Shmulsky, R.; Thompson, A.; Ingram, L.; Conners, T. [Mississippi State Univ., MS (United States)

    1998-07-01

    This study was initiated by an Institute of Paper Science and Technology finding that heating softwood in a low-headspace environment removed much of the VOCs without removing the water. This offered the possibility of removing VOCs from wet wood, capturing them as a product, and then drying the VOC-depleted wood conventionally with little or no VOC controls. Two means of low-headspace heating were explored: steam and radiofrequency (RF). It was found in the previous year, that while both steam and RF were able to drive out VOCs, steam was impracticably slow for lumber. Hence the effect of RF or microwave on wood was the principal focus of the work reported here. Finally, in order to understand the mechanism of VOC release, the transport of the VOCs in wood was studied, together with the seasonal effects that influence VOC concentration in trees.

  18. VocVille - A Casual Social Game for Learning Vocabulary

    OpenAIRE

    Jensen, Michel

    2012-01-01

    The document introduces VocVille, a causal online game for learning vocabularies. This application is created for the author's diploma thesis of his career as a Computervisualist (computer vision) for the University of Koblenz-Landau, which he terminated as an exchange student at the University of Cádiz, in which he developed this diploma thesis.

  19. Assessment of Industrial VOC Gas-Scrubber Performance

    Energy Technology Data Exchange (ETDEWEB)

    Saito, H

    2004-02-13

    Gas scrubbers for air-pollution control of volatile organic compounds (VOC) cover a wide range of technologies. In this review, we have attempted to evaluate the single-pass scrubber destruction and removal efficiencies (DREs) for a range of gas-scrubber technologies. We have focused primarily on typical industrial DREs for the various technologies, typical problems, and any DRE-related experiential information available. The very limited literature citations found suggest significant differences between actual versus design performance in some technologies. The potentially significant role of maintenance in maintaining DREs was also investigated for those technologies. An in-depth portrayal of the entire gas scrubbing industry is elusive. Available literature sources suggest significant differences between actual versus design performance in some technologies. Lack of scrubber system maintenance can contribute to even larger variances. ''Typical'' industrial single-pass performance of commonly used VOC gas scrubbers generally ranged from {approx}80 to 99%. Imperfect solid and/or liquid particulates capture (possibly as low as 95% despite design for 99+% capture efficiency) can also lead to VOC releases. Changing the VOC composition in the gas stream without modifying scrubber equipment or operating conditions could also lead to significant deterioration in attainable destruction and removal efficiencies.

  20. EVALUATION OF SINK EFFECTS ON VOCS FROM A LATEX PAINT

    Science.gov (United States)

    The sink strength of two common indoor materials, a carpet and a gypsum board, was evaluated by environmental chamber tests with four volatile organic compounds (VOCs): propylene glycol, ethylene glycol, 2-(2-butoxyethoxy)ethanol (BEE), and texanol. These oxygenated compounds rep...

  1. CASE STUDIES: LOW-VOC/HAP WOOD FURNITURE COATINGS

    Science.gov (United States)

    The report gives results of a study in which wood furniture manufacturing facilities were identified that had converted at least one of their primary coating steps to low-volatile organic compound (VOC)/hazardous Air pollutant (HAP) wood furniture coatings: high-solids, water...

  2. RESEARCH AND PRODUCT DEVELOPMENT OF LOW-VOC WOOD COATINGS

    Science.gov (United States)

    The report discusses a project, cofunded by the South Coast Air Quality Management District (SCAQMD) and the U.S. EPA, to develop a new, low volatile organic compound (VOC) wood coating. Traditional wood furniture coating technologies contain organic solvents which become air pol...

  3. Solid-phase microextraction and the human fecal VOC metabolome.

    Directory of Open Access Journals (Sweden)

    Emma Dixon

    Full Text Available The diagnostic potential and health implications of volatile organic compounds (VOCs present in human feces has begun to receive considerable attention. Headspace solid-phase microextraction (SPME has greatly facilitated the isolation and analysis of VOCs from human feces. Pioneering human fecal VOC metabolomic investigations have utilized a single SPME fiber type for analyte extraction and analysis. However, we hypothesized that the multifarious nature of metabolites present in human feces dictates the use of several diverse SPME fiber coatings for more comprehensive metabolomic coverage. We report here an evaluation of eight different commercially available SPME fibers, in combination with both GC-MS and GC-FID, and identify the 50/30 µm CAR-DVB-PDMS, 85 µm CAR-PDMS, 65 µm DVB-PDMS, 7 µm PDMS, and 60 µm PEG SPME fibers as a minimal set of fibers appropriate for human fecal VOC metabolomics, collectively isolating approximately 90% of the total metabolites obtained when using all eight fibers. We also evaluate the effect of extraction duration on metabolite isolation and illustrate that ex vivo enteric microbial fermentation has no effect on metabolite composition during prolonged extractions if the SPME is performed as described herein.

  4. DEVELOPMENT OF AEROBIC BIOFILTER DESIGN CRITERIA FOR TREATING VOCS

    Science.gov (United States)

    This paper reports preliminary results on the use of trickle bed biofilters with monolithic ceramic channelized microbial support structures for the treatment of VOCs typical of landfill leachate stripping. Toluene was used for the purpose of characterizing the trickle bed biofi...

  5. Accuracy of seven vapour intrusion algorithms for VOC in groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Provoost, Jeroen; Bronders, Jan; Seuntjens, Piet [Flemish Inst. for Technological Research (VITO), Mol (Belgium); Reijnders, Lucas [Dept. of Science, Open Univ. Netherlands (OU NL), Heerlen (Netherlands); Swartjes, Frank; Lijzen, Johannes [National Inst. for Public Health and the Environment (RIVM), Bilthoven (Netherlands)

    2009-02-15

    During the last decade, soil contamination with volatile organic contaminants (VOC) received special attention because of their potential to cause indoor air problems. Moreover, research has shown that people spend 64% to 94% of there time indoors; therefore, the indoor air quality is of a primary importance for exposure to VOC. Human health risks to VOC-in cases of soil contamination-are often dominated by the exposure route 'inhalation of indoor air'. Exposure is often a result of vapour transport from the soil or groundwater to the indoor air of the building. Within human health risk assessments, a variety of algorithms are available that calculate transfer of soil gas to the indoor air. These algorithms suffer from a relatively high uncertainty due to a lack of representation of spatial and temporal variability. For such an application, these algorithms need to be further verified empirically against field observations so that they can be sufficiently reliable for regulatory purposes. This paper presents the accuracy for seven algorithms by using observed and predicted soil and indoor air concentrations from three sites, where the groundwater had been contaminated with aromatic and chlorinated VOC. (orig.)

  6. DEVELOPMENT OF AEROBIC BIOFILTER DESIGN CRITERIA FOR TREATING VOCS

    Science.gov (United States)

    This paper reports preliminary results on the use of trickle bed biofilters with monolithic ceramic channelized microbial support structures for the treatment of VOCs typical of landfill leachate stripping. Toluene was used for the purpose of characterizing the trickle bed biofi...

  7. Accuracy of seven vapour intrusion algorithms for VOC in groundwater

    NARCIS (Netherlands)

    Provoost, J.; Reijnders, L.; Swartjes, F.; Bronders, J.; Seuntjens, P.; Lijzen, J.

    2009-01-01

    Background, aim and scope: During the last decade, soil contamination with volatile organic contaminants (VOC) received special attention because of their potential to cause indoor air problems. Moreover, research has shown that people spend 64% to 94% of there time indoors; therefore, the indoor ai

  8. VOC signatures from North American oil and gas sources (Invited)

    Science.gov (United States)

    Simpson, I. J.; Marrero, J.; Blake, N. J.; Barletta, B.; Hartt, G.; Meinardi, S.; Schroeder, J.; Apel, E. C.; Hornbrook, R. S.; Blake, D. R.

    2013-12-01

    Between 2008 and 2013 UC Irvine has used its whole air sampling (WAS) technique to investigate VOC source signatures from a range of oil and gas sources in North America, including five separate field campaigns at the Alberta oil sands (1 airborne, 4 ground-based); the 2010 Deepwater Horizon oil spill (airborne and ship-based); the 2012 airborne Deep Convective Clouds and Chemistry Project (DC3) mission over oil and gas wells in Colorado, Texas and Oklahoma; and the 2013 ground-based Barnett Shale Campaign in Texas. Each campaign has characterized more than 80 individual C1-C10 VOCs including alkanes, alkenes and aromatics. For example, oil sands are an extra-heavy, unconventional crude oil that is blended with diluent in order to flow, and upgraded into synthetic crude oil. The VOC signature at the oil sands mining and upgrading facilities is alkane-rich, and the fuel gas associated with these operations has an i-butane/n-butane ratio similar to that of liquefied petroleum gas (LPG). In addition to light alkanes, enhanced levels of benzene were observed over US oil and natural gas wells during DC3, likely because of its use in hydrofracking fluid. A series of VOC emission ratios from North American petrochemical sources will be presented and compared, including oil sands, conventional oil and hydrofracking operations.

  9. Steady-state and laser flash photolysis studies of 1-aziridinyl-1,2-dibenzoylalkenes

    Energy Technology Data Exchange (ETDEWEB)

    Barik, R.; Kumar, C.V.; Das, P.K.; George, M.V.

    1985-11-01

    Results of a photochemical study based on product analysis and 337.1-nm laser flash photolysis are reported for several cis- and trans-1,2-dibenzoylethylenes bearing aziridinyl groups at the 1-position. Products isolated from steady-state photolysis suggest facile ring expansions yielding pyrrolines as well as extrusion of alkenes from the aziridine moieties forming nitrene fragments, which subsequently undergo ring closure to give isoxazoles. Laser flash photolysis studies show transient absorption changes, explainable in terms of cis-trans photoisomerization and formation of azomethine ylides. The latter are also observed upon steady-state irradiation of these aziridinyl-1,2-dibenzoylethylenes in an EPA glass at 77 K. 46 references, 4 figures.

  10. Characterization of transient species in laser photolysis of aromatic amino acids using acetone as photosensitizer

    Institute of Scientific and Technical Information of China (English)

    宋钦华; 徐业平; 俞书勤; 陈从香; 马兴孝; 王文锋; 姚思德; 林念芸

    1999-01-01

    The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.

  11. Analysis of N-nitrosodiethylamine by ion chromatography coupled with UV photolysis pretreatment

    Directory of Open Access Journals (Sweden)

    Xueli Li

    2016-04-01

    Full Text Available Nitrosamines such as N-nitrosodiethylamine (NDEA are commonly detected by spectrophotometry after photolysis and Griess reaction (PG in food industries for lower cost. Results of this research indicate that NDEA decays rapidly under UV irradiation, and concentrations of the generated NO2− and NO3− ions vary with photolysis conditions. Thus, the measurement of the PG method may be inconsistent because it is based on the amount of photoproduced NO2−. In addition, more errors may be present in the PG method since NO3− cannot be measured colorimetrically using Griess reagent. In this work, the sum of the concentrations of photoproduced NO2− and NO3− was found to be equivalent to the initial NDEA before photolysis, and a photolysis–ion chromatography method was validated, which may serve as a feasible and accurate method to determine nitrosamines.

  12. Increasing competitiveness of wine producers in strategic alliances VOC

    Directory of Open Access Journals (Sweden)

    Martin Prokeš

    2012-01-01

    Full Text Available The paper describes the main reasons for the formation of new regional association of wineries, based on a different origin for wines in the wine region of Moravia in the southeast part of the Czech Republic. This research aim is to create a plan for new development of such strategic alliances on the basis of results of localization factors. There coefficient of localization is used for identification of cluster. Results are compared with already operating on associations for the appellation in Austria DAC. They were traced changes in consumer preferences in the Czech wine market. Consumers are placing more emphasis on the selection of wine on its descent from a particular area, growing community and the individual grower. This paper specifically introduces new associations for appellation system VOC. This alliance is described in the context of the establishment, operation, development and expansion, respectively the possibility of involvement of additional organizations suppliers and research institutions. The application of the results of research was a plan for the establishment of new alliance VOC Modré Hory, where are associated 30 wine producers of wine in 5 villages around the center Velké Pavlovice. Based on the experience of newly emerging VOC system of appellations was setting up a plan of formation association with the proposed methodological approach. Open cooperation between associations VOC appellation and other entities involving suppliers, customers, research institutions and universities has the possibility of creating an institutionalized wine cluster. The plan to create a wine cluster was proposed to establish cooperation between the newly emerging associations of VOC at three sub-regions of South Moravia, in order to achieve competitive advantage.

  13. HCO Cross Sections and Radical Yields From the Photolysis of Saturated Aldehydes

    Science.gov (United States)

    Flad, J. E.; Brown, S. S.; Burkholder, J. B.; Ravishankara, A. R.

    2005-12-01

    Aldehydes are a major component of oxygenated volatile organic compounds (OVOC) in the atmosphere. They are removed from the atmosphere primarily by reaction with OH or by photodissociation from ultraviolet (radicals. Determination of the radical yields from aldehyde photolysis as a function of temperature, pressure and wavelength has important implications for the HOx budget, particularly in the upper troposphere. Photolysis of formaldehyde and acetaldehyde has been studied extensively in the laboratory, although current parameterizations for radical yields are based in part on studies that have used indirect methods. A sensitive and direct method of measuring these radical yields is therefore of substantial interest. A new instrument has been developed to measure formyl (HCO) radical yields from the photodissociation of aldehydes. A pulsed, tunable ultraviolet laser is used to photolyze the aldehyde between 290 and 350 nm, and a second tunable laser is used to detect the HCO radicals using cavity ring-down spectroscopy on the A-X system (613 - 617 nm). The photolysis and probe lasers copropagate along the axis of the ring-down cell to maximize the overlap of the two laser beams for sensitive HCO detection. The absorption cross section of HCO has been determined by measuring the HCO product from the reaction of atomic chlorine with formaldehyde relative to the NO 3 product from the reaction of atomic chlorine with chlorine nitrate. Atomic chlorine was generated by photolysis of Cl 2 at 335 nm. The HCO quantum yield from the photolysis of acetaldehyde and formaldehyde and its dependence on photolysis wavelength, temperature, and pressure is being studied.

  14. Photolysis of RDX and nitroglycerin in the context of military training ranges.

    Science.gov (United States)

    Bordeleau, Geneviève; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

    2013-09-01

    Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and nitroglycerin (NG) are two energetic materials commonly found in the environment on military training ranges. They are deposited on the ground in the form of solid particles, which can then dissolve in infiltration water or in surface water bodies. The objective of this study was to evaluate whether photolysis by sunlight can significantly contribute to the natural attenuation of RDX and NG (as solid particles or dissolved in surface water) at mid-northern latitudes, where training ranges of Canada and many European countries are located. Experiments conducted at 46.9°N show that both compounds are degraded by sunlight when dissolved in water, with half-lives between 1 and 120d, depending on the compound and time of year. Numerical models may be useful in predicting such photolysis rates, but the models should take into account current ozone levels, as older radiation datasets, collected before the ozone depletion observed since the late 1970s, underestimate the RDX/NG photolysis rate. For solid RDX or NG-bearing particles, photolysis is slower (half-lives of 2-4months), but the degradation rate is still rapid enough to make this process significant in a natural attenuation context. However, photolysis of NG embedded within solid propellant particles cannot proceed to completion, due to the stable nitrocellulose matrix of the propellant. Nonetheless, photolysis clearly constitutes an important attenuation mechanism that should be considered in conceptual models and included in numerical modeling efforts. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Kinetics and mechanism of photolysis and TiO2 photocatalysis of triclosan.

    Science.gov (United States)

    Son, Hyun-Seok; Ko, Gwangpyo; Zoh, Kyung-Duk

    2009-07-30

    The degradations of triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol), a potent broad-spectrum antimicrobial agent, were compared in TiO2-only in the dark condition, photolysis, and TiO2 photocatalysis with a UV-A lamp. TiO2 photocatalysis more effectively degraded and mineralized triclosan compared to TiO2-only and photolysis conditions. While triclosan removed only 30% by TiO2-only condition within 20 min, the triclosan degradation in photolysis and photocatalysis at the same time was 75 and 82%, respectively, and TOC removal was significantly higher in photocatalysis than in photolysis. The data of kinetics showed that triclosan adsorption onto TiO2 was fitted to Langmuir isotherm, and TiO2 photocatalysis was fitted to Langmuir-Hinshelwood model (b=27.99 mM(-1), K(triclosan)=9.49 mM(-1)). The neutral range of pH was favorable to photocatalysis due to the charge effect between TiO2 and triclosan. The addition of 2-propanol, a radical scavenger, significantly reduced the degradation of triclosan both in photolysis and photocatalysis. Dioxin-type intermediates such as dibenzo-dichloro-p-dioxin (DCDD), dibenzo-p-dioxin were produced in photolysis with and without 2-propanol, and also in photocatalysis with 2-propanol, but these intermediates were not detected in photocatalysis without 2-propanol. This result indicates that the photocatalytic degradation of triclosan is mainly achieved by radicals, and these radicals can further degrade dioxin-type intermediates once they are produced in photocatalysis.

  16. Safety in the Chemical Laboratory. Organic Peroxides.

    Science.gov (United States)

    Shanley, Edward S.

    1990-01-01

    Discussed is the thermodynamic instability of organic peroxides. The process of autoxidation which results in peroxide formation is described. Precautions necessary to prevent autoxidation hazards associated with these reagents are suggested. (CW)

  17. Room temperature FePt nanoparticles formation kinetics by laser solution photolysis

    CSIR Research Space (South Africa)

    Nkosi, S

    2012-04-01

    Full Text Available Formation Kinetics by Laser solution photolysis S. Nkosi1, B.W. Mwakikunga2, E. Sideras-Haddad1 1University of the Witwatersrand 2 DST/NCNSM, Pretoria The 4th International Conference on Nanoscience and Nanotechnology 1 – 4 April 2012, University... emission during photolysis, � the produced either positive or negative metallic ions (liquid form). Theoretical consideration transabsreflLASER IIII ++= Energy conservation (Kirchoff’s law) lossestransferheat dt dNVH dt dTV V NCII ptransabs __+∆∆+∆== Slide...

  18. Photolysis and OH-Initiated oxidation of glycolaldehyde under atmospheric conditions.

    Science.gov (United States)

    Magneron, I; Mellouki, A; Le Bras, G; Moortgat, G K; Horowitz, A; Wirtz, K

    2005-05-26

    The photolysis and OH-initiated oxidation of glycolaldehyde (HOCH(2)CHO), which are relevant atmospheric processes, have been investigated under different conditions using complementary methods in three different laboratories. The UV absorption cross sections of glycolaldehyde determined in two of the laboratories are in excellent agreement. The photolysis of glycolaldehyde in air has been investigated in a quartz cell with sunlamps and in the EUPHORE chamber irradiated by sunlight. The mean photolysis rate measured under solar radiation was (1.1 +/- 0.3) x 10(-5) s(-1) corresponding to a mean effective photolysis quantum yield of (1.3 +/- 0.3). The major products detected were HCHO and CO, whereas CH(3)OH was also observed with an initial yield around 10%. Evidence for OH production was found in both experiments using either OH scavenger or OH tracer species. Photolysis of glycolaldehyde was used as the OH source to measure the reaction rate constants of OH with a series of dienes by the relative method and to identify and quantify the oxidation products of the OH-initiated oxidation of 2-propanol. The different experiments suggest that OH is produced by the primary channel: HOCH(2)CHO + hnu --> OH + CH(2)CHO (1). The rate constant of the OH reaction with glycolaldehyde has been measured at 298 K using the relative method: k(glyc) = (1.2 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1). The product study of the OH-initiated oxidation of glycolaldehyde in air has been performed using both a FEP bag and the EUPHORE chamber. HCHO was observed to be the major product with a primary yield of around 65%. Glyoxal (CHOCHO) was also observed in EUPHORE with a primary yield of (22 +/- 6)%. This yield corresponds to the branching ratio ( approximately 20%) of the H-atom abstraction channel from the CH(2) group in the OH + HOCH(2)CHO reaction, the major channel ( approximately 80%) being the H-atom abstraction from the carbonyl group. The data obtained in this work, especially the

  19. 21 CFR 582.1366 - Hydrogen peroxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrogen peroxide. 582.1366 Section 582.1366 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1366 Hydrogen peroxide. (a) Product. Hydrogen peroxide. (b) (c) Limitations,...

  20. Ozone and secondary organic aerosol production by interaction between and organophosphorous pesticide and biogenic VOCs mixture

    Science.gov (United States)

    Borrás, Esther; Ródenas, Mila; Vera, Teresa; Muñoz, Amalia

    2017-04-01

    Pesticides are the chemical compounds most widely used worldwide, and their toxicological characteristics can have harmful effects on human health. The entry into the atmosphere of pesticides occurs during application or subsequent processes. Once they are emitted, they can be distributed in the gas phase or particulate phase. However, most of them are in both phases, since they are semi-volatile compounds. As with other organic compounds, pesticides' removal in the atmosphere can be mainly accomplished by wet or dry deposition, by photolysis or by reaction with hydroxyl radicals (OH), nitrate radicals (NO3) and ozone (O3) [1]. All these processes give rise to the formation of other products, which could become more harmful than the starting compounds. It is therefore necessary to know all these processes to estimate the impact of pesticides in the atmosphere. In addition, it is important to study how the pesticides interact with organic compounds naturally emitted by crops and their possible impact on the formation of secondary organic aerosols, ozone and other compounds. In this work, the gas phase atmospheric degradation of an organothiophosphate insecticide has been investigated at the large outdoor European Photoreactor (EUPHORE) in the presence of a biogenic compound mixture typical from orange trees emissions. Its photolysis has been studied under sunlight conditions, in the presence of different concentration ratios of chlorpyrifos and biogenic VOCs mixture and in the absence of initial inorganic seeds. Reaction with ozone has also been studied. Gaseous phase compounds were determined by a Fourier Transform Infrared Spectrometer (FTIR), Proton Transfer Reaction - Mass Spectrometry (PTRMS), Solid Phase Microextraction (SPME) coupled to gas chromatography-mass spectrometry (GCMS) and NOx, O3 and SO2 monitors. Aerosol mass concentration was measured using a scanning mobility particle sizer (SMPS) and a tapered element oscillating monitor (TEOM). Chemical

  1. Accidental Ingestion of 35% Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Sean Pritchett

    2007-01-01

    Full Text Available Hydrogen peroxide is a commonly used oxidizing agent with a variety of uses depending on its concentration. Ingestion of hydrogen peroxide is not an uncommon source of poisoning, and results in morbidity through three main mechanisms: direct caustic injury, oxygen gas formation and lipid peroxidation. A case of a 39-year-old man who inadvertently ingested 250 mL of unlabelled 35% hydrogen peroxide intended for natural health use is presented. Hydrogen peroxide has purported benefits ranging from HIV treatment to cancer treatment. Its use in the natural health industry represents an emerging source for accidental poisonings.

  2. Modeling unsteady-state VOC transport in simulated waste drums. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    Liekhus, K.J.; Gresham, G.L.; Peterson, E.S.; Rae, C.; Hotz, N.J.; Connolly, M.J.

    1994-01-01

    This report is a revision of an EG&G Idaho informal report originally titled Modeling VOC Transport in Simulated Waste Drums. A volatile organic compound (VOC) transport model has been developed to describe unsteady-state VOC permeation and diffusion within a waste drum. Model equations account for three primary mechanisms for VOC transport from a void volume within the drum. These mechanisms are VOC permeation across a polymer boundary, VOC diffusion across an opening in a volume boundary, and VOC solubilization in a polymer boundary. A series of lab-scale experiments was performed in which the VOC concentration was measured in simulated waste drums under different conditions. A lab-scale simulated waste drum consisted of a sized-down 55-gal metal drum containing a modified rigid polyethylene drum liner. Four polyethylene bags were sealed inside a large polyethylene bag, supported by a wire cage, and placed inside the drum liner. The small bags were filled with VOC-air gas mixture and the VOC concentration was measured throughout the drum over a period of time. Test variables included the type of VOC-air gas mixtures introduced into the small bags, the small bag closure type, and the presence or absence of a variable external heat source. Model results were calculated for those trials where the permeability had been measured.

  3. CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

    KAUST Repository

    Galí, Martí

    2016-11-14

    Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (mol quanta)-1), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d-1), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

  4. The Influence of Photolysis Rate Constants in Ozone Production for the Paso del Norte Region

    Science.gov (United States)

    Becerra, Fernando; Fitzgerald, Rosa

    2012-03-01

    In this research work we are focusing on understanding the relationship between photolysis rates and the photochemical ozone changes observed in the Paso del Norte region. The city of El Paso, Texas together with Ciudad Juarez, Mexico, forms the largest contiguous bi-national metropolitan area. This region suffers year-round ozone pollution events, and a better understanding is needed to mitigate them. Previous studies have found that ambient ozone concentrations tend to be higher on weekends rather than on weekdays, this phenomenon being referred to, as the ``weekend effect.'' If the ozone standard is exceeded more frequently on weekends, then this phenomenon must be considered in the design of ozone control strategies. In this work we investigate some of the most representative weekend ozone episodes at El Paso, TX, during the years 2009, 2010 and 2011 using the ozone photolysis rates. In this research the TUV radiative-transfer model is used to calculate the local photolysis rates and a UV MFRSR instrument is used to obtain experimental parameters. Seasonal variations and the weekday-weekend effect is studied. The results of this research will help to understand the underlying behavior of the photolysis rate constants when different atmospheric conditions are present.

  5. Flash photolysis using a light emitting diode: an efficient, compact, and affordable solution.

    Science.gov (United States)

    Bernardinelli, Yann; Haeberli, Christian; Chatton, Jean-Yves

    2005-06-01

    Flash photolysis has become an essential technique for dynamic investigations of living cells and tissues. This approach offers several advantages for instantly changing the concentration of bioactive compounds outside and inside living cells with high spatial resolution. Light sources for photolysis need to deliver pulses of high intensity light in the near UV range (300-380 nm), to photoactivate a sufficient amount of molecules in a short time. UV lasers are often required as the light source, making flash photolysis a costly approach. Here we describe the use of a high power 365 nm light emitting diode (UV LED) coupled to an optical fiber to precisely deliver the light to the sample. The ability of the UV LED light source to photoactivate several caged compounds (CMNB-fluorescein, MNI-glutamate, NP-EGTA, DMNPE-ATP) as well as to evoke the associated cellular Ca(2+) responses is demonstrated in both neurons and astrocytes. This report shows that UV LEDs are an efficient light source for flash photolysis and represent an alternative to UV lasers for many applications. A compact, powerful, and low-cost system is described in detail.

  6. Derivatization and photolysis of a photoaffinity reagent for probing protein and cell surface interactions

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, H.; Harris, H.W. Jr.

    1986-05-01

    The synthesis of the novel, heterobifunctional, cleavable, photoactivable crosslinking reagent, N-(4-(p-azido-m-(/sup 125/I) iodophenylazo)benzoyl)-3-aminopropyl-N'-oxysulfosuccinimide has been described by Denny and Blobel. This reagent is desirable because after photolysis and azo bond cleavage the /sup 125/I is transferred from the reagent to the crosslinked molecule. The authors demonstrate that using the reported synthesis 99% of the desired reagent is destroyed during the chloramine-T iodination step. They report a synthesis revision which produces high yields of the uniodinated (U) reagent. The derivatized reagent may be used in its iodinated (I) or U forms. To study the U reagent, a horseradish peroxidase (HRP) molecule is derivatized with nine reagent molecules. The derivatized HRP has 70% of its original enzymatic activity. After photolysis, 14% of this activity is retained and SDS-PAGE electrophoresis shows a crosslinked complex of HRP molecules. After endocytosis by cells, photolysis attaches the soluble derivatized HRP to membranes allowing them to be traced in the electron microscope. To study the I reagent, an amino-dextran (MW 73-400) molecule is derivatized with three U reagent molecules. The U reagent molecules are then iodinated by the chloramine-T method. With photolysis and cleavage, the /sup 125/I labeled reagent on dextran transfers its label to bovine serum albumin or ovalbumin. The authors conclude this reagent is a versatile probe for study of protein or cell surface topography.

  7. Conformer of the peroxynitrite ion formed under photolysis of crystalline alkali nitrates – cis or trans?

    Science.gov (United States)

    Pak, V. Kh; Anan’ev, V. A.; Dyagileva, E. P.; Lyrshchikov, S. Yu; Miklin, M. B.; Rezvova, M. A.

    2017-01-01

    The optical and infrared reflectance spectra of the crystalline powders prepared by co-crystallization of caesium nitrate, nitrite, and peroxynitrite from alkali solution have been studied. We find that the trans conformer forms under photolysis of crystalline pure caesium nitrate. Under its dissolution the trans conformer transforms to the cis conformer.

  8. CHBr3 (bromoform): Revised UV Absorption Spectrum and Atmospheric Photolysis Rates

    Science.gov (United States)

    Burkholder, J. B.; Papanastasiou, D.; McKeen, S. A.

    2013-12-01

    CHBr3 (bromoform) is a short-lived atmospheric trace compound primarily of natural origin that is a source of reactive bromine in both the troposphere and stratosphere. Estimating the impact of CHBr3 on the environment and its transport to the stratosphere requires a thorough understanding of its atmospheric loss processes, which are primarily UV photolysis and reaction with the OH radical. In this presentation, new measurements of the UV absorption spectrum of CHBr3 will be presented. Spectra were measured at wavelengths between 300 and 345 nm at temperatures between 260 and 330 K using cavity ring-down spectroscopy. The present results will be compared with currently recommended values for use in atmospheric modeling taken from Moortgat et al. [The tropospheric chemistry of ozone in the polar regions, edited by H. Niki and K. H. Becker, Springer-Verlag Berlin Heidelberg, 1993]. The discrepancies and impact on CHBr3 photolysis lifetime will be discussed. A parameterization of the CHBr3 UV spectrum for use in atmospheric models will be presented and local photolysis rate calculations used to highlight the impact of the revised cross section data on local lifetimes and the relative importance of photolysis loss versus reaction with the OH radical. The results from the present study will contribute to a better understanding (and accuracy) of estimates of stratospheric ozone loss due to very short-lived brominated substances.

  9. Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

    Science.gov (United States)

    Kim, Tae-Kyoung; Moon, Bo-Ram; Kim, Taeyeon; Kim, Moon-Kyung; Zoh, Kyung-Duk

    2016-11-01

    We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates.

  10. Laser Flash Photolysis and Pulse Radiolysis of Iodate and Periodate in Aqueous Solution

    DEFF Research Database (Denmark)

    Kläning, U K; Sehested, Knud; Wolff, Thomas

    1981-01-01

    Species containing iodine in oxidation state six are formed by photolysis and radiolysis of aqueous iodate and periodate solutions in the following reactions: IO3–+ O–→ IO42–; IO3–+ OH → IO3; IVII+ eaq–→ IeVI and IVII [graphic omitted] I0VI+ O–(or OH). The present pulse radiolysis and laser flash...

  11. Photolysis of tembotrione and its main by-products under extreme artificial conditions:

    Energy Technology Data Exchange (ETDEWEB)

    Calvayrac, Christophe; Bontemps, Nataly [Laboratoire de Chimie des Biomolécules et de l' Environnement (LCBE, EA 4215), Université de Perpignan Via Domitia (UPVD), 52 avenue Paul Alduy, 66860 Perpignan (France); Nouga-Bissoue, Achille [Ecole Nationale Supérieure de l' Enseignement Technique (ENSET), Université de Douala, BP 2701 Douala (Cameroon); Romdhane, Sana; Coste, Camille-Michel [Laboratoire de Chimie des Biomolécules et de l' Environnement (LCBE, EA 4215), Université de Perpignan Via Domitia (UPVD), 52 avenue Paul Alduy, 66860 Perpignan (France); Cooper, Jean-Francois, E-mail: cooper@univ-perp.fr [Laboratoire de Chimie des Biomolécules et de l' Environnement (LCBE, EA 4215), Université de Perpignan Via Domitia (UPVD), 52 avenue Paul Alduy, 66860 Perpignan (France)

    2013-05-01

    The photolytic behaviour of tembotrione, a new chemical herbicide intended for foliar application in corn, was investigated under unnatural and extreme photochemical exposure in aqueous solutions in the laboratory. It appeared that degradation was dependent on pH and occurred more rapidly under acidic and neutral conditions, leading predominantly to the formation of a xanthenedione type compound by intramolecular cyclisation with loss of HCl. Trace amounts of benzoic acid by-products appeared also during UV-C irradiation (λ = 254 nm) of the parent compound. Results were comparable to those obtained with sulcotrione, another β-triketone herbicide. These extreme irradiation conditions clearly accelerated the phototransformation of sulcotrione vs. simulated sunlight irradiation. Furthermore, the photolysis of the degradation by-products, resulting from either photolysis, hydrolysis or biotic pathways of the two active ingredients, was also carried out. The benzoic acid by-products appeared more stable to photolysis than their parent molecules. Xanthenedione derivatives were degraded more rapidly with several differences depending on the pH value. - Highlights: • Tembotrione and sulcotrione water photolysis appeared enhanced under unnatural and extreme conditions. • Triketones were easily photodegraded under acidic and neutral conditions. • Xanthenedione derivatives were the predominant by-products. • Phototransformation of xanthenedione derivatives was pH-dependent. • Benzoic acid derivatives can be relatively stable.

  12. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones.

    Science.gov (United States)

    Bou-Hamdan, Farhan R; Lévesque, François; O'Brien, Alexander G; Seeberger, Peter H

    2011-01-01

    Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP) tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  13. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones

    Directory of Open Access Journals (Sweden)

    Farhan R. Bou-Hamdan

    2011-08-01

    Full Text Available Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  14. Natural solar photolysis of total organic chlorine, bromine and iodine in water.

    Science.gov (United States)

    Abusallout, Ibrahim; Hua, Guanghui

    2016-04-01

    Municipal wastewater has been increasingly used to augment drinking water supplies due to the growing water scarcity. Wastewater-derived disinfection byproducts (DBPs) may negatively affect the aquatic ecosystems and human health of downstream communities during water reuse. The objective of this research was to determine the degradation kinetics of total organic chlorine (TOCl), bromine (TOBr) and iodine (TOI) in water by natural sunlight irradiation. Outdoor solar photolysis experiments were performed to investigate photolytic degradation of the total organic halogen (TOX) formed by fulvic acid and real water and wastewater samples. The results showed that TOX degradation by sunlight irradiation followed the first-order kinetics with half-lives in the range of 2.6-10.7 h for different TOX compounds produced by fulvic acid. The TOX degradation rates were generally in the order of TOI > TOBr ≅ TOCl(NH2Cl) > TOCl(Cl2). High molecular weight TOX was more susceptible to solar photolysis than corresponding low molecular weight halogenated compounds. The nitrate and sulfite induced indirect TOX photolysis rates were less than 50% of the direct photolysis rates under the conditions of this study. Fulvic acid and turbidity in water reduced TOX photodegradation. These results contribute to a better understanding of the fate of chlorinated, brominated and iodinated DBPs in surface waters.

  15. PARAMETRIC EVALUATION OF VOC CONVERSION VIA CATALYTIC INCINERATION

    Directory of Open Access Journals (Sweden)

    Kaskantzis Neto G.

    1997-01-01

    Full Text Available Abstract - A pilot-scale catalytic incineration system was used to investigate the effectiveness of catalytic incineration as a means of reducing volatile organic compound (VOC air pollutants. The objectives of the study were: 1 to investigate the effects of operating and design variables on the reduction efficiency of VOCs; and 2 to evaluate reduction efficiencies for specific compounds in different chemical classes. The study results verified that the following factors affect the catalyst performance: inlet temperature, space velocity, compound type, and compound inlet concentration. Tests showed that reduction efficiencies exceeding 98% were possible, given sufficiently high inlet gas temperatures for the following classes of compounds: alcohols, acetates, ketones, hydrocarbons, and aromatics

  16. Use of Combined Observational- and Model-Derived Photochemical Indicators to Assess the O3-NOx-VOC System Sensitivity in Urban Areas

    Directory of Open Access Journals (Sweden)

    Edson R. Carrillo-Torres

    2017-01-01

    Full Text Available Tropospheric levels of O3 have historically exceeded the official annual Mexican standards within the Monterrey Metropolitan Area (MMA in NE Mexico. High-frequency and high-precision measurements of tropospheric O3, NOy, NO2, NO, CO, SO2, PM10 and PM2.5 were made at the Obispado monitoring site near the downtown MMA from September 2012 to August 2013. The seasonal cycles of O3 and NOy are driven by changes in meteorology and to a lesser extent by variations in primary emissions. The NOy levels were positively correlated with O3 precursors and inversely correlated with O3 and wind speed. Recorded data were used to assess the O3-Volatile Organic Compounds (VOC-NOx system’s sensitivity through an observational-based approach. The photochemical indicator O3/NOy was derived from measured data during the enhanced O3 production period (12:00–18:00 Central Daylight Time (CDT, GMT-0500. The O3/NOy ratios calculated for this time period showed that the O3 production within the MMA is VOC sensitive. A box model simulation of production rates of HNO3 (PHNO3 and total peroxides (Pperox carried out for O3 episodes in fall and spring confirmed the VOC sensitivity within the MMA environment. No significant differences were observed in O3/NOy from weekdays to weekends or for PHNO3/Pperox ratios, confirming the limiting role of VOCs in O3 production within the MMA. The ratified photochemical regime observed may allow the environmental authorities to revise and verify the current policies for air quality control within the MMA.

  17. Modeling the uncertainty of several VOC and its impact on simulated VOC and ozone in Houston, Texas

    Science.gov (United States)

    Pan, Shuai; Choi, Yunsoo; Roy, Anirban; Li, Xiangshang; Jeon, Wonbae; Souri, Amir Hossein

    2015-11-01

    A WRF-SMOKE-CMAQ modeling system was used to study Volatile Organic Compound (VOC) emissions and their impact on surface VOC and ozone concentrations in southeast Texas during September 2013. The model was evaluated against the ground-level Automated Gas Chromatograph (Auto-GC) measurement data from the Texas Commission on Environmental Quality (TCEQ). The comparisons indicated that the model over-predicted benzene, ethylene, toluene and xylene, while under-predicting isoprene and ethane. The mean biases between simulated and observed values of each VOC species showed clear daytime, nighttime, weekday and weekend variations. Adjusting the VOC emissions using simulated/observed ratios improved model performance of each VOC species, especially mitigating the mean bias substantially. Simulated monthly mean ozone showed a minor change: a 0.4 ppb or 1.2% increase; while a change of more than 5 ppb was seen in hourly ozone data on high ozone days, this change moved model predictions closer to observations. The CMAQ model run with the adjusted emissions better reproduced the variability in the National Aeronautics and Space Administration (NASA)'s Ozone Monitoring Instrument (OMI) formaldehyde (HCHO) columns. The adjusted model scenario also slightly better reproduced the aircraft HCHO concentrations from NASA's DISCOVER-AQ campaign conducted during the simulation episode period; Correlation, Mean Bias and RMSE improved from 0.34, 1.38 ppb and 2.15 ppb to 0.38, 1.33 ppb and 2.08 ppb respectively. A process analysis conducted for both industrial/urban and rural areas suggested that chemistry was the main process contributing to ozone production in both areas, while the impact of chemistry was smaller in rural areas than in industrial and urban areas. For both areas, the positive chemistry contribution increased in the sensitivity simulation largely due to the increase in emissions. Nudging VOC emissions to match the observed concentrations shifted the ozone hotspots

  18. Ensurdecimento vocálico em Zo’é

    Directory of Open Access Journals (Sweden)

    Ana Suelly Arruda Câmara Cabral

    2012-11-01

    Full Text Available Neste trabalho apresentamos uma descrição do fenômeno deensurdecimento vocálico na língua Zo’é (Tupi-Guarani. Sãoapresentadas ainda hipóteses acerca das restrições sincrônicas ativasno condicionamento deste fenômeno, além de uma hipótese acercada origem histórica do mesmo.

  19. Determination of VOC emission rates and compositions for offset printing.

    Science.gov (United States)

    Wadden, R A; Scheff, P A; Franke, J E; Conroy, L M; Keil, C B

    1995-07-01

    The release rates of volatile organic compounds (VOC) as fugitive emissions from offset printing are difficult to quantify, and the compositions are usually not known. Tests were conducted at three offset printing shops that varied in size and by process. In each case, the building shell served as the test "enclosure," and air flow and concentration measurements were made at each air entry and exit point. Emission rates and VOC composition were determined during production for (1) a small shop containing three sheetfed presses and two spirit duplicators (36,700 sheets, 47,240 envelopes and letterheads), (2) a medium-size industrial in-house shop with two webfed and three sheetfed presses, and one spirit duplicator (315,130 total sheets), and (3) one print room of a large commercial concern containing three webfed, heatset operations (1.16 x 10(6) ft) served by catalytic air pollution control devices. Each test consisted of 12 one-hour periods over two days. Air samples were collected simultaneously during each period at 7-14 specified locations within each space. The samples were analyzed by gas chromatography (GC) for total VOC and for 13-19 individual organics. Samples of solvents used at each shop were also analyzed by GC. Average VOC emission rates were 4.7-6.1 kg/day for the small sheetfed printing shop, 0.4-0.9 kg/day for the industrial shop, and 79-82 kg/day for the commercial print room. Emission compositions were similar and included benzene, toluene, xylenes, ethylbenzene, and hexane. Comparison of the emission rates with mass balance estimates based on solvent usage and composition were quite consistent.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. Peroxide-induced cell death and lipid peroxidation in C6 glioma cells.

    Science.gov (United States)

    Linden, Arne; Gülden, Michael; Martin, Hans-Jörg; Maser, Edmund; Seibert, Hasso

    2008-08-01

    Peroxides are often used as models to induce oxidative damage in cells in vitro. The aim of the present study was to elucidate the role of lipid peroxidation in peroxide-induced cell death. To this end (i) the ability to induce lipid peroxidation in C6 rat astroglioma cells of hydrogen peroxide (H2O2), cumene hydroperoxide (CHP) and t-butyl hydroperoxide (t-BuOOH) (ii) the relation between peroxide-induced lipid peroxidation and cell death in terms of time and concentration dependency and (iii) the capability of the lipid peroxidation chain breaking alpha-tocopherol to prevent peroxide-induced lipid peroxidation and/or cell death were investigated. Lipid peroxidation was characterised by measuring thiobarbituric acid reactive substances (TBARS) and, by HPLC, malondialdehyde (MDA), 4-hydroxynonenal (4-HNE) and hexanal. Within 2 h CHP, t-BuOOH and H2O2 induced cell death with EC50 values of 59+/-9 microM, 290+/-30 microM and 12+/-1.1 mM, respectively. CHP and t-BuOOH, but not H2O2 induced lipid peroxidation in C6 cells with EC50 values of 15+/-14 microM and 130+/-33 microM, respectively. The TBARS measured almost exclusively consisted of MDA. 4-HNE was mostly not detectable. The concentration of hexanal slightly increased with increasing concentrations of organic peroxides. Regarding time and concentration dependency lipid peroxidation preceded cell death. Pretreatment with alpha-tocopherol (10 microM, 24 h) prevented both, peroxide-induced lipid peroxidation and cell death. The results strongly indicate a major role of lipid peroxidation in the killing of C6 cells by organic peroxides but also that lipid peroxidation is not involved in H2O2 induced cell death.

  1. Biofiltration for control of volatile organic compounds (VOCS)

    Energy Technology Data Exchange (ETDEWEB)

    Bishop, D.F. [Environmental Protection Agency, Cincinnati, OH (United States); Govind, R. [Univ. of Cincinnati, OH (United States)

    1995-10-01

    Air biofiltration is a promising technology for control of air emissions of biodegradable volatile organic compounds (VOCs). In conjunction with vacuum extraction of soils or air stripping of ground water, it can be used to mineralize VOCs removed from contaminated soil or groundwater. The literature describes three major biological systems for treating contaminated air bioscrubbers, biotrickling filters and biofilters. Filter media can be classified as: bioactive fine or irregular particulates, such as soil, peat, compost or mixtures of these materials; pelletized, which are randomly packed in a bed; and structured, such as monoliths with defined or variable passage size and geometry. The media can be made of sorbing and non-absorbing materials. Non-bioactive pelletized and structured media require recycled solutions of nutrients and buffer for efficient microbial activity and are thus called biotrickling filters. Extensive work has been conducted to improve biofiltration by EPA`s Risk Reduction Engineering Laboratory and the University of Cincinnati in biofilters using pelletized and structured media and improved operational approaches. Representative VOCs in these studies included compounds with a range of aqueous solubilities and octanol-water partition coefficients. The compounds include iso-pentane, toluene, methylene chloride, trichloroethylene (TCE), ethyl benzene, chlorobenzene and perchloroethylene (PCE) and alpha ({alpha}-) pinene. Comparative studies were conducted with peat/compost biofilters using isopentane and {alpha}-pinene. Control studies were also conducted to investigate adsorption/desorption of contaminants on various media using mercuric chloride solution to insure the absence of bioactivity.

  2. Light dependency of VOC emissions from selected Mediterranean plant species

    Science.gov (United States)

    Owen, S. M.; Harley, P.; Guenther, A.; Hewitt, C. N.

    The light, temperature and stomatal conductance dependencies of volatile organic compound (VOC) emissions from ten plant species commonly found in the Mediterranean region were studied using a fully controlled leaf cuvette in the laboratory. At standard conditions of temperature and light (30°C and 1000 μmol m -2 s -1 PAR), low emitting species ( Arbutus unedo, Pinus halepensis, Cistus incanus, Cistus salvifolius, Rosmarinus officinalis and Thymus vulgaris) emitted between 0.1 and 5.0 μg (C) (total VOCs) g -1 dw h -1, a medium emitter ( Pinus pinea) emitted between 5 and 10 μg (C) g -1 dw h -1 and high emitters ( Cistus monspeliensis, Lavendula stoechas and Quercus sp.) emitted more than 10 μg (C) g -1 dw h -1. VOC emissions from all of the plant species investigated showed some degree of light dependency, which was distinguishable from temperature dependency. Emissions of all compounds from Quercus sp. were light dependent. Ocimene was one of several monoterpene compounds emitted by P. pinea and was strongly correlated to light. Only a fraction of monoterpene emissions from C. incanus exhibited apparent weak light dependency but emissions from this plant species were strongly correlated to temperature. Data presented here are consistent with past studies, which show that emissions are independent of stomatal conductance. These results may allow more accurate predictions of monoterpene emission fluxes from the Mediterranean region to be made.

  3. A demonstration of biofiltration for VOC removal in petrochemical industries.

    Science.gov (United States)

    Zhao, Lan; Huang, Shaobin; Wei, Zongmin

    2014-05-01

    A biotrickling filter demo has been set up in a petrochemical factory in Sinopec Group for about 10 months with a maximum inlet gas flow rate of 3000 m3 h(-1). The purpose of this project is to assess the ability of the biotrickling filter to remove hardly biodegradable VOCs such as benzene, toluene and xylene which are recalcitrant and poorly water soluble and commonly found in petrochemical factories. Light-weight hollow ceramic balls (Φ 5-8 cm) were used as the packing media treated with large amounts of circulating water (2.4 m3 m(-2) h(-1)) added with bacterial species. The controlled empty bed retention time (EBRT) of 240 s is a key parameter for reaching a removal efficiency of 95% for benzene, toluene, xylene, and 90% for total hydrocarbons. The demo has been successfully adopted and practically applied in waste air treatments in many petrochemical industries for about two years. The net inlet concentrations of benzene, toluene and xylene were varied from 0.5 to 3 g m(-3). The biofiltration process is highly efficient for the removal of hydrophobic and recalcitrant VOCs with various concentrations from the petrochemical factories. The SEM analysis of the bacterial community in the BTF during VOC removal showed that Pseudomonas putida and Klebsiella sp. phylum were dominant and shutdown periods could play a role in forming the community structural differences and leading to the changes of removal efficiencies.

  4. A mass transfer model for VOC emission from silage

    Science.gov (United States)

    Hafner, Sasha D.; Montes, Felipe; Rotz, C. Alan

    2012-07-01

    Silage has been shown to be an important source of emissions of volatile organic compounds (VOCs), which contribute to the formation of ground-level ozone. Measurements have shown that environmental conditions and silage properties strongly influence emission rates, making it difficult to assess the contribution of silage in VOC emission inventories. In this work, we present an analytical convection-diffusion-dispersion model for predicting emission of VOCs from silage. It was necessary to incorporate empirical relationships from wind tunnel trials for the response of mass transfer parameters to surface air velocity and silage porosity. The resulting model was able to accurately predict the effect of temperature on ethanol emission in wind tunnel trials, but it over-predicted alcohol and aldehyde emission measured using a mass balance approach from corn silage samples outdoors and within barns. Mass balance results confirmed that emission is related to gas-phase porosity, but the response to air speed was not clear, which was contrary to wind tunnel results. Mass balance results indicate that alcohol emission from loose silage on farms may approach 50% of the initial mass over six hours, while relative losses of acetaldehyde will be greater.

  5. Experiments in the EMRP project KEY-VOCs: Adsorption/desorption effects of VOCs in different tubing materials and preparation and analysis of a zero gas

    Science.gov (United States)

    Englert, Jennifer; Claude, Anja; Kubistin, Dagmar; Tensing, Erasmus; Michl, Katja; Plass-Duelmer, Christian

    2017-04-01

    Atmospheric chemistry and composition are influenced by volatile organic compounds (VOCs) emitted from natural and anthropogenic sources. Due to their toxicity and their crucial role in ozone and aerosol formation VOCs impact air quality and climate change and high quality observations are demanded. The European Metrology Research Programme (EMRP) project KEY-VOCs has targeted the improvement of VOC measurement capabilities with the focus on VOCs relevant for indoor air as well as for air quality and climate monitoring programmes. One major uncertainty is the influence of surface effects of the measurement devices. By developing a test system the adsorption/desorption effects of certain VOCs can be systematically examined. Different tubing materials e.g. stainless steel and PFA were analysed with the oxygenated VOC methanol and results of these experiments will be presented. In air quality monitoring very low levels of VOCs have to be measured. Purified air or nitrogen is widely used as a zero gas to characterize measurement systems and procedures as well as for instrument calibration. A high quality zero gas is an important contributor to the quality of the measurements and generally achieved by using state-of-the-art purification technologies. The efficiency of several air purifiers was assessed and the results have been analysed.

  6. Primary VOC emissions from Commercial Aircraft Jet Engines

    Science.gov (United States)

    Kilic, Dogushan; Huang, Rujin; Slowik, Jay; Brem, Benjamin; Durdina, Lukas; Rindlisbacher, Theo; Baltensperger, Urs; Prevot, Andre

    2014-05-01

    Air traffic is growing continuously [1]. The increasing number of airplanes leads to an increase of aviation emissions giving rise to environmental concerns globally by high altitude emissions and, locally on air quality at the ground level [2]. The overall impact of aviation emissions on the environment is likely to increase when the growing air transportation trend [2] is considered. The Aviation Particle Regulatory Instrumentation Demonstration Experiment (APRIDE)-5 campaign took place at Zurich Airport in 2013. In this campaign, aircraft exhaust is sampled during engine acceptance tests after engine overhaul at the facilities of SR Technics. Direct sampling from the engine core is made possible due to the unique fixed installation of a retractable sampling probe and the use of a standardized sampling system designed for the new particulate matter regulation in development for aircraft engines. Many of the gas-phase aircraft emissions, e.g. CO2, NOX, CO, SO2, hydrocarbons, and volatile organic compounds (VOC) were detected by the instruments in use. This study, part of the APRIDE-5 campaign, focuses on the primary VOC emissions in order to produce emission factors of VOC species for varying engine operating conditions which are the surrogates for the flight cycles. Previously, aircraft plumes were sampled in order to quantify VOCs by a proton transfer reaction quadrupole mass spectrometer (PTR-MS) [3]. This earlier study provided a preliminary knowledge on the emission of species such as methanol, acetaldehyde, acetone, benzene and toluene by varying engine thrust levels. The new setup was (i) designed to sample from the diluted engine exhaust and the new tool and (ii) used a high resolution time of flight PTR-MS with higher accuracy for many new species, therefore providing a more detailed and accurate inventory. We will present the emission factors for species that were quantified previously, as well as for many additional VOCs detected during the campaign

  7. Volatile organic compound (VOC) determination in working atmospheres; Determinacion de compuestos organicos volatiles (VOC) en ambiente laboral

    Energy Technology Data Exchange (ETDEWEB)

    Blass A, Georgina; Panama T, Luz A; Corrales C, Deyanira [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

    2003-07-01

    The present work describes, in a synthesized way, the implementation and application of procedures based on the normativity related to the subject of the volatile organic compounds (Volatile Organic Compounds VOC), that allow to sample, quantify and evaluate the present contamination in the working atmosphere of a refinery due to the fugitive emissions of VOC and other substances. In accordance with the corresponding normativity, more than 189 organic compounds denominated dangerous air polluting agents (Hazardous Air Pollutants, HAP) can be found in a working atmosphere, but they are the 11 main HAP that can be found in a refinery. In the present article the work made for the sampling and quantification of 5 of the 11 dangerous polluting agents of the air: benzene, toluene, xylene, iso-octane and naphthalene. [Spanish] El presente trabajo describe, de manera sintetizada, la implementacion y aplicacion de procedimientos basados en la normatividad relacionada al tema de los compuestos organicos volatiles (Volatil Organic Compounds, VOC), que permiten muestrear, cuantificar y evaluar la contaminacion presente en el ambiente laboral de una refineria debido a las emisiones fugitivas de VOC y otras sustancias. De acuerdo con la normatividad correspondiente, mas de 189 compuestos organicos denominados contaminantes peligrosos del aire (Hazardous Air Pollutants, HAP), pueden ser encontrados en un ambiente laboral, pero son 11 los principales HAP que pueden ser hallados en una refineria. En el presente articulo se informa el trabajo realizado para el muestreo y cuantificacion de 5 de los 11 contaminantes peligrosos del aire: benceno, tolueno, xileno, iso-octano y naftaleno.

  8. Volatile Organic Compound (VOC Removal by Vapor Permeation at Low VOC Concentrations: Laboratory Scale Results and Modeling for Scale Up

    Directory of Open Access Journals (Sweden)

    Philippe Moulin

    2011-03-01

    Full Text Available Petroleum transformation industries have applied membrane processes for solvent and hydrocarbon recovery as an economic alternative to reduce their emissions and reuse evaporated components. Separation of the volatile organic compounds (VOCs (toluene-propylene-butadiene from air was performed using a poly dimethyl siloxane (PDMS/α-alumina membrane. The experimental set-up followed the constant pressure/variable flow set-up and was operated at ~21 °C. The membrane is held in a stainless steel module and has a separation area of 55 × 10−4 m². Feed stream was set to atmospheric pressure and permeate side to vacuum between 3 and 5 mbar. To determine the performance of the module, the removed fraction of VOC was analyzed by Gas Chromatography/Flame Ionization Detector (GC/FID. The separation of the binary, ternary and quaternary hydrocarbon mixtures from air was performed at different flow rates and more especially at low concentrations. The permeate flux, permeance, enrichment factor, separation efficiency and the recovery extent of the membrane were determined as a function of these operating conditions. The permeability coefficients and the permeate flux through the composite PDMS-alumina membrane follow the order given by the Hildebrand parameter: toluene > 1,3-butadiene > propylene. The simulated data for the binary VOC/air mixtures showed fairly good agreement with the experimental results in the case of 1,3-butadiene and propylene. The discrepancies observed for toluene permeation could be minimized by taking into account the effects of the porous support and an influence of the concentration polarization. Finally, the installation of a 0.02 m2 membrane module would reduce 95% of the VOC content introduced at real concentration conditions used in the oil industry.

  9. Volatile Organic Compound (VOC) Removal by Vapor Permeation at Low VOC Concentrations: Laboratory Scale Results and Modeling for Scale Up.

    Science.gov (United States)

    Rebollar-Perez, Georgette; Carretier, Emilie; Lesage, Nicolas; Moulin, Philippe

    2011-03-03

    Petroleum transformation industries have applied membrane processes for solvent and hydrocarbon recovery as an economic alternative to reduce their emissions and reuse evaporated components. Separation of the volatile organic compounds (VOCs) (toluene-propylene-butadiene) from air was performed using a poly dimethyl siloxane (PDMS)/α-alumina membrane. The experimental set-up followed the constant pressure/variable flow set-up and was operated at ~21 °C. The membrane is held in a stainless steel module and has a separation area of 55 × 10-4 m². Feed stream was set to atmospheric pressure and permeate side to vacuum between 3 and 5 mbar. To determine the performance of the module, the removed fraction of VOC was analyzed by Gas Chromatography/Flame Ionization Detector (GC/FID). The separation of the binary, ternary and quaternary hydrocarbon mixtures from air was performed at different flow rates and more especially at low concentrations. The permeate flux, permeance, enrichment factor, separation efficiency and the recovery extent of the membrane were determined as a function of these operating conditions. The permeability coefficients and the permeate flux through the composite PDMS-alumina membrane follow the order given by the Hildebrand parameter: toluene > 1,3-butadiene > propylene. The simulated data for the binary VOC/air mixtures showed fairly good agreement with the experimental results in the case of 1,3-butadiene and propylene. The discrepancies observed for toluene permeation could be minimized by taking into account the effects of the porous support and an influence of the concentration polarization. Finally, the installation of a 0.02 m2 membrane module would reduce 95% of the VOC content introduced at real concentration conditions used in the oil industry.

  10. Volatile Organic Compound (VOC measurements in the Pearl River Delta (PRD region, China

    Directory of Open Access Journals (Sweden)

    Chih-chung Chang

    2008-03-01

    Full Text Available We measured levels of ambient volatile organic compounds (VOCs at seven sites in the Pearl River Delta (PRD region of China during the Air Quality Monitoring Campaign spanning 4 October to 3 November 2004. Two of the sites, Guangzhou (GZ and Xinken (XK, were intensive sites at which we collected multiple daily canister samples. The observations reported here provide a look at the VOC distribution, speciation, and photochemical implications in the PRD region. Alkanes constituted the largest percentage (>40% in mixing ratios of the quantified VOCs at six sites; the exception was one major industrial site that was dominated by aromatics (about 52%. Highly elevated VOC levels occurred at GZ during two pollution episodes; however, the chemical composition of VOCs did not exhibit noticeable changes during these episodes. We calculated the OH loss rate to estimate the chemical reactivity of all VOCs. Of the anthropogenic VOCs, alkenes played a predominant role in VOC reactivity at GZ, whereas the contributions of reactive aromatics were more important at XK. Our preliminary analysis of the VOC correlations suggests that the ambient VOCs at GZ came directly from local sources (i.e., automobiles; those at XK were influenced by both local emissions and transportation of air mass from upwind areas.

  11. [Study on control and management for industrial volatile organic compounds (VOCs) in China].

    Science.gov (United States)

    Wang, Hai-Lin; Zhang, Guo-Ning; Nei, Lei; Wang, Yu-Fei; Hao, Zheng-Ping

    2011-12-01

    Volatile organic compounds (VOCs) emitted from industrial sources account for a large percent of total anthropogenic VOCs. In this paper, VOCs emission characterization, control technologies and management were discussed. VOCs from industrial emissions were characterized by high intensity, wide range and uneven distribution, which focused on Bejing-Tianjin Joint Belt, Shangdong Peninsula, Yangtze River Delta and the Pearl River Delta. The current technologies for VOCs treatment include adsorption, catalytic combustion, bio-degradation and others, which were applied in petrochemical, oil vapor recovery, shipbuilding, printing, pharmaceutical, feather manufacturing and so on. The scarcity of related regulations/standards plus ineffective supervision make the VOCs management difficult. Therefore, it is suggested that VOCs treatment be firstly performed from key areas and industries, and then carried out step by step. By establishing of actual reducing amount control system and more detailed VOCs emission standards and regulations, applying practical technologies together with demonstration projects, and setting up VOCs emission registration and classification-related-charge system, VOCs could be reduced effectively.

  12. Role of UV photolysis in accelerating the biodegradation of 2,4,6-TCP.

    Science.gov (United States)

    Wang, Wenbing; Kirumba, George; Zhang, Yongming; Wu, Yanqing; Rittmann, Bruce E

    2015-09-18

    2,4,6-TCP, a kind of chlorinated aromatic and aliphatic compound, is difficult to be biodegraded by ordinary microorganisms. UV photolysis and biodegradation of 2,4,6-TCP by Bacillus amyloliquefaciens intimate coupling is a potential means to accelerate its biotransformation. The initial steps of 2,4,6-TCP biodegradation involve mono-oxygenation reactions that have molecular oxygen and an intracellular electron carrier as cosubstrates. It was demonstrated that B. amyloliquefaciens has the 2,4,6-TCP monooxygenase gene tcpA which could encode 2,4,6-TCP monooxygenase (TCP-MO). TCP-MO would catalytically decompose 2,4,6-TCP into 2,6-DCHQ. We employed an internal loop photolytic biofilm reactor for 2,4,6-TCP degradation. Sequentially coupled photolysis and biodegradation experimental results suggested that 2,4,6-TCP removal rate in P + B (TCP(UV) + phenol) protocol was higher by 77 and 103 % when compared to B (TCP + phenol) and B (TCP-only) protocols respectively. The corresponding loss rate coefficient (k) values were 0.069, 0.039, 0.034 mg/L·min(-1) respectively. This is because UV photolysis converted 2,4,6-TCP into its intermediates: 2,4-dichlorophenol (2,4-DCP), 4-monochlorophenol (4-MCP), phenol, 2,6-dichloro-p-hydroquinone (2,6-DCHQ), with all displaying less inhibition to bacterial action. In addition, phenol was the crucial UV-photolysis product from 2,4,6-TCP, its catabolic oxidation generating internal electron carriers that may accelerate the initial steps of 2,4,6-TCP biodegradation. Intimately coupled photolysis and biodegradation experimental results suggested that 2,4,6-TCP removal rate in P&B (TCP + phenol) protocol was higher by 166 and 681 % when compared to P&B (TCP-only) and P + B protocols respectively. The corresponding loss rate coefficient (k) values were 0.539, 0.203, 0.069 mg/L·min(-1) respectively. It provided sufficient evidence to demonstrate that intimately coupled photolysis and biodegradation accelerated 2,4,6-TCP

  13. Peroxides and peroxide-degrading enzymes in the thyroid.

    Science.gov (United States)

    Schweizer, Ulrich; Chiu, Jazmin; Köhrle, Josef

    2008-09-01

    Iodination of thyroglobulin is the key step of thyroid hormone biosynthesis. It is catalyzed by thyroid peroxidase and occurs within the follicular space at the apical plasma membrane. Hydrogen peroxide produced by thyrocytes as an oxidant for iodide may compromise cellular and genomic integrity of the surrounding cells, unless these are sufficiently protected by peroxidases. Thus, peroxidases play two opposing roles in thyroid biology. Both aspects of peroxide biology in the thyroid are separated in space and time and respond to the different physiological states of the thyrocytes. Redox-protective peroxidases in the thyroid are peroxiredoxins, glutathione peroxidases, and catalase. Glutathione peroxidases are selenoenzymes, whereas selenium-independent peroxiredoxins are functionally linked to the selenoenzymes of the thioredoxin reductase family through their thioredoxin cofactors. Thus, selenium impacts directly and indirectly on protective enzymes in the thyroid, a link that has been supported by animal experiments and clinical observations. In view of this relationship, it is remarkable that rather little is known about selenoprotein expression and their potential functional roles in the thyroid. Moreover, selenium-dependent and -independent peroxidases have rarely been examined in the same studies. Therefore, we review the relevant literature and present expression data of both selenium-dependent and -independent peroxidases in the murine thyroid.

  14. Hydrogen peroxide enteritis: the "snow white" sign.

    Science.gov (United States)

    Bilotta, J J; Waye, J D

    1989-01-01

    Hydrogen peroxide is a useful disinfectant that has achieved widespread utility in varied clinical settings. We report an epidemic of hydrogen peroxide enteritis that developed in seven patients in our gastrointestinal endoscopy unit during a 2-week period in early 1988. During endoscopy, using recently sterilized endoscopes that were flushed with 3% hydrogen peroxide after the glutaraldehyde cycle, instantaneous blanching (the "snow white" sign) and effervescence were noted on the mucosal surfaces when the water button was depressed. No patient subsequently suffered morbidity or mortality associated with this peroxide enteritis, and the biopsy specimens revealed nonspecific inflammation. The toxicity of hydrogen peroxide when used in enema form is reviewed, as well as the pathogenesis of peroxide enteritis.

  15. Coating for components requiring hydrogen peroxide compatibility

    Science.gov (United States)

    Yousefiani, Ali (Inventor)

    2010-01-01

    The present invention provides a heretofore-unknown use for zirconium nitride as a hydrogen peroxide compatible protective coating that was discovered to be useful to protect components that catalyze the decomposition of hydrogen peroxide or corrode when exposed to hydrogen peroxide. A zirconium nitride coating of the invention may be applied to a variety of substrates (e.g., metals) using art-recognized techniques, such as plasma vapor deposition. The present invention further provides components and articles of manufacture having hydrogen peroxide compatibility, particularly components for use in aerospace and industrial manufacturing applications. The zirconium nitride barrier coating of the invention provides protection from corrosion by reaction with hydrogen peroxide, as well as prevention of hydrogen peroxide decomposition.

  16. Post-treatment of biologically treated wastewater containing organic contaminants using a sequence of H2O2 based advanced oxidation processes: photolysis and catalytic wet oxidation.

    Science.gov (United States)

    Rueda-Márquez, J J; Sillanpää, M; Pocostales, P; Acevedo, A; Manzano, M A

    2015-03-15

    In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3).

  17. Hydrogen peroxide on the surface of Europa

    Science.gov (United States)

    Carlson, R.W.; Anderson, M.S.; Johnson, R.E.; Smythe, W.D.; Hendrix, A.R.; Barth, C.A.; Soderblom, L.A.; Hansen, G.B.; McCord, T.B.; Dalton, J.B.; Clark, R.N.; Shirley, J.H.; Ocampo, A.C.; Matson, D.L.

    1999-01-01

    Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

  18. PEROXIDE BLEACHING OF LOW-FREENESS TMP

    Institute of Scientific and Technical Information of China (English)

    ZhongLiu; Y.Ni; Z.Li,G.Court

    2004-01-01

    Peroxide bleaching is an essential unit operation toproduce value-added mechanical pulp-based papergrade. In this paper, we presented the results fromperoxide bleaching of low-freeness TMP for theproduction of SC paper. Two aspects wereaddressed; the effect of pulp strength and theformation of anionic trashes. The strength properties,such as tensile, burst and zero-span tensile, areimproved after the peroxide bleaching process. Theamount of anionic trashes formed is almostproportional to the hydrogen peroxide charge.

  19. PEROXIDE PROCESS FOR SEPARATION OF RADIOACTIVE MATERIALS

    Science.gov (United States)

    Seaborg, G.T.; Perlman, I.

    1958-09-16

    reduced state, from hexavalent uranium. It consists in treating an aqueous solution containing such uranium and plutonium ions with sulfate ions in order to form a soluble uranium sulfate complex and then treating the solution with a soluble thorium compound and a soluble peroxide compound in order to ferm a thorium peroxide carrier precipitate which carries down with it the plutonium peroxide present. During this treatment the pH of the solution must be maintained between 2 and 3.

  20. Theoretical study of simultaneous water and VOCs adsorption and desorption in a silica gel rotor

    DEFF Research Database (Denmark)

    Zhang, G.; Zhang, Y.F.; Fang, Lei

    2008-01-01

    One-dimensional partial differential equations were used to model the simultaneous water and VOC (Volatile Organic Compound) adsorption and desorption in a silica gel rotor which was recommended for indoor air cleaning. The interaction among VOCs and moisture in the adsorption and desorption...... by the temperatures of the rotor and the air stream. The VOC transfer equations were solved by discretizing them into explicit up-wind finite differential equations. The model was validated with experimental data. The calculated results suggested that the regeneration time designed for dehumidification may...... process was neglected in the model as the concentrations of VOC pollutants in typical indoor environment were much lower than that of moisture and the adsorbed VOCs occupied only a minor portion of adsorption capacity of the rotor. Consequently VOC transfer was coupled with heat and moisture transfer only...

  1. Volatile organic compounds (VOCs) in surface coating materials: Their compositions and potential as an alternative fuel.

    Science.gov (United States)

    Dinh, Trieu-Vuong; Choi, In-Young; Son, Youn-Suk; Song, Kyu-Yong; Sunwoo, Young; Kim, Jo-Chun

    2016-03-01

    A sampling system was designed to determine the composition ratios of VOCs emitted from 31 surface coating materials (SCMs). Representative architectural, automotive, and marine SCMs in Korea were investigated. Toluene, ethylbenzene, and xylene were the predominant VOCs. The VOC levels (wt%) from automotive SCMs were significantly higher than those from architectural and marine paints. It was found that target SCMs comprised mainly VOCs with 6-10 carbon atoms in molecules, which could be adsorbed by activated carbon. The saturated activated carbon which had already adsorbed toluene, ethylbenzene, and m-xylene was combusted. The saturated activated carbon was more combustible than new activated carbon because it comprised inflammable VOCs. Therefore, it could be an alternative fuel when using in a "fuelization system". To use the activated carbon as a fuel, a control technology of VOCs from a coating process was also designed and introduced.

  2. Purge and trap method to determine alpha factors of VOC liquid-phase mass transfer coefficients

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A theoretical approach and laboratory practice of determining the alpha factors of volatile organic compound (VOC) liquid-phase mass transfer coefficients are present in this study.Using Purge Trap Concentrator, VOC spiked water samples are purged by high-purity nitrogen in the laboratory, the VOC liquid-phase mass transfer rate constants under the laboratory conditions are then obtained by observing the variation of VOCs purged out of the water with the purge time.The alpha factors of VOC liquid-phase mass transfer coefficients are calculated as the ratios of the liquid-phase mass transfer rate constants in real water samples to their counterparts in pure water under the same experimental conditions. This direct and fast approach is easy to control in the laboratory, and would benefit mutual comparison among researchers, so might be useful for thestudy of VOC mass transfer across the liquid-gas interface.

  3. Major reactive species of ambient volatile organic compounds (VOCs) and their sources in Beijing

    Institute of Scientific and Technical Information of China (English)

    SHAO; Min; FU; Linlin; LIU; Ying; LU; Sihua; ZHANG; Yuanhan

    2005-01-01

    Volatile organic compounds (VOCs) are important precursors of atmospheric chemical processes. As a whole mixture, the ambient VOCs show very strong chemical reactivity. Based on OH radical loss rates in the air, the chemical reactivity of VOCs in Beijing was calculated. The results revealed that alkenes, accounting for only about 15% in the mixing ratio of VOCs, provide nearly 75% of the reactivity of ambient VOCs and the C4 to C5 alkenes were the major reactive species among the alkenes. The study of emission characteristics of various VOCs sources indicated that these alkenes are mainly from vehicle exhaust and gasoline evaporation. The reduction of alkene species in these two sources will be effective in photochemical pollution control in Beijing.

  4. [Study on the chemical compositions of VOCs emitted by cooking oils based on GC-MS].

    Science.gov (United States)

    He, Wan-Qing; Nie, Lei; Tian, Gang; Li, Jing; Shao, Xia; Wang, Min-Yan

    2013-12-01

    Volatile organic compounds (VOCs) are key precursors of ozone and secondary organic aerosols in air, and the differences in the compositions of VOCs lead to their different contribution to atmospheric reaction. Cooking oil fume is one of the important sources of atmospheric VOCs, and its chemical compositions are distinct under different conditions of oil types, food types, cooking methods and heating temperatures etc. In this study, the production of cooking oil fume was simulated by heating typical pure vegetable oils (peanut oil, sunflower oil, soybean oil, olive oil and blend oil) at different temperatures in beakers to investigate the chemical compositions of VOCs. The emitted VOCs were sampled with a Tenax adsorption tube and analyzed using GC-MS after thermal desorption. According to spectral library search and map analysis, using area normalized semi-quantitative method, preliminary qualitative and quantitative tests were conducted for the specific components of VOCs under different conditions.

  5. PEROXIDE BLEACHING OF LOW-FREENESS TMP

    Institute of Scientific and Technical Information of China (English)

    Zhong Liu; Y. Ni; Z. Li; G. Court

    2004-01-01

    Peroxide bleaching is an essential unit operation to produce value-added mechanical pulp-based paper grade. In this paper, we presented the results from peroxide bleaching of low-freeness TMP for the production of SC paper. Two aspects were addressed; the effect of pulp strength and the formation of anionic trashes. The strength properties,such as tensile, burst and zero-span tensile, are improved after the peroxide bleaching process. The amount of anionic trashes formed is almost proportional to the hydrogen peroxide charge.

  6. Characteristics of Ambient Volatile Organic Compounds (VOCs Measured in Shanghai, China

    Directory of Open Access Journals (Sweden)

    Guang-Qiang Zhou

    2010-08-01

    Full Text Available To better understand the characteristics of ambient abundance of volatile organic compounds (VOCs in Shanghai, one of the biggest metropolis of China, VOCs were measured with a gas chromatography system equipped with a mass-selective detector (GC/MSD from July 2006 to February 2010. An intensive measurement campaign was conducted (eight samples per day with a 3 hour interval during May 2009. The comparison of ambient VOCs collected in different regions of Shanghai shows that the concentrations are slightly higher in the busy commercial area (28.9 ppbv at Xujiaui than in the urban administrative area (24.3 ppbv at Pudong. However, during the intensive measurement period, the concentrations in the large steel industrial area (28.7 ppbv at Baoshan were much higher than in the urban administrative area (18 ppbv at Pudong, especially for alkanes, alkenes, and toluene. The seasonal variations of ambient VOC concentrations measured at the Xujiahui sampling site indicate that the VOC concentrations are significantly affected by meteorological conditions (such as wind direction and precipitation. In addition, although alkanes are the most abundant VOCs at the Xujiahui measurement site, the most important VOCs contributing to ozone formation potential (OFP are aromatics, accounting for 57% of the total OFP. The diurnal variations of VOC concentrations show that VOC concentrations are higher on weekdays than in weekends at the Xujiahui sampling site, suggesting that traffic condition and human activities have important impacts on VOC emissions in Shanghai. The evidence also shows that the major sources of isoprene are mainly resulted from gasoline evaporation at a particular time (06:00–09:00 in the busy commercial area. The results gained from this study provide useful information for better understanding the characteristics of ambient VOCs and the sources of VOCs in Shanghai.

  7. Time-activity relationships to VOC personal exposure factors

    Science.gov (United States)

    Edwards, Rufus D.; Schweizer, Christian; Llacqua, Vito; Lai, Hak Kan; Jantunen, Matti; Bayer-Oglesby, Lucy; Künzli, Nino

    Social and demographic factors have been found to play a significant role in differences between time-activity patterns of population subgroups. Since time-activity patterns largely influence personal exposure to compounds as individuals move across microenvironments, exposure subgroups within the population may be defined by factors that influence daily activity patterns. Socio-demographic and environmental factors that define time-activity subgroups also define quantifiable differences in VOC personal exposures to different sources and individual compounds in the Expolis study. Significant differences in exposures to traffic-related compounds ethylbenzene, m- and p-xylene and o-xylene were observed in relation to gender, number of children and living alone. Categorization of exposures further indicated time exposed to traffic at work and time in a car as important determinants. Increased exposures to decane, nonane and undecane were observed for males, housewives and self-employed. Categorization of exposures indicated exposure subgroups related to workshop use and living downtown. Higher exposures to 3-carene and α-pinene commonly found in household cleaning products and fragrances were associated with more children, while exposures to traffic compounds ethylbenzene, m- and p-xylene and o-xylene were reduced with more children. Considerable unexplained variation remained in categorization of exposures associated with home product use and fragrances, due to individual behavior and product choice. More targeted data collection methods in VOC exposure studies for these sources should be used. Living alone was associated with decreased exposures to 2-methyl-1-propanol and 1-butanol, and traffic-related compounds. Identification of these subgroups may help to reduce the large amount of unexplained variation in VOC exposure studies. Further they may help in assessing impacts of urban planning that result in changes in behavior of individuals, resulting in shifts in

  8. Temperature-dependent Kinetics on Laser Induced Photolysis of Aqueous CS2-HONO Solutions

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH-HONO. Temperature dependent rate coefficients for the reaction are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 273-313 K (units are L.mol-1.s-1):ln k = (31.6 ± 0.6)-{(4.1 ± 0.2) ×103/T}, and the activation energy in unit of kJ.mol-1 is 32.47with the temperature accuracy 0.2 K.

  9. Studying the activation of epithelial ion channels using global whole-field photolysis.

    Science.gov (United States)

    Almassy, Janos; Yule, David I

    2013-01-01

    The production of saliva by parotid acinar cells is stimulated by Ca(2+) activation of Cl(-) and K(+) channels located in the apical plasma membrane of these polarized cells. Here we provide a detailed description of a flash photolysis experiment designed to give a global and relatively uniform photorelease of inositol 1,4,5-trisphosphate (InsP(3)) or Ca(2+) from caged precursors (NPE-InsP(3) or NP-EGTA) combined with the simultaneous measurement of whole-cell Ca(2+)-activated currents. The photolysis light source can be either an ultraviolet (UV) flash lamp or alternatively the output from a 375-nm diode laser, which is defocused to illuminate the entire field.

  10. Analyzing Ca(2+) dynamics in intact epithelial cells using spatially limited flash photolysis.

    Science.gov (United States)

    Almassy, Janos; Yule, David I

    2013-01-01

    The production of saliva by parotid acinar cells is stimulated by Ca(2+) activation of Cl(-) and K(+) channels located in the apical plasma membrane of these polarized cells. Here we describe a paradigm for the focal photorelease of either Ca(2+) or an inositol 1,4,5 trisphosphate (InsP(3)) analog. The protocol is designed to be useful for investigating subcellular Ca(2+) dynamics in polarized cells with minimal experimental intervention. Parotid acinar cells are loaded with cell-permeable versions of the caged precursors (NP-EGTA-AM or Ci-InsP(3)/PM). Photolysis is accomplished using a spatially limited, focused diode laser, but the experiment can be readily modified to whole-field photolysis using a xenon flash lamp.

  11. Literature survey of the aqueous chemistry of technetium related to photolysis. [115 references

    Energy Technology Data Exchange (ETDEWEB)

    Friedman, H.A.

    1981-07-01

    A literature survey was made to accumulate information about the chemistry of technetium as it relates to photolysis. The electrochemical potentials and the reactions of the various technetium compounds and complexes are discussed, along with the various absorption spectra of the different species. The TcCl/sub 6//sup 2 -/ ion has been shown to be photochemically active in HCl solutions. Hexachlorotechnetate(IV) is oxidized when exposed to sunlight in concentrated HCl. A ligand change occurs when it is exposed to either 254- or 34-nm radiation in more dilute HCl. No other photolysis reactions were found in the literature. It is possible that, under appropriate conditions, other valence states of technetium would be photochemically active, resulting in either redox or ligand exchange reactions. Proposals for investigating the photochemical reduction of the pertechnetate in HNO/sub 3/ and other media are discussed.

  12. Postcolumn photolysis of pesticides for fluorometric determination by high-performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Miles, C.J.; Moye, H.A.

    1988-02-01

    A high-performance liquid chromatography postcolumn reaction detector that employs UV photolysis with an optional reaction by using o-phthalaldehyde-2-mercaptoethanol (OPA-MERC) followed by fluorescence detection was found to be useful for several classes of pesticides. In the presence of the OPA-MERC reagent, most carbamates, carbamoyl oximes, carbamothioic acids, and substituted ureas gave a sensitive response while the response of dithiocarbamates, phenylamides, and phenylcarbamates varied. The response of most of the pesticides tested was significantly affected by the solvent used. Method detection limits for aldicarb sulfoxide, aldicarb, propoxur, thiram, and neburon in ground water were 2.5, 2.3, 3.3, 3.8, and 2.0 ..mu..g/L, respectively. In the absence of OPA-MERC reagent, several of the substituted aromatic compounds also gave strong fluorescence after photolysis. This detector is applicable to a broad range of nitrogenous pesticides.

  13. Non-invasive bleaching of the human lens by femtosecond laser photolysis

    DEFF Research Database (Denmark)

    Kessel, L.; Eskildsen, Lars; Poel, Mike van der

    2010-01-01

    were susceptible to photobleaching by a non-invasive procedure and whether this would lead to optical rejuvenation of the lens. Methodology/Principal Findings: Nine human donor lenses were treated with an 800 nm infra-red femtosecond pulsed laser in a treatment zone measuring 1 x 1 x 0.52 mm. After...... laser treatment the age-induced yellow discoloration of the lens was markedly reduced and the transmission of light was increased corresponding to an optical rejuvenation of 3 to 7 years. Conclusions/Significance: The results demonstrate that the age-induced yellowing of the human lens can be bleached...... by a non-invasive procedure based on femtosecond laser photolysis. Cataract is a disease associated with old age. At the current technological stage, lens aging is delayed but with a treatment covering the entire lens volume complete optical rejuvenation is expected. Thus, femtosecond photolysis has...

  14. Direct observation of ClO from chlorine nitrate photolysis. [as mechanism of polar ozone depletion

    Science.gov (United States)

    Minton, Timothy K.; Nelson, Christine M.; Moore, Teresa A.; Okumura, Mitchio

    1992-01-01

    Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

  15. Dependence of Upper Atmosphere Photochemistry on the Shape of the Diurnal Cycle of the Photolysis Rates

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A photochemical model of the atmosphere constitutes a non-linear, non-autonomous dynamical system, enforced by the Earth's rotation. Some studies have shown that the region of the mesopause tends towards non-linear responses such as period-doubling cascades and chaos. In these studies, simple approximations for the diurnal variations of the photolysis rates are assumed. The goal of this article is to investigate what happens if the more realistic, calculated photolysis rates are introduced. It is found that,if the usual approximations-sinusoidal and step fiunctions-are assumed, the responses of the system are similar: it converges to a 2-day periodic solution. If the more realistic, calculated diurnal cycle is introduced, a new 4-day subharmonic appear.

  16. Photolysis of alpha-azidoacetophenones: direct detection of triplet alkyl nitrenes in solution.

    Science.gov (United States)

    Singh, Pradeep N D; Mandel, Sarah M; Robinson, Rachel M; Zhu, Zhendong; Franz, Roberto; Ault, Bruce S; Gudmundsdóttir, Anna D

    2003-10-17

    We report the first detection of triplet alkyl nitrenes in fluid solution by laser flash photolysis of alpha-azido acetophenone derivatives, 1. Alphazides 1 contain an intramolecular triplet sensitizer, which ensures formation of the triplet alkyl nitrene by bypassing the singlet nitrene intermediate. At room temperature, azides 1 cleave to form benzoyl and methyl azide radicals in competition with triplet energy transfer to form triplet alkyl nitrene. The major photoproduct 3 arises from interception of the triplet alkyl nitrene with benzoyl radicals. The triplet alkyl nitrene intermediates are also trapped with molecular oxygen to yield the corresponding 2-nitrophenylethanone. Laser flash photolysis of 1 reveals that the triplet alkyl nitrenes have absorption around 300 nm. The triplet alkyl nitrenes were further characterized by obtaining their UV and IR spectra in argon matrices. (13)C and (15)N isotope labeling studies allowed us to characterize the C-N stretch of the nitrene intermediate at 1201 cm(-)(1).

  17. Pressure dependent deuterium fractionation in the formation of molecular hydrogen in formaldehyde photolysis

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Andersen, Vibeke Friis; Skov, Henrik;

    2009-01-01

    the channels has been estimated using available values for the absorption 10 cross section and quantum yield. As a result of the change in pressure with altitude the isotope effect for production of molecular hydrogen is found to change from a value of kH/kD=1.8±0.2 at the surface to unity at 50 km....... The relative importance of the two product channels changes with altitude as a result of changes in both pressure and actinic flux. The study concludes that the D of photochemical hydrogen produced in 15 situ will increase substantially with altitude.......The pressure dependence of the relative photolysis rates of HCHO and HCDO has been investigated using a new photochemical reactor at the University of Copenhagen. The relative photolysis rate of HCHO vs. HCDO under UVA lamp irradiation was mea- 5 sured at total pressures of 50, 200, 400, 600...

  18. Low HAP/VOC Compliant Resins for Military Applications

    Science.gov (United States)

    2011-09-01

    on lauric acid FAVE-O fatty acid vinyl ester resin system based on octanoic acid FTIR Fourier transform infrared GIC Mode 1 fracture energy...temperature and could potentially produce smog-promoting ozone as well as long-term and acute health effects. VOC/HAPs are emitted during all phases of...Viscosity ា cP at 25 °C (MOct) Unreacted epoxy FTIR *, NMR* No epoxy present None detected Correct reactant ratios NMR Methacrylate to FA ratio of 1:1

  19. Biodegradation of mixture of VOC's in a biofilter

    Institute of Scientific and Technical Information of China (English)

    D. Arulneyam; T. Swaminathan

    2004-01-01

    Volatile organic compounds(VOC' s) in air have become major concem in recent years. Biodegradation of a mixture of ethanol and methanol vapor was evaluated in a laboratory biofilter with a bed of compost and polystyrene particles using an acclimated mixed culture. The continuous performance of the biofilter was studied with different proportion of ethanol and methanol at different initial concentration and flow rates. The result showed significant removal for both ethanol and methanol, which were composition dependent.The presence of either compound in the mixture inhibited the biodegradation of the other.

  20. DESORPTION OF VOCs FROM POLYMERIC ADSORBENTS UNDER MICROWAVE FIELD

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Desorption of volatile organic compounds (VOCs)from polymeric adsorbents by microwave was investigated experimentally. Two kinds of organic compounds, benzene and toluene,were separately used as adsorbates in this work. Results showed that the application of microwave to regenerate the polymeric adsorbents not only can get higher regeneration efficiency in comparison with the use of heat regeneration, but also make the temperatures of the fixed beds much lower than that when using the heat regeneratton The weaker the polarity of a polymeric adsorbent, the easier its regeneration was.

  1. DESORPTION OF VOCs FROM POLYMERIC ADSORBENTS UNDER MICROWAVE FIELD

    Institute of Scientific and Technical Information of China (English)

    LIXiang; LIZhong; 等

    2001-01-01

    Desorption of volatile organic compounds(VOCs) from polymeric adsorbents by microwave was investigated experimentally.Two kinds of organic compounds.benzene and toluene.were separately used as adsorbates in this work Results showed that the application of microwave to regenerate the polymeric adsorbents not only can get higher regeneration efficiency in comparison with the use of heat regeneration,but also make the temperatures of the fixed beds much lower than that when using the heat regeneration the weaker the polarity of a polymericadsorbent,the easier its regeneration was.

  2. VoCS : Sistema de almacenamiento voluntario en la nube

    OpenAIRE

    Schiavón Raineri, Ignacio Nicolás

    2012-01-01

    La computación en la nube responde a las necesidades del aumento de dispositivos conectados a Internet y el creciente volumen de datos manejados, ofreciendo acceso ubicuo y transparente a la información de forma segura. Esto ha tenido como consecuencia la apertura del mercado, ofreciendo muchas aplicaciones basadas en la nube como SkyDrive, Google Drive o Dropbox. VoCS (Volunteer Cloud Storage) es un sistema de almacenamiento voluntario en la nube de código abierto y seguro, que pretende ofre...

  3. Plant leaves as indoor air passive samplers for volatile organic compounds (VOCs).

    Science.gov (United States)

    Wetzel, Todd A; Doucette, William J

    2015-03-01

    Volatile organic compounds (VOCs) enter indoor environments through internal and external sources. Indoor air concentrations of VOCs vary greatly but are generally higher than outdoors. Plants have been promoted as indoor air purifiers for decades, but reports of their effectiveness differ. However, while air-purifying applications may be questionable, the waxy cuticle coating on leaves may provide a simple, cost-effective approach to sampling indoor air for VOCs. To investigate the potential use of plants as indoor air VOC samplers, a static headspace approach was used to examine the relationship between leaf and air concentrations, leaf lipid contents and octanol-air partition coefficients (Koa) for six VOCs and four plant species. The relationship between leaf and air concentrations was further examined in an actual residence after the introduction of several chlorinated VOC emission sources. Leaf-air concentration factors (LACFs), calculated from linear regressions of the laboratory headspace data, were found to increase as the solvent extractable leaf lipid content and Koa value of the VOC increased. In the studies conducted in the residence, leaf concentrations paralleled the changing air concentrations, indicating a relatively rapid air to leaf VOC exchange. Overall, the data from the laboratory and residential studies illustrate the potential for plant leaves to be used as cost effective, real-time indoor air VOC samplers.

  4. FEV manoeuvre induced changes in breath VOC compositions: an unconventional view on lung function tests

    Science.gov (United States)

    Sukul, Pritam; Schubert, Jochen K.; Oertel, Peter; Kamysek, Svend; Taunk, Khushman; Trefz, Phillip; Miekisch, Wolfram

    2016-06-01

    Breath volatile organic compound (VOC) analysis can open a non-invasive window onto pathological and metabolic processes in the body. Decades of clinical breath-gas analysis have revealed that changes in exhaled VOC concentrations are important rather than disease specific biomarkers. As physiological parameters, such as respiratory rate or cardiac output, have profound effects on exhaled VOCs, here we investigated VOC exhalation under respiratory manoeuvres. Breath VOCs were monitored by means of real-time mass-spectrometry during conventional FEV manoeuvres in 50 healthy humans. Simultaneously, we measured respiratory and hemodynamic parameters noninvasively. Tidal volume and minute ventilation increased by 292 and 171% during the manoeuvre. FEV manoeuvre induced substance specific changes in VOC concentrations. pET-CO2 and alveolar isoprene increased by 6 and 21% during maximum exhalation. Then they decreased by 18 and 37% at forced expiration mirroring cardiac output. Acetone concentrations rose by 4.5% despite increasing minute ventilation. Blood-borne furan and dimethyl-sulphide mimicked isoprene profile. Exogenous acetonitrile, sulphides, and most aliphatic and aromatic VOCs changed minimally. Reliable breath tests must avoid forced breathing. As isoprene exhalations mirrored FEV performances, endogenous VOCs might assure quality of lung function tests. Analysis of exhaled VOC concentrations can provide additional information on physiology of respiration and gas exchange.

  5. VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

    Science.gov (United States)

    Louie, Peter K. K.; Ho, Josephine W. K.; Tsang, Roy C. W.; Blake, Donald R.; Lau, Alexis K. H.; Yu, Jian Zhen; Yuan, Zibing; Wang, Xinming; Shao, Min; Zhong, Liuju

    2013-09-01

    Ambient air measurements of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) were conducted and characterised during a two-year grid study in the Pearl River Delta (PRD) region of southern China. The present grid study pioneered the systematic investigation of the nature and characteristics of complex VOC and OVOC sources at a regional scale. The largest contributing VOCs, accounting over 80% of the total VOCs mixing ratio, were toluene, ethane, ethyne, propane, ethene, butane, benzene, pentane, ethylbenzene, and xylenes. Sub-regional VOC spatial characteristics were identified, namely: i) relatively fresh pollutants, consistent with elevated vehicular and industrial activities, around the PRD estuary; and ii) a concentration gradient with higher mixing ratios of VOCs in the west as compared with the eastern part of PRD. Based on alkyl nitrate aging determination, a high hydroxyl radical (OH) concentration favoured fast hydrocarbon reactions and formation of locally produced ozone. The photochemical reactivity analysis showed aromatic hydrocarbons and alkenes together consisted of around 80% of the ozone formation potential (OFP) among the key VOCs. We also found that the OFP from OVOCs should not be neglected since their OFP contribution was more than one-third of that from VOCs alone. These findings support the choice of current air pollution control policy which focuses on vehicular sources but warrants further controls. Industrial emissions and VOCs emitted by solvents should be the next targets for ground-level ozone abatement.

  6. Low VOC drying of lumber and wood panel products. Progress report No. 5

    Energy Technology Data Exchange (ETDEWEB)

    Wild, P.; Yan, Hui; Banerjee, S. [and others

    1997-10-01

    This progress report summarizes three accomplishments in a study of low volatile organic compound (VOC) drying of lumber and wood panel products. A mathematical model for predicting moisture emissions from particle was constructed and is being extended to VOCs. VOCs emissions from drying boards show that VOCs appear to be evenly released from all surfaces. Preliminary results from monthly analyses of loblolly pines indicate that resin acids appear to decrease between March to August, and that no consistent trends are apparent for terpenes. 3 refs., 13 figs., 1 tab.

  7. Implementation of VOC source reduction practices in a manufactured house and in school classrooms

    Energy Technology Data Exchange (ETDEWEB)

    Hodgson, A.T.; Apte, M.G.; Shendell, D.G.; Beal, D.; McIlvaine, J.E.R.

    2002-01-01

    Detailed studies of a new manufactured house and four new industrialized relocatable school classrooms were conducted to determine the emission sources of formaldehyde and other VOCs and to identify and implement source reduction practices. Procedures were developed to generate VOC emission factors that allowed reasonably accurate predictions of indoor air VOC concentrations. Based on the identified sources of formaldehyde and other aldehydes, practices were developed to reduce the concentrations of these compounds in new house construction. An alternate ceiling panel reduced formaldehyde concentrations in the classrooms. Overall, the classrooms had relatively low VOC concentrations.

  8. Determination of common anions in oxalate by ion chromatography coupled with UV photolysis pretreatment

    Institute of Scientific and Technical Information of China (English)

    Sheng Lin Cao; Ming Li Ye; Wei De Lv; Guang Wen Pan; Ting Ting Zhang; Zhong Yang Hu; Li Na Liang; Yan Zhu

    2012-01-01

    A new and simple method was developed to determine anions in oxalate of analytical reagent grade.After UV photolysis with optimal 1% H2O2 in 10,000 mg/L oxalate in the fabricated photoreactor,sample was directly injected into IC system.Satisfactory linearity,detections limits,good repeatability and spiked recovery were obtained.The method was successfully applied to determine anions in two commercial oxalate samples.

  9. Identification of Products of Merocyanine 540 Decay by Photolysis and Thermolysis

    Science.gov (United States)

    Bazyl', O. K.; Svetlichnyi, V. A.

    2016-08-01

    Possible products of merocyanine 540 decay are studied using quantum-chemical calculations. The results of calculation are compared with experimental investigations of the spectral-luminescent properties, and the products of photo- and thermodecay of the merocyanine 540 molecule in water are identified. It is shown that different products are formed by thermolysis (decay in the ground electronic state S0) and photolysis (decay in an excited electronic state).

  10. Kinetics of the photolysis and OH reaction of 4-hydroxy-4-methyl-2-pentanone: Atmospheric implications

    Science.gov (United States)

    Aslan, L.; Laversin, H.; Coddeville, P.; Fittschen, C.; Roth, E.; Tomas, A.; Chakir, A.

    2017-02-01

    This study provides the first kinetic and mechanistic study of the photolysis of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) and the determination of the temperature dependence of the relative rate coefficient for the reaction of OH radicals with 4H4M2P. The UV absorption spectrum of 4H4M2P was determined in the spectral range 200-360 nm. The photolysis frequency of this compound in the atmosphere was evaluated relative to actinometers and found to be J4 H 4M 2 P atm = 4.2 ×10-3h-1 , corresponding to a lifetime of about 10 days. Using 4H4M2P cross section measurements, an atmospheric effective quantum yield of 0.15 was calculated. The main primary photolysis products were acetone (121 ± 4) % and formaldehyde (20 ± 1) %. A low methanol yield of (3.0 ± 0.3) % was also determined. These results enabled us to propose a mechanistic scheme for the photolysis. Rate coefficients for the reaction of 4H4M2P with OH radicals were determined over the temperature range 298-354 K and the following Arrhenius expression was obtained: kOH+4M4H2P = (1.12 ± 0.40) × 10-12exp(461.5 ± 60/T) cm3 molecule-1 s-1. The lifetimes of 4H4M2P due to reaction with OH radicals has been estimated to ∼2.5 days and indicates that the gas-phase reaction with the OH could be the main loss process for this compound.

  11. The Reaction Kinetics of Neutral Free Radicals and Radical Ions Studied by Laser Flash Photolysis

    OpenAIRE

    Friedline, Robert Alan

    2004-01-01

    t-Butoxyl radical has been used as a chemical model for hydrogen abstractions in many enzymatic and biological systems. However, the question has arisen as to how well this reactive intermediate mimics these systems. In addressing this concern, absolute rate constants and Arrhenius parameters for hydrogen abstraction by t-butoxyl radical were measured for a broad class of substrates including amines, hydrocarbons, and alcohols using laser flash photolysis. Initially, no obvious reactivity ...

  12. Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater.

    Science.gov (United States)

    Xing, Rui; Zheng, Zhongyuan; Wen, Donghui

    2015-03-01

    In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%-35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD5/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%-47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH4+-N), 17% more nitrite nitrogen (NO2--N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO3--N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.

  13. Nanosecond photolysis of rhodopsin: evidence for a new, blue-shifted intermediate.

    Science.gov (United States)

    Hug, S J; Lewis, J W; Einterz, C M; Thorgeirsson, T E; Kliger, D S

    1990-02-13

    Early photolysis intermediates of native bovine rhodopsin (RHO) are investigated by nanosecond laser photolysis near physiological temperature. Absorption difference spectra are collected after excitation with 477-, 532-, and 560-nm laser pulses of various energies and with 477-nm laser excitation at 5, 12, 17, 21, and 32 degrees C. The data are analyzed by using singular-value decomposition (SVD) and a global exponential fitting routine. Two rate constants associated with distinct spectral changes are observed during the time normally associated with the decay of bathorhodopsin to lumirhodopsin. Various models consistent with this observation are considered. A sequential model in which there is a reversible step between a bathorhodopsin intermediate and a new intermediate (BSI), which is blue-shifted relative to lumirhodopsin, is shown to best fit the data. The temperature dependence of the observed and calculated rate constants leads to linear Arrhenius plots. Extrapolation of the temperature dependence suggests that BSI should not be observable after rhodopsin photolysis at temperatures below -100 degrees C. The results are discussed with regard to the artificial visual pigments cis-5,6-dihydroisorhodopsin and 13-demethylrhodopsin. It is proposed that the rate of the BATHO to BSI transition is limited by the relaxation of the strained all-trans-retinal chromophore within a tight protein environment. The transition to LUMI involves chromophore relaxation concurrent with protein relaxation. While the first process is strongly affected by changes in the chromophore, the second transition seems to be determined more by protein relaxation.

  14. Photolysis of pure solid O3 and O2 films at 193 nm

    CERN Document Server

    Raut, U; Famá, M; Baragiola, R A

    2010-01-01

    We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at saturation is 0.03, nearly 10-30 times larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, {\\Phi} (O3) = 0.18 and for destruction of ozone and oxygen in their parent solids, {\\Phi} (- O3) = 1.7 and {\\Phi} (-O2) = 0.28. Combined with known photoabsorption cross sections, we estimate probabilities for germinate recombination of 0.15 for O3 fragments and 0.90 for oxygen atoms from O2 dissociation. Using ...

  15. Vacuum UV photolysis of CO 2. Rare-gas oxide formation in matrices

    Science.gov (United States)

    Fournier, J.; Mohammed, H. H.; Deson, J.; Maillard, D.

    1982-08-01

    In this paper, we report experimental results obtained upon photolysis of CO 2 trapped at low concentrations (0.1%) in neon, argon and krypton matrices. The mixture are photolysed using a xenon resonance lamp emitting photons at 8.4 eV. Only in a neon matrix does the photolysis of CO 2 lead to O( 1D) → O( 3P) emission. Furthermore, oxygen atoms are shown to diffuse at all temperatures in a neon matrix (as detected by molecular oxygen emission), whereas in the other matrices this occurs only when the sample is warmed even though irradiation is performed at high temperature. In argon and krypton matrices, O( 1S) → O( 1D) emission is observed even though there is not enough energy to form an O( 1S) atom in a primary photodecomposition process. This suggests that O( 1D) becomes bound to argon or krypton atoms as a stable rare-gas oxide RGO excimer, which is subsequently excited and photolysed by 8.4 eV photons. These observed features are explained using a model for the interaction between oxygen ( 3P, 1D, 1S) and rare-gas atoms ( 1S) which had previously been proposed to account for the emission spectra of oxygen atoms observed during photolysis of oxygenated compounds.

  16. Photochemistry of insecticide imidacloprid:direct and sensitized photolysis in aqueous medium

    Institute of Scientific and Technical Information of China (English)

    ZHENG Wei; LIU Wei-ping; WEN Yue-zhong; Sang-jin Lee

    2004-01-01

    The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine. were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO2, Cl- and NO3- . Complete photo-oxidation of nitrogen to NO3- occurred very slowly via the intermediate formation of NH4+ and NO2- .

  17. Comparison of the degradations of diphenamid by homogeneous photolysis and heterogeneous photocatalysis in aqueous solution.

    Science.gov (United States)

    Liang, Hai-chao; Li, Xiang-zhong; Yang, Yin-hua; Sze, Kong-hung

    2010-06-01

    In this work, the homogeneous and heterogeneous degradations of diphenamid (DPA) in aqueous solution were conducted by direct photolysis with UVC (254nm) and by photocatalysis with TiO(2)/UVA (350nm), and the experimental results were compared. It was found that the homogeneous photolysis by UVC irradiation alone was quite efficient to degrade DPA up to 100% after 360min, but was very inefficient to mineralize its intermediates in terms of dissolved organic carbon reduction of only 8%. In contrast, the heterogeneous photocatalysis with TiO(2)/UVA showed relatively a lower degree of DPA degradation (51%), but a higher degree of its mineralization (11%) after 360min. These results reveal that the photocatalysis process has relatively poor selectivity to degrade different compounds including various intermediates from the DPA degradation, which is beneficial to its mineralization. In addition, over 20 intermediates were identified by LC-MS and (1)H NMR analyses. Based on the identified intermediates, the reaction mechanisms and the detailed pathways of the DPA degradation by photolysis and photocatalysis were proposed, and are presented in this paper.

  18. Photolysis of flumequine: identification of the major phototransformation products and toxicity measures.

    Science.gov (United States)

    Sirtori, Carla; Zapata, Ana; Gernjak, Wolfgang; Malato, Sixto; Agüera, Ana

    2012-07-01

    Direct photolysis of flumequine (FLU, 20 mg L(-1)) in different types of water (demineralised water (DW) and synthetic seawater (SW)), was conducted in a Suntest CPS+solar simulator to evaluate its persistence and toxicity, and to identify the major phototransformation products (PTPs) generated during photolysis in DW. It was observed that FLU is susceptible to transformation when subjected to direct solar radiation. The composition of the water affects the FLU degradation kinetics, which is slower in SW. Photolytic transformation products generated during direct photolysis were identified by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Fourteen PTPs generated in DW were identified. The transformation of FLU begins with the opening of the heterocyclic ring by oxidation of the double bond. Loss of the fluorine atom and the hydroxylation of the aromatic ring also appear as the majority, especially in the early stages. Comparative acute toxicity evaluation by Vibrio fischeri and Daphnia magna bioassays was performed for the first and last irradiated solutions in both matrices studied. These bioassays demonstrated that in the SW matrix, the most persistent PTPs are highly toxic to D. magna but less so to V. fischeri.

  19. Photolysis of Iron (III) carboxylate complexes relevant for tropospheric aqueous particles and cloud droplets

    Science.gov (United States)

    Herrmann, H.; Weller, C.; Bräuer, P.; Tilgner, A.

    2012-12-01

    Absorption spectra and Fe(II) quantum yields of iron(III) coordination complexes with oxalate, malonate, succinate, glutarate, tartronate, tartrate, gluconate, glyoxalate and pyruvate were experimentally determined. Measured quantum yields of malonate, glutarate and gluconate complexes are in the range of 0.02 tartrate, pyruvate, glyoxylate and tartronate complexes show values between 0.12 tartrate and, surprisingly, in the case of succinate complexes a higher quantum yield was observed at 351 nm under increased oxygen concentrations in solution. In the case of oxalate, a dependence of the quantum yield on the initial concentration of iron(III) oxalato complexes was observed. A kinetic simulation of the reaction system after the photolysis was performed for oxalate, succinate, glyoxalate and tartrate complexes to characterize the influence of secondary thermal reactions on the quantum yield. A tropospheric chemistry simulation with the multiphase chemistry mechanism CAPRAM involving the photolysis of the studied complexes and subsequent reactions of the resulting species shows that the contribution of the iron complex photochemistry to the formation of oxidants such as the hydroperoxyl radical and its anion, the hydroxyl radical and H2O2 is low in comparison to other sources. However, it is shown that Fe(III) complex photolysis represents a major sink for some ligands in addition to the oxidation via free radicals.

  20. Is Amino-Acid Homochirality Due To Asymmetric Photolysis In Space?

    CERN Document Server

    Cerf, C

    1999-01-01

    Amino acids occurring in proteins are, with rare exceptions, exclusively of the L-configuration. Among the many scenarios put forward to explain the origin of this chiral homogeneity (i.e., homochirality), one involves the asymmetric photolysis of amino acids present in space, triggered by circularly polarized UV radiation. The recent observation of circularly polarized light (CPL) in the Orion OMC-1 star-forming region (Bailey et al. 1998, Science 281, 672) has been presented as providing a strong validation of this scenario. The present paper reviews the situation. It is stressed for example that one important condition for the asymmetric photolysis by CPL to be at the origin of the terrestrial homochirality of natural amino acids is generally overlooked, namely, the asymmetric photolysis should favour the L-enantiomer for ALL the primordial amino acids involved in the genesis of life (i.e., biogenic amino acids). Although this condition is probably satisfied for aliphatic amino acids, some non-aliphatic am...

  1. [Nitric oxide and lipid peroxidation].

    Science.gov (United States)

    Cristol, J P; Maggi, M F; Guérin, M C; Torreilles, J; Descomps, B

    1995-01-01

    Nitric oxide (NO) is a free radical produced enzymatically in biological systems from the guanidino group of L-arginine. Its large spectrum of biological effects is achieved through chemical interactions with different targets including oxygen (O2), superoxide (O2o-) and other oxygen reactive species (ROS), transition metals and thiols. Superoxide anions and other ROS have been reported to react with NO to produce peroxynitrite anions that can decompose to form nitrogen dioxide (NO2) and hydroxyl radial (OHo). Thus, NO has been reported to have a dual effect on lipid peroxidation (prooxidant via the peroxynitrite or antioxydant via the chelation of ROS). In the present study we have investigated in different models the in vitro and in vivo action of NO on lipid peroxidation. Copper-induced LDL oxidation were used as an in vitro model. Human LDL (100 micrograms ApoB/ml) were incubated in oxygene-saturated PBS buffer in presence or absence of Cu2+ (2.5 microM) with increasing concentrations of NO donnors (sodium nitroprussiate or nitroso-glutathione). LDL oxidation was monitored continuously for conjugated diene formation (234 nm) and 4-hydroxynonenal (HNE) accumulation. Exogenous NO prevents in a dose dependent manner the progress of copper-induced oxidation. Ischaemia-reperfusion injury (I/R), characterized by an overproduction of ROS, is used as an in vivo model. Anaesthetized rats were submitted to 1 hour renal ischaemia following by 2 hours of reperfusion. Sham-operated rats (SOP) were used as control. Lipid peroxidation was evaluated by measuring the HNE accumulated in rats kidneys in presence or absence of L-arginine or D-arginine infusion. L-arginine, but not D-arginine, enhances HNE accumulation in I/R but not in SOP (< 0.050 pmol/g tissue in SOP versus 0.6 nmol/g tissue in I/R), showing that, in this experimental conditions, NO produced from L-arginine, enhances the toxicity of ROS. This study shows that the pro- or antioxydant effects of NO are different

  2. Gaseous VOCs rapidly modify particulate matter and its biological effects - Part 2: Complex urban VOCs and model PM

    Science.gov (United States)

    Ebersviller, S.; Lichtveld, K.; Sexton, K. G.; Zavala, J.; Lin, Y.-H.; Jaspers, I.; Jeffries, H. E.

    2012-12-01

    This is the second study in a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOCs), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber, both in the dark and in sunlight. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model living receptors. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. Our exposure systems permit side-by-side, gas-only- and PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure for either gases or PM. In Part 1 (Ebersviller et al., 2012a), we demonstrated the existence of PM "effect modification" (NAS, 2004) for the case of a single gas-phase toxicant and an inherently non-toxic PM (mineral oil aerosol, MOA). That is, in the presence of the single gas-phase toxicant in the dark, the initially non-toxic PM became toxic to lung cells in the PM-only-biological exposure system. In this Part 2 study, we used sunlit-reactive systems to create a large variety of gas-phase toxicants from a complex mixture of oxides of nitrogen and 54 VOCs representative of those measured in US city air. In these mostly day-long experiments, we have designated the period in the dark just after injection (but before sunrise) as the "Fresh" condition and the period in the dark after sunset as the "Aged" condition. These two conditions were used to expose cells and to collect chemical characterization samples. We used the same inherently non-toxic PM from the Part 1 study as the target PM for "effect

  3. Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 2: Complex urban VOCs and model PM

    Directory of Open Access Journals (Sweden)

    S. Ebersviller

    2012-03-01

    Full Text Available This is the second study in a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOCs, particulate matter (PM, and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber, both in the dark and in sunlight. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model living receptors. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects from cells exposed to chamber air relative to cells exposed to clean air. Our exposure systems permit side-by-side, gas-only- and PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure for either gases or PM.

    In Part 1 (Ebersviller et al., 2012a, we demonstrated the existence of PM "effect modification" (NAS, 2004 for the case of a single gas-phase toxicant and an inherently non-toxic PM (mineral oil aerosol, MOA. That is, in the presence of the single gas-phase toxicant in the dark, the initially non-toxic PM became toxic to lung cells in the PM-only-biological exposure system. In this Part 2 study, we used sunlit-reactive systems to create a large variety of gas-phase toxicants from a complex mixture of oxides of nitrogen and 54 VOCs representative of those measured in US city air. In these mostly day-long experiments, we have designated the period in the dark just after injection (but before sunrise as the "Fresh" condition and the period in the dark after sunset as the "Aged" condition. These two conditions were used to expose cells and to collect chemical characterization samples. We used the same inherently non-toxic PM from the Part 1 study as the

  4. Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 2: Complex urban VOCs and model PM

    Directory of Open Access Journals (Sweden)

    H. E. Jeffries

    2012-12-01

    Full Text Available This is the second study in a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOCs, particulate matter (PM, and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber, both in the dark and in sunlight. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model living receptors. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects from cells exposed to chamber air relative to cells exposed to clean air. Our exposure systems permit side-by-side, gas-only- and PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure for either gases or PM. In Part 1 (Ebersviller et al., 2012a, we demonstrated the existence of PM "effect modification" (NAS, 2004 for the case of a single gas-phase toxicant and an inherently non-toxic PM (mineral oil aerosol, MOA. That is, in the presence of the single gas-phase toxicant in the dark, the initially non-toxic PM became toxic to lung cells in the PM-only-biological exposure system. In this Part 2 study, we used sunlit-reactive systems to create a large variety of gas-phase toxicants from a complex mixture of oxides of nitrogen and 54 VOCs representative of those measured in US city air. In these mostly day-long experiments, we have designated the period in the dark just after injection (but before sunrise as the "Fresh" condition and the period in the dark after sunset as the "Aged" condition. These two conditions were used to expose cells and to collect chemical characterization samples. We used the same inherently non-toxic PM from the Part 1 study as the target PM

  5. 7 CFR 58.431 - Hydrogen peroxide.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Hydrogen peroxide. 58.431 Section 58.431 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards... Material § 58.431 Hydrogen peroxide. The solution shall comply with the specification of the...

  6. [Advances in peroxide-based decontaminating technologies].

    Science.gov (United States)

    Xi, Hai-ling; Zhao, San-ping; Zhou, Wen

    2013-05-01

    With the boosting demand for eco-friendly decontaminants, great achievements in peroxide-based decontaminating technologies have been made in recent years. These technologies have been applied in countering chemical/biological terrorist attacks, dealing with chemical/biological disasters and destructing environmental pollutants. Recent research advances in alpha-nucleophilic/oxidative reaction mechanisms of peroxide-based decontamination against chemical warfare agents were reviewed, and some classical peroxide-based decontaminants such as aqueous decontaminating solution, decontaminating foam, decontaminating emulsions, decontaminating gels, decontaminating vapors, and some newly developed decontaminating media (e.g., peroxide-based self-decontaminating materials and heterogeneous nano-catalytic decontamination systems) were introduced. However, currently available peroxide-based decontaminants still have some deficiencies. For example, their decontamination efficiencies are not as high as those of chlorine-containing decontaminants, and some peroxide-based decontaminants show relatively poor effect against certain agents. More study on the mechanisms of peroxide-based decontaminants and the interfacial interactions in heterogeneous decontamination media is suggested. New catalysts, multifunctional surfactants, self-decontaminating materials and corrosion preventing technologies should be developed before peroxide-based decontaminants really become true "green" decontaminants.

  7. Alcohol induced alterations to the human fecal VOC metabolome.

    Directory of Open Access Journals (Sweden)

    Robin D Couch

    Full Text Available Studies have shown that excessive alcohol consumption impacts the intestinal microbiota composition, causing disruption of homeostasis (dysbiosis. However, this observed change is not indicative of the dysbiotic intestinal microbiota function that could result in the production of injurious and toxic products. Thus, knowledge of the effects of alcohol on the intestinal microbiota function and their metabolites is warranted, in order to better understand the role of the intestinal microbiota in alcohol associated organ failure. Here, we report the results of a differential metabolomic analysis comparing volatile organic compounds (VOC detected in the stool of alcoholics and non-alcoholic healthy controls. We performed the analysis with fecal samples collected after passage as well as with samples collected directly from the sigmoid lumen. Regardless of the approach to fecal collection, we found a stool VOC metabolomic signature in alcoholics that is different from healthy controls. The most notable metabolite alterations in the alcoholic samples include: (1 an elevation in the oxidative stress biomarker tetradecane; (2 a decrease in five fatty alcohols with anti-oxidant property; (3 a decrease in the short chain fatty acids propionate and isobutyrate, important in maintaining intestinal epithelial cell health and barrier integrity; (4 a decrease in alcohol consumption natural suppressant caryophyllene; (5 a decrease in natural product and hepatic steatosis attenuator camphene; and (6 decreased dimethyl disulfide and dimethyl trisulfide, microbial products of decomposition. Our results showed that intestinal microbiota function is altered in alcoholics which might promote alcohol associated pathologies.

  8. Oxygenated VOC and monoterpene emissions from a boreal coniferous forest

    Science.gov (United States)

    Taipale, R.; Rantala, P.; Kajos, M. K.; Patokoski, J.; Ruuskanen, T. M.; Aalto, J.; Kolari, P.; Bäck, J.; Hari, P.; Kulmala, M.; Rinne, J.

    2012-04-01

    Compared with terpenoids, emissions of oxygenated volatile organic compounds (VOCs) from boreal ecosystems have been poorly characterized. We measured ecosystem scale emissions of three oxygenated compounds (methanol, acetaldehyde, and acetone) and monoterpenes from a Scots pine dominated forest in southern Finland during the summers 2006-2008. The measurements were conducted using the disjunct eddy covariance method combined with proton transfer reaction mass spectrometry. The contribution of the three oxygenated compounds to the measured total emissions was 40-60 %. The highest oxygenated VOC emissions were those of methanol, comprising 20-30 % of the total, followed by acetone with a share of 10-20 %. The acetaldehyde emissions were 5-10 % of the total. This emission composition will be compared with that obtained from shoot enclosure measurements. Methanol showed deposition during some periods although its overall flux was towards the atmosphere. The monoterpene emissions had a light dependent component, suggesting that part of the emissions originated directly from monoterpene biosynthesis. Diurnal, seasonal, and inter-annual variations in the emissions, along with temperature and light dependencies, will be discussed.

  9. O sistema vocálico alemão

    Directory of Open Access Journals (Sweden)

    Carine Haupt

    2007-11-01

    Full Text Available 0 presente trabalho explica, de forma simplificada, o sistema vocálico alemão através dos traços de duração, abertura e recuo. Na discussão sobre o assunto, é feita uma abordagem sobre a relação de dependência entre a duração e os traços de abertura, além de discutir a relevância de manter a duração em todo o sistema. Através do modelo de Fonologia Autossegmental, é possível verificar que a estrutura silábica das vogais longas e breves é diferente, além de verificar em que contextos silábicos elas podem ocorrer (especificamente em posição tônica. Já em posição átona, ocorre o schwa, uma variante da vogal lei, que fará parte do sistema vocálico alemão, constituído, então, de 15 vogais em posição tônica e uma variante átona.

  10. Simple, field portable colorimetric detection device for organic peroxides and hydrogen peroxide

    Science.gov (United States)

    Pagoria, Philip F.; Mitchell, Alexander R.; Whipple, Richard E.; Carman, M. Leslie; Reynolds, John G.; Nunes, Peter; Shields, Sharon J.

    2010-11-09

    A simple and effective system for the colorimetric determination of organic peroxides and hydrogen peroxide. A peroxide pen utilizing a swipe material attached to a polyethylene tube contains two crushable vials. The two crushable vials contain a colorimetric reagent separated into dry ingredients and liquid ingredients. After swiping a suspected substance or surface the vials are broken, the reagent is mixed thoroughly and the reagent is allowed to wick into the swipe material. The presence of organic peroxides or hydrogen peroxide is confirmed by a deep blue color.

  11. Development of biogenic VOC emission inventories for the boreal forest

    Energy Technology Data Exchange (ETDEWEB)

    Tarvainen, V.

    2008-07-01

    The volatile organic compounds (VOCs) emitted by vegetation, especially forests, can affect local and regional atmospheric photochemistry through their reactions with atmospheric oxidants. Their reaction products may also participate in the formation and growth of new particles which affect the radiation balance of the atmosphere, and thus climate, by scattering and absorbing shortwave and longwave radiation and by modifying the radiative properties, amount and lifetime of clouds. Globally, anthropogenic VOC emissions are far surpassed by the biogenic ones, making biogenic emission inventories an integral element in the development of efficient air quality and climate strategies. The inventories are typically constructed based on landcover information, measured emissions of different plants or vegetation types, and empirical dependencies of the emissions on environmental variables such as temperature and light. This thesis is focused on the VOC emissions from the boreal forest, the largest terrestrial biome with characteristic vegetation patterns and strong seasonality. The isoprene, monoterpene and sesquiterpene emissions of the most prevalent boreal tree species in Finland, Scots pine, have been measured and their seasonal variation and dependence on temperature and light have been studied. The measured emission data and other available observations of the emissions of the principal boreal trees have been used in a biogenic emission model developed for the boreal forests in Finland. The model utilizes satellite landcover information, Finnish forest classification and hourly meteorological data to calculate isoprene, monoterpene, sesquiterpene and other VOC emissions over the growing season. The principal compounds emitted by Scots pine are DELTA3-carene and alpha-pinene in the south boreal zone and alpha- and beta-pinene in the north boreal zone. The monoterpene emissions are dependent on temperature and have a clear seasonal cycle with high emissions in spring

  12. Vapor Hydrogen Peroxide Sterilization Certification

    Science.gov (United States)

    Chen, Fei; Chung, Shirley; Barengoltz, Jack

    For interplanetary missions landing on a planet of potential biological interest, United States NASA planetary protection currently requires that the flight system must be assembled, tested and ultimately launched with the intent of minimizing the bioload taken to and deposited on the planet. Currently the only NASA approved microbial reduction method is dry heat sterilization process. However, with utilization of such elements as highly sophisticated electronics and sensors in modern spacecraft, this process presents significant materials challenges and is thus an undesirable bioburden reduction method to design engineers. The objective of this work is to introduce vapor hydrogen peroxide (VHP) as an alternative to dry heat microbial reduction to meet planetary protection requirements. The VHP sterilization technology is widely used by the medical industry, but high doses of VHP may degrade the performance of flight hardware, or compromise material compatibility. The goal of our study is determine the minimum VHP process conditions for PP acceptable microbial reduction levels. A series of experiments were conducted using Geobacillus stearothermophilus to determine VHP process parameters that provided significant reductions in spore viability while allowing survival of sufficient spores for statistically significant enumeration. In addition to the obvious process parameters -hydrogen peroxide concentration, number of pulses, and exposure duration -the investigation also considered the possible effect of environmental pa-rameters. Temperature, relative humidity, and material substrate effects on lethality were also studied. Based on the results, a most conservative D value was recommended. This recom-mended D value was also validated using VHP "hardy" strains that were isolated from clean-rooms and environmental populations collected from spacecraft relevant areas. The efficiency of VHP at ambient condition as well as VHP material compatibility will also be

  13. Rearrangements of organic peroxides and related processes

    Science.gov (United States)

    Yaremenko, Ivan A; Vil’, Vera A; Demchuk, Dmitry V

    2016-01-01

    Summary This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately. PMID:27559418

  14. Inorganic precursor peroxides for antifouling coatings

    DEFF Research Database (Denmark)

    Olsen, S.M.; Pedersen, L.T.; Hermann, M.H.

    2009-01-01

    Modern antifouling coatings are generally based on cuprous oxide (Cu2O) and organic biocides as active ingredients. Cu2O is prone to bioaccumulation, and should therefore be replaced by more environmentally benign compounds when technically possible. However, cuprous oxide does not only provide...... antifouling properties, it is also a vital ingredient for the antifouling coating to obtain its polishing and leaching mechanism. In this paper, peroxides of strontium, calcium, magnesium, and zinc are tested as pigments in antifouling coatings. The peroxides react with seawater to create hydrogen peroxide...... and highly seawater-soluble ions of the metal. The goals have been to establish the antifouling potency of an antifouling coating that releases hydrogen peroxide as biocide, and to investigate the potential use of peroxides as water-soluble polishing and leaching pigments. The investigations have shown...

  15. Rearrangements of organic peroxides and related processes.

    Science.gov (United States)

    Yaremenko, Ivan A; Vil', Vera A; Demchuk, Dmitry V; Terent'ev, Alexander O

    2016-01-01

    This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O-O-bond cleavage. Detailed information about the Baeyer-Villiger, Criegee, Hock, Kornblum-DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

  16. MEASUREMENT AND MODELING OF THE DRY DEPOSITION OF PEROXIDES

    Science.gov (United States)

    Measurements of the dry deposition velocity (Vd) of hydrogen peroxide (H2O2) and total organic peroxides (ROOH) were made during four experiments at three forested sites. Details and uncertainties associated with the measurement of peroxide...

  17. A MCM modeling study of the effects of nitryl chloride on oxidant budgets, ozone production, VOC lifetimes, and halogen recycling in polluted regions

    Science.gov (United States)

    Riedel, T. P.; Thornton, J. A.; Wolfe, G. M.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Bon, D.; Vlasenko, A. L.; Li, S.; Williams, E. J.; Lerner, B. M.; Veres, P. R.; Roberts, J. M.

    2012-12-01

    Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing particles. Nitryl chloride is photolyzed during the day to liberate highly reactive chlorine atoms. This chemistry takes place primarily in urban environments where the concentrations of N2O5 precursors (NOx and ozone) are high, though it can likely occur in remote regions at lower intensity. Recent field measurements have illustrated the potential importance of ClNO2 as a chlorine atom source and a NOx reservoir. However, the fate of these chlorine atoms and the overall impact of ClNO2 remain unclear. To this end we have incorporated ClNO2 production, photolysis, and subsequent Cl-atom reactions into an existing Master Chemical Mechanism (MCM version 3.2) based model framework. Cl-atom reactions with alkenes and alcohols not presently part of the MCM have also been added. Using observational constraints from the CalNex 2010 field study, we assess the dominant reactive sinks and sources of chlorine atoms over the course of a model day. Relative to model runs excluding ClNO2 formation, the presence of ClNO2 produces marked changes on a variety of species important to tropospheric chemistry and air quality (e.g. O3, RO2, OH, HO2, ClOx). For example a 50% yield of ClNO2 (max ClNO2 of 1.5 ppb) from nighttime N2O5 reactions leads to a ~10% enhancement in integrated ozone production. VOC and NOx lifetimes are shorter due primarily to enhanced OH from propagation of RO2 produced by Cl-atom chemistry under high NOx. The impact of ClNO2 on daytime halogen atom recycling is substantial, with order of magnitude higher daytime Cl2 production predicted with ClNO2 chemistry than without. In fact, incorporation of ClNO2 could help explain daytime levels of Cl2 observed in polluted coastal regions. Additionally, we highlight a set of chlorinated VOC oxidation products that are predicted to form at small, but potentially detectable levels in regions with similar VOC

  18. 40 CFR 60.502 - Standard for Volatile Organic Compound (VOC) emissions from bulk gasoline terminals.

    Science.gov (United States)

    2010-07-01

    ... (VOC) emissions from bulk gasoline terminals. 60.502 Section 60.502 Protection of Environment... SOURCES Standards of Performance for Bulk Gasoline Terminals § 60.502 Standard for Volatile Organic Compound (VOC) emissions from bulk gasoline terminals. On and after the date on which § 60.8(a) requires a...

  19. 40 CFR 60.312 - Standard for volatile organic compounds (VOC).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for volatile organic compounds (VOC). 60.312 Section 60.312 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Surface Coating of Metal Furniture § 60.312 Standard for volatile organic compounds (VOC). (a) On...

  20. Evaluation of the Snap Sampler for Sampling Ground Water Monitoring Wells for VOCs and Explosives

    Science.gov (United States)

    2007-08-01

    23 Table 4. Results from the holding- time study with...the opposite order. First Holding- Time Study for VOCs The purpose of this study was to determine whether analyte concentra- tions of samples... Study for VOCs The procedure for this study was the same as for the previous holding- time study except that that the Snap Samplers were equilibrated

  1. POLLUTION PREVENTION CASE STUDIES: LOW-VOC/HAP WOOD FURNITURE COATINGS

    Science.gov (United States)

    This article provides a brief profile of the wood furniture industry, discusses pollution prevention activities typically implemented, describes the four low-VOC/HAP coating technologies studied. and summarizes one case study for each of the low-VOC/HAP coating yechnologies inves...

  2. Removal of dissolved VOCs from water with an air stripper/membrane vapor separation system

    NARCIS (Netherlands)

    Wijmans, J.G.; Kamaruddin, H.D.; Segelke, S.V.; Wessling, Matthias; Baker, R.W.

    1997-01-01

    Treatment of water contaminated with volatile organic compounds (VOCs) is a major problem for the United States chemical industry. Currently, VOCs are removed from moderately contaminated wastewater streams by processes such as steam stripping and from dilute wastewaters by air stripping combined wi

  3. Low VOC drying of lumber and wood panel products. Progress report No. 4, annual summary

    Energy Technology Data Exchange (ETDEWEB)

    Boerner, J.; Su, Wei; Yan, Hui [and others

    1997-07-01

    Heating softwood in a low-headspace environment draws out the VOCs from the wood, without removing the water. The VOCs can be collected from the headspace, and represent a valuable product. The VOC-depleted wood can then be dried conventionally with much reduced emissions. Heating can be accomplished through radiofrequency (RF) or steam. For lumber, steam is inefficient, but brief RF treatment under low-headspace conditions draws out 80% of the VOCs. The power used is quite low, since the RF energy is not used to remove water, but only to maintain the wood at a set temperature. The technology is now at the pre-pilot stage. Either steam or RF can be used for particle, OSB, and veneer, again under low-headspace conditions. Increasing steam temperature facilitates VOC removal. In order to understand the mechanism of VOC release in lumber, the transport of water and VOCs to the surface is being studied as a function of sample size and orientation. Characterization of the terpenes and resin/fatty acids from a control set of trees is underway in order to define the seasonal influence on VOCs.

  4. Smartphone-based sensing system using ZnO and graphene modified electrodes for VOCs detection.

    Science.gov (United States)

    Liu, Lei; Zhang, Diming; Zhang, Qian; Chen, Xing; Xu, Gang; Lu, Yanli; Liu, Qingjun

    2017-07-15

    Volatile organic compounds (VOCs) detection is in high demand for clinic treatment, environment monitoring, and food quality control. Especially, VOCs from human exhaled breath can serve as significant biomarkers of some diseases, such as lung cancer and diabetes. In this study, a smartphone-based sensing system was developed for real-time VOCs monitoring using alternative current (AC) impedance measurement. The interdigital electrodes modified with zinc oxide (ZnO), graphene, and nitrocellulose were used as sensors to produce impedance responses to VOCs. The responses could be detected by a hand-held device, sent out to a smartphone by Bluetooth, and reported with concentration on an android program of the smartphone. The smartphone-based system was demonstrated to detect acetone at concentrations as low as 1.56ppm, while AC impedance spectroscopy was used to distinguish acetone from other VOCs. Finally, measurements of the exhalations from human being were carried out to obtain the concentration of acetone in exhaled breath before and after exercise. The results proved that the smartphone-based system could be applied on the detection of VOCs in real settings for healthcare diagnosis. Thus, the smartphone-based system for VOCs detection provided a convenient, portable and efficient approach to monitor VOCs in exhaled breath and possibly allowed for early diagnosis of some diseases. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Total OH reactivity study from VOC photochemical oxidation in the SAPHIR chamber

    Science.gov (United States)

    Yu, Z.; Tillmann, R.; Hohaus, T.; Fuchs, H.; Novelli, A.; Wegener, R.; Kaminski, M.; Schmitt, S. H.; Wahner, A.; Kiendler-Scharr, A.

    2015-12-01

    It is well known that hydroxyl radicals (OH) act as a dominant reactive species in the degradation of VOCs in the atmosphere. In recent field studies, directly measured total OH reactivity often showed poor agreement with OH reactivity calculated from VOC measurements (e.g. Nölscher et al., 2013; Lu et al., 2012a). This "missing OH reactivity" is attributed to unaccounted biogenic VOC emissions and/or oxidation products. The comparison of total OH reactivity being directly measured and calculated from single component measurements of VOCs and their oxidation products gives us a further understanding on the source of unmeasured reactive species in the atmosphere. This allows also the determination of the magnitude of the contribution of primary VOC emissions and their oxidation products to the missing OH reactivity. A series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, to explore in detail the photochemical degradation of VOCs (isoprene, ß-pinene, limonene, and D6-benzene) by OH. The total OH reactivity was determined from the measurement of VOCs and their oxidation products by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS) with a GC/MS/FID system, and directly measured by a laser-induced fluorescence (LIF) at the same time. The comparison between these two total OH reactivity measurements showed an increase of missing OH reactivity in the presence of oxidation products of VOCs, indicating a strong contribution to missing OH reactivity from uncharacterized oxidation products.

  6. Lipid peroxides level in the Indonesian elderly

    Directory of Open Access Journals (Sweden)

    Purwantyastuti Purwantyastuti

    2005-06-01

    Full Text Available A cross-sectional study was done to see the possible association of plasma lipid peroxides in the elderly with age and other factors. Plasma lipid peroxides is a product of free radical reactions which according to the latest theory of aging is the cause of aging process. Lipid peroxides were also found high in coronary heart disease. Four hundred forty relatively healthy elderly, age 55-85 years, were randomly chosen from free living elderly under guidance of health care centers (PUSKESMAS in Jakarta. Anamnesis and physical examination were done in the morning in the health centers. Blood samples were taken in fasting conditions, plasma lipids and lipid peroxides were measured according to standard methods. There was an age difference of lipid peroxides level in the elderly, which increased with age up to 70 years old. Elderly 70 years old and over had low plasma lipid peroxides. The level was not related to high plasma lipids. Higher level was found when more chronic degenerative diseases were found. (Med J Indones 2005; 14: 71-7Keywords: lipid peroxides, aging

  7. Concentrations and flux measurements of volatile organic compounds (VOC) in boreal forest soil

    Science.gov (United States)

    Mäki, Mari; Aaltonen, Hermanni; Heinonsalo, Jussi; Hellén, Heidi; Pumpanen, Jukka; Bäck, Jaana

    2017-04-01

    Volatile organic compounds (VOC) impact soil processes as VOCs transmit signals between roots and rhizosphere (Ditengou et al., 2015), VOCs can regulate microbial activity (Asensio et al., 2012), and VOCs can also promote root growth (Hung et al., 2012). Belowground concentrations of VOCs have not been measured in situ and for this reason, knowledge of how different soil organisms such as roots, rhizosphere and decomposers contribute to VOC production is limited. The aim of this study was to determine and quantify VOC fluxes and concentrations of different horizons from boreal forest soil. The VOC concentrations and fluxes were measured from Scots pine (Pinus sylvestris) forest soil at the SMEAR II station in southern Finland from 21th of April to 2nd of December in 2016. VOC fluxes were measured using dynamic (flow-through) chambers from five soil collars placed on five different locations. VOC concentrations were also measured in each location from four different soil horizons with the measurement depth 1-107 cm. VOCs were collected from underground gas collectors into the Tenax-Carbopack-B adsorbent tubes using portable pumps ( 100 ml min-1). The VOC concentrations and fluxes of isoprene, 11 monoterpenes, 13 sesquiterpenes and different oxygenated VOCs were measured. Sample tubes were analyzed using thermal desorption-gas chromatograph-mass spectrometry (TD-GC-MS). Soil temperature and soil water content were continuously monitored for each soil horizon. Our preliminary results show that the primary source of VOCs is organic soil layer and the contribution of mineral soil to the VOC formation is minor. VOC fluxes and concentrations were dominated by monoterpenes such as α-pinene, camphene, β-pinene, and Δ3-carene. Monoterpene concentration is almost 10-fold in organic soil compared to the deeper soil layers. However, the highest VOC fluxes on the soil surface were measured in October, whereas the monoterpene concentrations in organic soil were highest in July

  8. Efficient control of odors and VOC emissions via activated carbon technology.

    Science.gov (United States)

    Mohamed, Farhana; Kim, James; Huang, Ruey; Nu, Huong Ton; Lorenzo, Vlad

    2014-07-01

    This research study was undertaken to enhance the efficiency and economy of carbon scrubbers in controlling odors and volatile organic compounds (VOCs) at the wastewater collection and treatment facilities of the Bureau of Sanitation, City of Los Angeles. The butane activity and hydrogen sulfide breakthrough capacity of activated carbon were assessed. Air streams were measured for odorous gases and VOCs and removal efficiency (RE) determined. Carbon towers showed average to excellent removal of odorous compounds, VOCs, and siloxanes; whereas, wet scrubbers demonstrated good removal of odorous compounds but low to negative removal of VOCs. It was observed that the relative humidity and empty bed contact time are one of the most important operating parameters of carbon towers impacting the pollutant RE. Regular monitoring of activated carbon and VOCs has resulted in useful information on carbon change-out frequency, packing recommendations, and means to improve performance of carbon towers.

  9. Non-labeling multiplex surface enhanced Raman scattering (SERS) detection of volatile organic compounds (VOCs)

    DEFF Research Database (Denmark)

    Wong, Chi Lok; Dinish, U. S.; Schmidt, Michael Stenbæk

    2014-01-01

    In this paper, we report multiplex SERS based VOCs detection with a leaning nano-pillar substrate. The VOCs analyte molecules adsorbed at the tips of the nano-pillars produced SERS signal due to the field enhancement occurring at the localized surface plasmon hot spots between adjacent leaning nano...... chemical sensing layer for the enrichment of gas molecules on sensor surface. The leaning nano-pillar substrate also showed highly reproducible SERS signal in cyclic VOCs detection, which can reduce the detection cost in practical applications. Further, multiplex SERS detection on different combination...... of acetone and ethanol vapor was also successfully demonstrated. The vibrational fingerprints of molecular structures provide specific Raman peaks for different VOCs contents. To the best of our knowledge, this is the first multiplex VOCs detection using SERS. We believe that this work may lead to a portable...

  10. Pollution characteristic of VOCs of ambient air in winter and spring in Shijiazhuang City

    Directory of Open Access Journals (Sweden)

    Qing CHANG

    2015-06-01

    Full Text Available In order to further explore the pollution characteristics of volatile organic compounds in ambient air in winter and spring in Shijiazhuang City, the pollution characteristics of 62 volatile organic compounds (VOCs, monthly and quarterly variation, the correlation between VOCs and PM2.5, and the main sources of VOCs are investigated by using EPA TO-15 method. It shows that 40 organic compounds of the 64 VOCs have been quantitatively determined in winter and spring in the city, which are mainly acetone, benzene, carbon tetrachloride, dichloromethane, toluene, ethyl acetate, etc.. In the no-quantitatively determined components, higher ethanol, butyl acetate, butane etc. are detected. The VOCs concentration has positive correlation with the PM2.5 concentration during haze days.

  11. Titanium corrosion in alkaline hydrogen peroxide environments

    Science.gov (United States)

    Been, Jantje

    1998-12-01

    The corrosion of Grade 2 titanium in alkaline hydrogen peroxide environments has been studied by weight loss corrosion tests, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) measurements and potentiodynamic polarography. Calcium ions and wood pulp were investigated as corrosion inhibitors. In alkaline peroxide, the titanium corrosion rate increased with increasing pH, temperature, and hydrogen peroxide concentration. The corrosion controlling mechanism is thought to be the reaction of the oxide with the perhydroxyl ion. No evidence of thermodynamically stable calcium titanate was found in the surface film of test coupons exposed to calcium-inhibited alkaline peroxide solutions. Calcium inhibition is probably the result of low local alkali and peroxide concentrations at the metal surface produced by reaction of adsorbed calcium with hydrogen peroxide. It has been shown that the inhibiting effect of calcium is temporary, possibly through an effect of calcium on the chemical and/or physical stability of the surface oxide. Pulp is an effective and stable corrosion inhibitor. Raising the pulp concentration decreased the corrosion rate. The inhibiting effect of pulp may be related to the adsorption and interaction of the pulp fibers with H 2O2, thereby decreasing the peroxide concentration and rendering the solution less corrosive. The presence of both pulp and calcium led to higher corrosion rates than obtained by either one inhibitor alone. Replacement of hydrofluoric acid with alkaline peroxide for pickling of titanium was investigated. Titanium corrosion rates in alkaline peroxide exceeded those obtained in the conventional hydrofluoric acid bath. General corrosion was observed with extensive roughening of the surface giving a dull gray appearance. Preferred dissolution of certain crystallographic planes was investigated through the corrosion of a titanium single crystal. Whereas the overall effect on the corrosion rate was small

  12. Anthropogenic VOC speciation in emission inventories: a method for improvement and evaluation

    Science.gov (United States)

    von Schneidemesser, E.; D'angiola, A.; Granier, C.; Monks, P. S.; Law, K.

    2011-12-01

    Volatile organic compounds (VOCs) are important precursor compounds for the formation of ozone and other secondary organic aerosols. Anthropogenic sources of VOCs are dominated by industrial usage and transportation sources, the latter being extremely important in urban areas. Megacities and large urban conglomerations are emission hot spots that exert disproportionately large adverse health effects on the population and surrounding environment, owing to their high population density and concentrated emission sources. Exceedances of ozone air quality standards are a problem in many urban areas. Improvements in the modelling of ozone precursors would benefit our understanding of the impact of changes in emissions and the effect of future legislation on air quality. As many VOCs are extremely reactive in the atmosphere and have high ozone forming potential, improved speciation of VOCs in models could lead to better predictions of ozone levels and secondary organic aerosol formation. Previously, VOC and carbon monoxide (CO) data from urban areas around the world were compared. Significant differences in VOC concentrations were observed, however, when normalized to CO, the VOC-CO ratios were similar for many locations and over time, even as emission reductions were implemented. The largest variation was found in the lighter alkanes due to the use of alternative transportation fuels in various world regions. These ratios were grouped by region and used to develop a new speciation for surface emissions of VOCs, by applying the regional observed VOC-CO ratios to the CO emissions for the urban areas. Urban areas were defined as 150 inhabitants per km2 or greater. Model simulations were performed using the MOZART-4 chemistry transport model to assess the improved speciation of the VOC emissions. The model outputs were compared to urban observational data where available. The impact of the new speciation of the distribution of CO, OH and ozone at the global scale will be

  13. Assessment of Volatile Organic Compounds (VOCs) in indooor parking facilities at Houston, Texas

    Science.gov (United States)

    Kristanto, Gabriel Andari

    This dissertation identified the types, magnitudes, sources, and assessed risk exposure of VOCs in different types of indoor parking facilities. VOCs are ones of major pollutants emitted from automobiles. The indoor parking facilities included were attached garages, grounds, and underground parking. Modification of method TO15 by EPA had been applied for identifying types and magnitudes of VOCs. Results of these identifications are presented. Eight most abundant VOCs could be identified in every sampling location with toluene as the most abundant compound followed by m,p-xylene, ethylbenzene and benzene. Compare to ground and underground parking, attached garages have the highest concentration of TVOCs. For sources identification, BTEX, m,p-xylene and benzene, and toluene and benzene ratios are calculated. BTEX ratios for ground and underground parking are similar compare to attached garage due to the similar pattern of driving speed and the content of gasoline fuel. On the other hand the ratios of m,p-xylene and benzene and toluene and benzene in attached garage are higher compare to the same ratios for ground and underground parking due to other significant contributor of VOCs such as solvent, household cleanings stored. Cancer and noncancer risk assessment were also calculated. Results showed that cancer and noncancer risk due human exposures to VOC in indoor parking facilities were relatively low. However the risk of the human exposure to VOCs from indoor parking facilities has to be considered as a part of total risks of VOC exposures on human during their daily activities. When people in Houston have already exposed to high VOC concentrations from outdoor environment activities such as traffic and refineries and petrochemical facilities, additional activities causing VOC exposures will add the risk significantly.

  14. Raman scattering investigation of VOCs in interaction with ice particles

    Science.gov (United States)

    Facq, Sébastien; Oancea, Adriana; Focsa, Cristian; Chazallon, Bertrand

    2010-05-01

    Cirrus clouds that form in the Earth's upper troposphere (UT) are known to play a significant role in the radiation budget and climate [1]. These clouds that cover about 35% of the Earth's surface [2] are mainly composed of small ice particles that can provide surfaces for trace gas interactions [3]. Volatile Organic Compounds (VOCs) are present in relative high abundance in the UT [4][5]. They promote substantial sources of free OH radicals that are responsible for driving photochemical cycles in the atmosphere. Their presence can both influence the oxidizing capacity and the ozone budget of the atmosphere. VOCs can interact with ice particles via different trapping processes (adsorption, diffusion, freezing, and co-deposition, i.e., incorporation of trace gases during growing ice conditions) which can result in the perturbation of the chemistry and photochemistry of the UT. Knowledge of the incorporation processes of VOCs in ice particles is important in order to understand and predict their impact on the ice particles structure and reactivity and more generally on the cirrus cloud formation. This proceeds via the in-situ characterization of the ice condensed phase in a pressure and temperature range of the UT. An important mechanism of UT cirrus cloud formation is the heterogeneous ice freezing process. In this study, we examine and characterize the interaction of a VOC, i.e., ethanol (EtOH) with ice particles during freezing. Vibrational spectra of water O-H and EtOH C-H spectral regions are analysed using confocal micro-Raman spectroscopy. Information at the molecular level on the surface structure can be derived from accompanying changes observed in band shapes and vibrational mode frequencies. Depending of the EtOH content, different crystalline phases have been identified and compared to hydrates previously reported for the EtOH-water system. Particular attention is paid on the effect of EtOH aqueous solutions cooling rate and droplet sizes on the phases

  15. 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.

  16. High temperature decomposition of hydrogen peroxide

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2011-01-01

    Nitric oxide (NO) is oxidized into nitrogen dioxide (NO.sub.2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

  17. Detection of new VOC compounds with iCRDS

    Science.gov (United States)

    Huang, H.; Leen, J. B.; Gardner, A.; Gupta, M.; Baer, D. S.

    2015-12-01

    The instrument at Los Gatos Research (a member of ABB Inc.) which is based on incoherent cavity ringdown spectroscopy (iCRDS) that operates in the mid-infrared (bands from 860-1060 cm-1 or 970-1280 cm-1) is capable of detecting a broad range of VOCs, in situ, continuously and autonomously, for example, BTEX compounds (benzene, toluene, ethylbenzene, xylene), including differentiation of xylene isomers. Previously, we have demonstrated the measurement of trichloroethylene (TCE) in zero air with a precision of 0.17 ppb (1σ in 4 minutes), and the measurement of tetrachloroethylene (PCE) with a precision of 0.15 ppb (1σ in 4 minutes). Both of these measured precisions exceed the EPA's commercial building action limit, which for TCE is 0.92 ppb (5 µg/m3) and for PCE is 0.29 ppb (2 µg/m3). This ability has been fully demonstrated by the deployment of the instrument to the Superfund site at Moffett Naval Air Station in Mountain View, California where contaminated ground water results in vapor intrusion of TCE and PCE. For two weeks, the instrument operated continuously and autonomously, successfully measuring TCE and PCE concentrations in both the breathing zone and steam tunnel air, in excellent agreement with previous TO-15 data. In this poster, we present laboratory performance data targeting new toxic molecules with the same instrument. We have demonstrated the measurement of trichlorofluolomethane (Freon 11) in zero air with a precision of 1 ppb (3σ at 1075cm-1), and hexafluoropropene in zero air with a precision of about 0.3 ppb (3σ per spectrum). The iCRDS instrument has shown the ability to continuously and autonomously measure sub-ppb levels of toxic VOCs in the lab/field, offering an unprecedented picture of the short term dynamics associated with vapor intrusion and ground water pollution.

  18. Membrane transport of hydrogen peroxide.

    Science.gov (United States)

    Bienert, Gerd P; Schjoerring, Jan K; Jahn, Thomas P

    2006-08-01

    Hydrogen peroxide (H2O2) belongs to the reactive oxygen species (ROS), known as oxidants that can react with various cellular targets thereby causing cell damage or even cell death. On the other hand, recent work has demonstrated that H2O2 also functions as a signalling molecule controlling different essential processes in plants and mammals. Because of these opposing functions the cellular level of H2O2 is likely to be subjected to tight regulation via processes involved in production, distribution and removal. Substantial progress has been made exploring the formation and scavenging of H2O2, whereas little is known about how this signal molecule is transported from its site of origin to the place of action or detoxification. From work in yeast and bacteria it is clear that the diffusion of H2O2 across membranes is limited. We have now obtained direct evidence that selected aquaporin homologues from plants and mammals have the capacity to channel H2O2 across membranes. The main focus of this review is (i) to summarize the most recent evidence for a signalling role of H2O2 in various pathways in plants and mammals and (ii) to discuss the relevance of specific transport of H2O2.

  19. Detection of interstellar hydrogen peroxide

    CERN Document Server

    Bergman, P; Liseau, R; Larsson, B; Olofsson, H; Menten, K M; Güsten, R

    2011-01-01

    The molecular species hydrogen peroxide, HOOH, is likely to be a key ingredient in the oxygen and water chemistry in the interstellar medium. Our aim with this investigation is to determine how abundant HOOH is in the cloud core {\\rho} Oph A. By observing several transitions of HOOH in the (sub)millimeter regime we seek to identify the molecule and also to determine the excitation conditions through a multilevel excitation analysis. We have detected three spectral lines toward the SM1 position of {\\rho} Oph A at velocity-corrected frequencies that coincide very closely with those measured from laboratory spectroscopy of HOOH. A fourth line was detected at the 4{\\sigma} level. We also found through mapping observations that the HOOH emission extends (about 0.05 pc) over the densest part of the {\\rho} Oph A cloud core. We derive an abundance of HOOH relative to that of H_2 in the SM1 core of about 1\\times10^(-10). To our knowledge, this is the first reported detection of HOOH in the interstellar medium.

  20. Oxygen isotope fractionation during spin-forbidden photolysis of CO2: Relevance to the atmosphere of Mars

    Science.gov (United States)

    Lyons, J. R.; Stark, G.; Pack, A.; de Oliveira, N.; Nahon, L.

    2015-12-01

    The oxygen isotope composition of the Martian atmosphere is of interest for comparison with recent MSL SAM results, and to understand the origin of oxygen isotope anomalies (i.e., mass-independent fractionation or MIF) in secondary minerals in SNC meteorites. Our focus here is on spin-forbidden photolysis of CO2, CO2 + hv (>167 nm) → CO(X1S) + O(3P). The spin-forbidden photolysis of CO2 is unusual in the Martian atmosphere because of its high reaction rate from the upper atmosphere (80 km) all the way to the ground. This range of altitudes spans 4 orders of magnitude in atmospheric pressure, and occurs because of the gradual decrease in the CO2 cross sections from 167 to ~200 nm. Previous laboratory photolysis experiments on CO2 in the spin-allowed and spin-forbidden regions have yielded a remarkably large MIF signature (17O excess ~ 100 permil) in O2 product for photolysis at 185 nm. Recent theoretical cross sections for CO2 isotopologues argue for a much smaller MIF signature from spin-forbidden photolysis. Here, we report the results of photolysis experiments on CO2 at the Soleil synchrotron DESIRS beamline. High purity, natural isotope abundance CO2 was placed in a 20 cm photocell with MgF2 windows. Experiments were performed at 3 wavelengths (7% FWHM): 160 nm (spin-allowed), and at 175 nm and 185 nm (spin-forbidden). After VUV exposure, aliquots of the photolyzed CO2 were sent to the Department of Isotope Geology at the University of Goettingen for O isotope analysis. The isotope results show that the spin-allowed photolysis yields normal, mass-dependent fractionation in agreement with earlier work. Photolysis at 175 nm, which is mostly spin-forbidden, yields a small positive (or zero) MIF signature. Photolysis at 185 nm, which is entirely spin-forbidden, yields O2 with a negative MIF signature (D17O ~ -8 to -10 permil). The results at 185 nm disagree in magnitude and sign with the very large positive MIF signature previously reported, and provides support

  1. Model-aided radiometric determination of photolysis frequencies in a sunlit atmosphere simulation chamber

    Directory of Open Access Journals (Sweden)

    B. Bohn

    2004-10-01

    Full Text Available In this work diurnal and seasonal variations of mean photolysis frequencies for the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich are calculated. SAPHIR has a complex construction with UV permeable teflon walls allowing natural sunlight to enter the reactor volume. The calculations are based on external measurements of solar spectral actinic flux and a model considering the time-dependent impact of shadows from construction elements as well as the influence of the teflon walls. Overcast and clear-sky conditions are treated in a consistent way and different assumptions concerning diffuse sky radiance distributions are tested. Radiometric measurements inside the chamber are used for an inspection of model predictions. Under overcast conditions we obtain 74% and 67% of external values for photolysis frequencies j(NO2 (NO2+hν→NO+O(3P and j(O1D (O3+hν→O2+O(1D, respectively. On a clear sky summer day these values are time-dependent within ranges 0.65–0.86 and 0.60–0.73, for j(NO2 and j(O1D, respectively. A succeeding paper (Bohn et al., 2004 is dealing with an on-road test of the model approach by comparison with photolysis frequencies from chemical actinometry experiments within SAPHIR.

  2. Absolute absorption cross-section and photolysis rate of I2

    Directory of Open Access Journals (Sweden)

    J. M. C. Plane

    2004-05-01

    Full Text Available Following recent observations of molecular iodine (I2 in the coastal marine boundary layer (MBL (Saiz-Lopez and Plane, 2004, it has become important to determine the absolute absorption cross-section of I2 at reasonably high resolution, and also to evaluate the rate of photolysis of the molecule in the lower atmosphere. The absolute absorption cross-section (σ of gaseous I2 at room temperature and pressure (295 K, 760 Torr was therefore measured between 182 and 750 nm using a Fourier Transform spectrometer at a resolution of 4 cm−1 (0.1 nm at λ=500 nm. The maximum absorption cross-section in the visible region was observed at λ=533.0 nm to be σ=(4.84±0.60×10−18cm2 molecule−1. The spectrum is available as supplementary material accompanying this paper. The photo-dissociation rate constant (J of gaseous I2 was also measured directly in a solar simulator, yielding J(I2=0.12±0.03 s−1 for the lower troposphere. This agrees well with the value of 0.15±0.03 s−1 calculated using the measured absorption cross-section, terrestrial solar flux for clear sky conditions and assuming a photo-dissociation yield of unity. A two-stream radiation transfer model was then used to determine the variation in photolysis rate with solar zenith angle (SZA, from which an analytic expression is derived for use in atmospheric models. Photolysis appears to be the dominant loss process for I2 during daytime, and hence an important source of iodine atoms in the lower atmosphere.

  3. Chlorine-catalyzed ozone destruction: Cl atom production from ClOOCl photolysis.

    Science.gov (United States)

    Wilmouth, David M; Hanisco, Thomas F; Stimpfle, Richard M; Anderson, James G

    2009-12-24

    Recent laboratory measurements of the absorption cross sections of the ClO dimer, ClOOCl, have called into question the validity of the mechanism that describes the catalytic removal of ozone by chlorine. Here we describe direct measurements of the rate-determining step of that mechanism, the production of Cl atoms from the photolysis of ClOOCl, under laboratory conditions similar to those in the stratosphere. ClOOCl is formed in a cold-temperature flowing system, with production initiated by a microwave discharge of Cl(2) or photolysis of CF(2)Cl(2). Excimer lasers operating at 248, 308, and 352 nm photodissociate ClOOCl, and the Cl atoms produced are detected with time-resolved atomic resonance fluorescence. Cl(2), the primary contaminant, is measured directly for the first time in a ClOOCl cross section experiment. We find the product of the quantum yield of the Cl atom production channel of ClOOCl photolysis and the ClOOCl absorption cross section, (phisigma)(ClOOCl) = 660 +/- 100 at 248 nm, 39.3 +/- 4.9 at 308 nm, and 8.6 +/- 1.2 at 352 nm (units of 10(-20) cm(2) molecule(-1)). The data set includes 468 total cross section measurements over a wide range of experimental conditions, significantly reducing the possibility of a systematic error impacting the results. These new measurements demonstrate that long-wavelength photons (lambda = 352 nm) are absorbed by ClOOCl directly, producing Cl atoms with a probability commensurate with the observed rate of ozone destruction in the atmosphere.

  4. Degradation pathways of lamotrigine under advanced treatment by direct UV photolysis, hydroxyl radicals, and ozone.

    Science.gov (United States)

    Keen, Olya S; Ferrer, Imma; Michael Thurman, E; Linden, Karl G

    2014-12-01

    Lamotrigine is recently recognized as a persistent pharmaceutical in the water environment and wastewater effluents. Its degradation was studied under UV and ozone advanced oxidation treatments with reaction kinetics of lamotrigine with ozone (≈4 M(-1)s(-1)), hydroxyl radical [(2.1 ± 0.3) × 10(9)M(-1)s(-1)] and by UV photolysis with low and medium pressure mercury vapor lamps [quantum yields ≈0 and (2.7 ± 0.4)× 10(-4) respectively] determined. All constants were measured at pH 6 and at temperature ≈20°C. The results indicate that lamotrigine is slow to respond to direct photolysis or oxidation by ozone and no attenuation of the contaminant is expected in UV or ozone disinfection applications. The compound reacts rapidly with hydroxyl radicals indicating that advanced oxidation processes would be effective for its treatment. Degradation products were identified under each treatment process using accurate mass time-of-flight spectrometry and pathways of decay were proposed. The main transformation pathways in each process were: dechlorination of the benzene ring during direct photolysis; hydroxyl group addition to the benzene ring during the reaction with hydroxyl radicals; and triazine ring opening after reaction with ozone. Different products that form in each process may be to a varying degree less environmentally stable than the parent lamotrigine. In addition, a novel method of ozone quenching without addition of salts is presented. The new quenching method would allow subsequent mass spectrometry analysis without a solid phase extraction clean-up step. The method involves raising the pH of the sample to approximately 10 for a few seconds and lowering it back and is therefore limited to applications for which temporary pH change is not expected to affect the outcome of the analysis.

  5. Hydrolysis and Photolysis of Herbicide Clomazone in Aqueous Solutions and Natural Water Under Abiotic Conditions

    Institute of Scientific and Technical Information of China (English)

    CAO Jia; DIAO Xiao-ping; HU Ji-ye

    2013-01-01

    The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identiifed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions ((25±2)°C, pH (4.5±0.1), pH (7.4±0.1), pH (9.0±0.1);(50±2)°C, pH (4.5±0.1), pH (7.4±0.1)) or in natural water up to 90 d. At pH (9.0±0.1) and (50±2)°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed ifrst-order kinetics. Degradation rates were faster under UV light (half-life of 51-59 min) compared to sunlight (half-life of 87-136 d). Under UV light, four major photoproducts were detected and tentatively identiifed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-(2-benzyl)-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl-3-isoxazolidinone and 2-[(4,6-dihydroxyl-2-chlorine phenol)]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways:1) dehalogenation;2) substitution of chlorine group by hydroxyl;3) cleavage of the side chain. Photosensitizers, such as H2O2 and ribolfavin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.

  6. Brominated 7-hydroxycoumarin-4-ylmethyls: Photolabile protecting groups with biologically useful cross-sections for two photon photolysis

    Science.gov (United States)

    Furuta, Toshiaki; Wang, Samuel S.-H.; Dantzker, Jami L.; Dore, Timothy M.; Bybee, Wendy J.; Callaway, Edward M.; Denk, Winfried; Tsien, Roger Y.

    1999-01-01

    Photochemical release (uncaging) of bioactive messengers with three-dimensional spatial resolution in light-scattering media would be greatly facilitated if the photolysis could be powered by pairs of IR photons rather than the customary single UV photons. The quadratic dependence on light intensity would confine the photolysis to the focus point of the laser, and the longer wavelengths would be much less affected by scattering. However, previous caged messengers have had very small cross sections for two-photon excitation in the IR region. We now show that brominated 7-hydroxycoumarin-4-ylmethyl esters and carbamates efficiently release carboxylates and amines on photolysis, with one- and two-photon cross sections up to one or two orders of magnitude better than previously available. These advantages are demonstrated on neurons in brain slices from rat cortex and hippocampus excited by glutamate uncaged from N-(6-bromo-7-hydroxycoumarin-4-ylmethoxycarbonyl)-l-glutamate (Bhc-glu). Conventional UV photolysis of Bhc-glu requires less than one-fifth the intensities needed by one of the best previous caged glutamates, γ-(α-carboxy-2-nitrobenzyl)-l-glutamate (CNB-glu). Two-photon photolysis with raster-scanned femtosecond IR pulses gives the first three-dimensionally resolved maps of the glutamate sensitivity of neurons in intact slices. Bhc-glu and analogs should allow more efficient and three-dimensionally localized uncaging and photocleavage, not only in cell biology and neurobiology but also in many technological applications. PMID:9990000

  7. Thermal response and recyclability of poly(stearylacrylate-co-ethylene glycol dimethacrylate) gel as a VOCs absorbent

    Science.gov (United States)

    The development of absorbent materials for volatile organic compounds (VOCs) is in demand for a variety of environmental applications including protective barriers for VOCs point sources. One of the challenges for the currently available VOCs absorbents is their recyclability. In this study, we syn...

  8. Chemically Patterned Inverse Opal Created by a Selective Photolysis Modification Process.

    Science.gov (United States)

    Tian, Tian; Gao, Ning; Gu, Chen; Li, Jian; Wang, Hui; Lan, Yue; Yin, Xianpeng; Li, Guangtao

    2015-09-01

    Anisotropic photonic crystal materials have long been pursued for their broad applications. A novel method for creating chemically patterned inverse opals is proposed here. The patterning technique is based on selective photolysis of a photolabile polymer together with postmodification on released amine groups. The patterning method allows regioselective modification within an inverse opal structure, taking advantage of selective chemical reaction. Moreover, combined with the unique signal self-reporting feature of the photonic crystal, the fabricated structure is capable of various applications, including gradient photonic bandgap and dynamic chemical patterns. The proposed method provides the ability to extend the structural and chemical complexity of the photonic crystal, as well as its potential applications.

  9. Laser photolysis of interaction of poly-guanylic acid (5′) with anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    马建华; 林维真; 王文峰; 韩镇辉; 姚思德; 林念芸

    2002-01-01

    The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly- guanylic acid (5′) in CH3CN-H2O (97:3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.

  10. Laser photolysis of interaction of poly-guanylic acid (5’) with anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    马建华; 韩镇辉; 林维真; 姚思德; 王文峰; 林念芸

    2002-01-01

    The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5’) in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.

  11. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

    Science.gov (United States)

    Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

    2014-06-28

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the

  12. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Science.gov (United States)

    Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

    2014-06-01

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of 15ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well

  13. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël [Laboratoire de Glaciologie et Géophysique de l’Environnement, CNRS, F-38041 Grenoble (France); Univ. Grenoble Alpes, LGGE, F-38041 Grenoble (France); Meusinger, Carl; Johnson, Matthew S. [Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Jost, Rémy [Laboratoire de Interdisciplinaire de Physique (LIPHY) Univ. de Grenoble, Grenoble (France); Bhattacharya, S. K. [Research Center for Environmental Changes, Academia Sinica, Nangang, Taipei 115, Taiwan (China)

    2014-06-28

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying

  14. Degradation of Dissolved Organic Carbon from Discontinuous Permafrost Due to Photolysis and Different Inoculants

    Science.gov (United States)

    Aukes, P.; Schiff, S. L.

    2013-12-01

    Northern areas with permafrost are very susceptible to a warming climate. Temperature increases can alter hydrologic flow paths, increase the depth and biogeochemistry of the active layer, and degrade and reduce the amount of remaining permafrost. Particularly, loss of permafrost will release large stores of previously unavailable frozen carbon to the environment. Dissolved organic carbon (DOC) plays many important roles that affect both ecosystem health and drinking water quality. Comprised of countless different molecules, DOC absorbs harmful ultra-violet (UV) radiation and controls thermal regimes of lakes, is an important energy and nutrient source for heterotrophic microbes, complexes with and transports heavy metals, and reacts during chlorination of drinking water to form carcinogenic disinfection by-products. Since the ultimate fate of DOC depends on its reactivity with the surrounding environment, the implications of DOC released from permafrost for ecosystems and drinking water quality will vary across the landscape. We used 90-day lab incubations to assess the differences in quality of DOC by observing the susceptibility for DOC to degrade among various discontinuous-permafrost sources. Specifically, UV-photolysis and two surface water inoculants (pond and creek water filtered to 2.0μm) were used to represent the dominant degradation pathways encountered within the environment. Samples were taken in July 2013 from three locations (pond, creek, and wetland porewater) in a region of discontinuous permafrost near Yellowknife, NWT, Canada. We observed changes to the composition and quality of DOC resulting from photolysis and degradation by two inoculants over 90 days, where DOC quality was determined by Liquid Chromatography - Organic Carbon Detection, DOC:DON, UV-absorbance, and changes to other constituents (DIC, δ13C-DIC, CO2). We hypothesize that UV-photolysis and microbial degradation will readily degrade easily accessible and reactive components of

  15. Influence of satellite-derived photolysis rates and NOx emissions on Texas ozone modeling

    Directory of Open Access Journals (Sweden)

    W. Tang

    2014-09-01

    Full Text Available Uncertain photolysis rates and emission inventory impair the accuracy of state-level ozone (O3 regulatory modeling. Past studies have separately used satellite-observed clouds to correct the model-predicted photolysis rates, or satellite-constrained top-down NOx emissions to identify and reduce uncertainties in bottom-up NOx emissions. However, the joint application of multiple satellite-derived model inputs to improve O3 State Implementation Plan (SIP modeling has rarely been explored. In this study, Geostationary Operational Environmental Satellite (GOES observations of clouds are applied to derive the photolysis rates, replacing those used in Texas SIP modeling. This changes modeled O3 concentrations by up to 80 ppb and improves O3 simulations by reducing modeled normalized mean bias (NMB and normalized mean error (NME by up to 0.1. A sector-based discrete Kalman filter (DKF inversion approach is incorporated with the Comprehensive Air Quality Model with extensions (CAMx-Decoupled Direct Method (DDM model to adjust Texas NOx emissions using a high resolution Ozone Monitoring Instrument (OMI NO2 product. The discrepancy between OMI and CAMx NO2 vertical column densities (VCD is further reduced by increasing modeled NOx lifetime and adding an artificial amount of NO2 in the upper troposphere. The sector-based DKF inversion tends to scale down area and non-road NOx emissions by 50%, leading to a 2–5 ppb decrease in ground 8 h O3 predictions. Model performance in simulating ground NO2 and O3 are improved using inverted NOx emissions, with 0.25 and 0.04 reductions in NMBs and 0.13 and 0.04 reductions in NMEs, respectively. Using both GOES-derived photolysis rates and OMI-constrained NOx emissions together reduces modeled NMB and NME by 0.05 and increases the model correlation with ground measurement in O3 simulations and makes O3 more sensitive to NOx emissions in the O3 non-attainment areas.

  16. Time-resolved circular dichroism and absorption studies of the photolysis reaction of (carbonmonoxy)myoglobin.

    OpenAIRE

    Milder, S J; Bjorling, S.C.; Kuntz, I D; Kliger, D S

    1988-01-01

    Time-resolved circular dichroism (TRCD) and absorption spectroscopy are used to follow the photolysis reaction of (carbonmonoxy)myoglobin (MbCO). Following the spectral changes associated with the initial loss of CO, a subtle change is observed in the visible absorption spectrum of the Mb product on a time scale of a few hundred nanoseconds. No changes are seen in the CD spectrum of Mb in the visible and near-UV regions subsequent to the loss of CO. The data suggest the existence of an interm...

  17. A Laser Flash Photolysis Study of Azo-Compound Formation from Aryl Nitrenes at Room Temperature.

    Science.gov (United States)

    Ribblett, Alec Q; Poole, James S

    2016-06-30

    The species 4-nitrenopyridine 1-oxide is known to exhibit triplet nitrene dominated chemistry to yield azo-dimer products exclusively, even at room temperature. As such, this species, and its analogue 4-nitrenoquinoline 1-oxide, are useful models to probe the mechanism of formation of azo-dimers, which is postulated to proceed by self-reaction of the nitrene or reaction of nitrene with the parent azide. A laser flash photolysis study is described where the kinetics of formation of azo-dimer were found to be most adequately modeled by competition between both mechanisms, and rate coefficients for the competing reactions were determined.

  18. 21 CFR 529.1150 - Hydrogen peroxide.

    Science.gov (United States)

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS CERTAIN OTHER DOSAGE FORM NEW ANIMAL DRUGS § 529.1150 Hydrogen... group. Eggs: Some strains of rainbow trout eggs are sensitive to hydrogen peroxide treatment at a time...

  19. Isothermal Decomposition of Hydrogen Peroxide Dihydrate

    Science.gov (United States)

    Loeffler, M. J.; Baragiola, R. A.

    2011-01-01

    We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H2O2 and H2O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.

  20. Ultrafast Photoinduced Electron Transfer from Peroxide Dianion.

    Science.gov (United States)

    Anderson, Bryce L; Maher, Andrew G; Nava, Matthew; Lopez, Nazario; Cummins, Christopher C; Nocera, Daniel G

    2015-06-18

    The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)3(2+) and the peroxide dianion occurs with a rate constant of 2.0 × 10(10) M(-1) s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 × 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)3(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

  1. Lipid peroxidation in experimental uveitis: sequential studies.

    Science.gov (United States)

    Goto, H; Wu, G S; Chen, F; Kristeva, M; Sevanian, A; Rao, N A

    1992-06-01

    Previously we have detected the occurrence of retinal lipid peroxidation initiated by phagocyte-derived oxygen radicals in experimental autoimmune uveitis (EAU). In the current studies, the confirmation of inflammation-mediated lipid peroxidation was proceeded further to include measurement of multiple parameters, including conjugated dienes, ketodienes, thiobarbituric acid reactive substances and fluorescent chromolipids. The assay for myeloperoxidase, a measure for the number of polymorphonuclear leukocytes in the inflammatory sites was also carried out. The levels of all these parameters were followed through the course of EAU development. The sequential evaluation of histologic changes using both light and electron microscopy was also carried out and the results were correlated with lipid peroxidation indices. These data suggest that the retinal lipid peroxidation plays a causative role in the subsequent retinal degeneration.

  2. Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 1: Simple VOCs and model PM

    Directory of Open Access Journals (Sweden)

    H. E. Jeffries

    2012-12-01

    Full Text Available This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC, particulate matter (PM, and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit virtually gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure. Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity. Airborne mixtures were then created with each compound to which we added PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own. Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells. We observed that, even if the gas-phase pollutants

  3. Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 1: Simple VOCs and model PM

    Directory of Open Access Journals (Sweden)

    H. E. Jeffries

    2012-02-01

    Full Text Available This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC, particulate matter (PM, and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure. Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity. Airborne mixtures were then created with each compound and PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and it exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own. Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells – even if the gas-phase pollutants are not

  4. Gaseous VOCs rapidly modify particulate matter and its biological effects - Part 1: Simple VOCs and model PM

    Science.gov (United States)

    Ebersviller, S.; Lichtveld, K.; Sexton, K. G.; Zavala, J.; Lin, Y.-H.; Jaspers, I.; Jeffries, H. E.

    2012-12-01

    This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit virtually gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure. Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity). Airborne mixtures were then created with each compound to which we added PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA) was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own. Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells). We observed that, even if the gas-phase pollutants are not

  5. Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

    Science.gov (United States)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

    2012-11-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O2-reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O2, which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

  6. Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell

    Science.gov (United States)

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.

    2012-01-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O2-reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O2, which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells. PMID:23457415

  7. EFFLUENT TREATMENT FACILITY PEROXIDE DESTRUCTION CATALYST TESTING

    Energy Technology Data Exchange (ETDEWEB)

    HALGREN DL

    2008-07-30

    The 200 Area Effluent Treatment Facility (ETF) main treatment train includes the peroxide destruction module (PDM) where the hydrogen peroxide residual from the upstream ultraviolet light/hydrogen peroxide oxidation unit is destroyed. Removal of the residual peroxide is necessary to protect downstream membranes from the strong oxidizer. The main component of the PDM is two reaction vessels utilizing granular activated carbon (GAC) as the reaction media. The PDM experienced a number of operability problems, including frequent plugging, and has not been utilized since the ETF changed to groundwater as the predominant feed. The unit seemed to be underperforming in regards to peroxide removal during the early periods of operation as well. It is anticipated that a functional PDM will be required for wastewater from the vitrification plant and other future streams. An alternate media or methodology needs to be identified to replace the GAC in the PDMs. This series of bench scale tests is to develop information to support an engineering study on the options for replacement of the existing GAC method for peroxide destruction at the ETF. A number of different catalysts will be compared as well as other potential methods such as strong reducing agents. The testing should lead to general conclusions on the viability of different catalysts and identify candidates for further study and evaluation.

  8. Characterisation and treatment of VOCs in process water from upgrading facilities for compressed biogas (CBG).

    Science.gov (United States)

    Nilsson Påledal, S; Arrhenius, K; Moestedt, J; Engelbrektsson, J; Stensen, K

    2016-02-01

    Compression and upgrading of biogas to vehicle fuel generates process water, which to varying degrees contains volatile organic compounds (VOCs) originating from the biogas. The compostion of this process water has not yet been studied and scientifically published and there is currently an uncertainty regarding content of VOCs and how the process water should be managed to minimise the impact on health and the environment. The aim of the study was to give an overview about general levels of VOCs in the process water. Characterisation of process water from amine and water scrubbers at plants digesting waste, sewage sludge or agricultural residues showed that both the average concentration and composition of particular VOCs varied depending on the substrate used at the biogas plant, but the divergence was high and the differences for total concentrations from the different substrate groups were only significant for samples from plants using waste compared to residues from agriculture. The characterisation also showed that the content of VOCs varied greatly between different sampling points for same main substrate and between sampling occasions at the same sampling point, indicating that site-specific conditions are important for the results which also indicates that a number of analyses at different times are required in order to make an more exact characterisation with low uncertainty. Inhibition of VOCs in the anaerobic digestion (AD) process was studied in biomethane potential tests, but no inhibition was observed during addition of synthetic process water at concentrations of 11.6 mg and 238 mg VOC/L.

  9. CAN SORBENT-BASED GAS PHASE AIR CLEANING FOR VOCS SUBSTITUTE FOR VENTILATION IN COMMERCIAL BUILDINGS?

    Energy Technology Data Exchange (ETDEWEB)

    Fisk, William; Fisk, William J.

    2007-08-01

    This paper reviews current knowledge about the suitability of sorbent-based air cleaning for removing volatile organic compounds (VOCs) from the air in commercial buildings, as needed to enable reductions in ventilation rates and associated energy savings. The principles of sorbent air cleaning are introduced, criteria are suggested for sorbent systems that can counteract indoor VOC concentration increases from reduced ventilation, major findings from research on sorbent performance for this application are summarized, and related priority research needs are identified. Major conclusions include: sorbent systems can remove a broad range of VOCs with moderate to high efficiency, sorbent technologies perform effectively when challenged with VOCs at the low concentrations present indoors, and there is a large uncertainty about the lifetime and associated costs of sorbent air cleaning systems when used in commercial buildings for indoor VOC control. Suggested priority research includes: experiments to determine sorbent system VOC removal efficiencies and lifetimes considering the broad range and low concentration of VOCs indoors; evaluations of in-situ regeneration of sorbents; and an updated analysis of the cost of sorbent air cleaning relative to the cost of ventilation.

  10. Comparison of VOC and ammonia emissions from individual PVC materials, adhesives and from complete structures.

    Science.gov (United States)

    Järnström, H; Saarela, K; Kalliokoski, P; Pasanen, A-L

    2008-04-01

    Emission rates of volatile organic compounds (VOCs) and ammonia measured from six PVC materials and four adhesives in the laboratory were compared to the emission rates measured on site from complete structures. Significantly higher specific emission rates (SERs) were generally measured from the complete structures than from individual materials. There were large differences between different PVC materials in their permeability for VOCs originating from the underlying structure. Glycol ethers and esters from adhesives used in the installation contributed to the emissions from the PVC covered structure. Emissions of 2-ethylhexanol and TXIB (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) were common. High ammonia SERs were measured from single adhesives but their contribution to the emissions from the complete structure did not appear as obvious as for VOCs. The results indicate that three factors affected the VOC emissions from the PVC flooring on a structure: 1) the permeability of the PVC product for VOCs, 2) the VOC emission from the adhesive used, and 3) the VOC emission from the backside of the PVC product.

  11. Assessment of ambient volatile organic compounds (VOCs) near major roads in urban Nanjing, China

    Science.gov (United States)

    Wang, P.; Zhao, W.

    2008-08-01

    Volatile organic compounds (VOCs) are a major component of atmospheric pollutants in Nanjing, a large city in the east of China. Accordingly, 12-h diurnal monitoring for ten consecutive days was performed adjacent to major roads in five districts, ca.1.5 m above ground level, in April, July and October 2006, and January 2007. The most numerous species of VOCs (benzene, toluene, ethylbenzene, m/ p-xylene, o-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, tetrachloromethane, trichloroethane and tetrachloroethane) were selected as the target pollutants for this field study of atmospheric distribution. The eleven VOCs were mostly found in gas phase due to their high vapor pressures. Gas-phase concentrations ranged between 0.6 and 67.9 μg m - 3 . Simultaneously, the levels of those VOCs measured near major roads were associated slightly with their regional background level. For all these areas, as expected, the high traffic area was the highest in terms of concentration. A positive correlation was also found between the VOC levels and traffic density. Our studies also provided VOC distribution, and vertical/horizontal profiles. The results show that traffic-related exposure to VOCs in major road microenvironments is higher than elsewhere and poses a potential threat to pedestrians, commuters, and traffic-exposed workers.

  12. Indoor contaminants from Hardcopy Devices: Characteristics of VOCs in photocopy centers

    Science.gov (United States)

    Sarkhosh, Maryam; Mahvi, Amir Hossein; Zare, Mohammad Reza; Fakhri, Yadolah; Shamsolahi, Hamid Reza

    2012-12-01

    Indoor air pollution in working places is widely recognized as one of the most serious potential environment risks to human health. Mean volatile organic compound (VOC) concentrations of 144 samples from four copy centers in Tehran, Iran in two seasons were monitored for the purpose of quantifying the various VOCs in these areas. Area samples were collected in thermal desorption tubes and were analyzed using gas chromatography/mass selective detector. Real-time personal total volatile organic compounds were measured using a data-logging photo-ionization detector. Simultaneously, BTEX (benzene, toluene, ethylbenzene, xylenes) outdoor measurements were performed in the same manner as were the indoor measurements. Nineteen different VOCs were detected in the area samples. The results show that in all photocopy centers, the indoor levels of toluene were much higher than the outdoor levels. During business hours, the VOC levels increased, especially toluene indoor concentration. The ventilation decreased the indoor VOC concentrations. The background and indoor VOC concentrations were higher in winter than in spring. The minimum ratio of the indoor to outdoor concentration of BTEX was estimated to be more than 42. This value proved that buildings with photocopiers can be a site of VOC accumulation.

  13. VOC reactivity and its effect on ozone production during the HaChi summer campaign

    Directory of Open Access Journals (Sweden)

    L. Ran

    2011-05-01

    Full Text Available Measurements of ozone and its precursors conducted within the HaChi (Haze in China project in summer 2009 were analyzed to characterize volatile organic compounds (VOCs and their effects on ozone photochemical production at a suburban site in the North China Plain (NCP. Ozone episodes, during which running 8-h average ozone concentrations exceeding 80 ppbv lasted for more than 4 h, occurred on about two thirds of the observational days during the 5-week field campaign. This suggests continuous ozone exposure risks in this region in the summer. Average concentrations of nitrogen oxides (NOx and VOCs are about 20 ppbv and 650 ppbC, respectively. On average, total VOC reactivity is dominated by anthropogenic VOCs. The contribution of biogenic VOCs to total ozone-forming potential, however, is also considerable in the daytime. Key species associated with ozone photochemical production are 2-butenes (18 %, isoprene (15 %, trimethylbenzenes (11 %, xylenes (8.5 %, 3-methylhexane (6 %, n-hexane (5 % and toluene (4.5 %. Formation of ozone is found to be NOx-limited as indicated by measured VOCs/NOx ratios and further confirmed by a sensitivity study using a photochemical box model NCAR_MM. The Model simulation suggests that ozone production is also sensitive to changes in VOC reactivity under the NOx-limited regime, although this sensitivity depends strongly on how much NOx is present.

  14. Temporal variability and sources of VOCs in urban areas of the eastern Mediterranean

    Science.gov (United States)

    Kaltsonoudis, Christos; Kostenidou, Evangelia; Florou, Kalliopi; Psichoudaki, Magda; Pandis, Spyros N.

    2016-11-01

    During the summer of 2012 volatile organic compounds (VOCs) were monitored by proton transfer reaction mass spectrometry (PTR-MS) in urban sites, in Athens and Patras, two of the largest cities in Greece. Also, during the winter of 2013, PTR-MS measurements were conducted in the center of the city of Athens. Positive matrix factorization (PMF) was applied to the VOC measurements to gain insights about their sources. In summer most of the measured VOCs were due to biogenic and traffic emissions. Isoprene, monoterpenes, and several oxygenated VOCs (oVOCs) originated mainly from vegetation either directly or as oxidation products. Isoprene average concentrations in Patras and Athens were 1 and 0.7 ppb respectively, while the monoterpene concentrations were 0.3 and 0.9 ppb respectively. Traffic was the main source of aromatic compounds during summer. For Patras and Athens the average concentrations of benzene were 0.1 and 0.2 ppb, of toluene 0.3 and 0.8 ppb, and of the xylenes 0.3 and 0.7 ppb respectively. Winter measurements in Athens revealed that biomass burning used for residential heating was a major VOC source contributing both aromatic VOCs and biogenic compounds such as monoterpenes. Several episodes related to biomass burning were identified and emission ratios (ERs) and emission factors (EFs) were estimated.

  15. VOCs in industrial, urban and suburban neighborhoods—Part 2: Factors affecting indoor and outdoor concentrations

    Science.gov (United States)

    Jia, Chunrong; Batterman, Stuart; Godwin, Christopher

    Many microenvironmental and behavioral factors can affect concentrations of and exposures to volatile organic compounds (VOCs). Identifying these determinants is important to understand exposures and risks, and also to design policies and strategies that minimize concentrations. This study is aimed at determining factors associated with VOC concentrations found indoors in residences and outdoors in ambient air. It utilizes results from a comprehensive field study in which 98 VOCs were measured both inside and outside of 159 residences in three communities in southeast Michigan, USA. Additional measurements included indoor CO 2 concentrations, temperature, relative humidity, building and neighborhood characteristics, and occupant activities, assessed using a questionnaire and comprehensive walkthrough investigation. Factors potentially affecting concentrations were identified using bivariate and multivariate analyses. Outdoors, seasonal and community effects were observed. Indoors, seasonal effects were limited to the urban and industrial communities, largely due to changes in ambient levels. Elevated indoor VOC concentrations were associated with eight sources or activities: the presence of an attached garage; recent renovations; older residences; indoor smoking; less frequent window or door opening; higher CO 2 concentrations; and lower ventilation rates. VOC levels were uninfluenced by building materials (wood vs. brick), flooring type (carpeting vs. wood), stove type (gas or electric), number of occupants, air freshener use, and hobbies involving arts and crafts. Factor analyses identified up to five factors for the ambient VOC measurements, and up to 10 factors for the indoor measurements, which further helped to explain the variability of concentrations and associations between VOCs.

  16. Development of metal organic fromwork-199 immobilized zeolite foam for adsorption of common indoor VOCs.

    Science.gov (United States)

    Saini, Vipin K; Pires, João

    2017-05-01

    Reticulated foam shaped adsorbents are more efficient for the removal of volatile organic compounds (VOCs), particularly from low VOC-concentration indoor air streams. In this study composite structure of zeolite and metal organic frameworks (MOFs), referred as ZMF, has been fabricated by immobilization of fine MOF-199 powder on foam shaped Zeolite Socony Mobil-5 (ZSM-5) Zeolitic structure, referred as ZF. The ZMF possess a uniform and well-dispersed coating of MOF-199 on the porous framework of ZF. It shows higher surface area, pore volume, and VOCs adsorption capacity, as compared to ZF-structure. Post-fabrication changes in selective adsorption properties of ZMF were studied with three common indoor VOCs (benzene, n-hexane, and cyclohexane), using gravimetric adsorption technique. The adsorption capacity of ZMF with different VOCs follow the order of benzene>n-hexane>cyclohexane. In comparison with MOF-199 and ZF, the composite structure ZMF shows improvement in selectivity for benzene from other two VOCs. Further, improvement in efficiency and stability of prepared ZMF was found to be associated with its high MOF loading capacity and unique morphological and structural properties. The developed composite structure with improved VOCs removal and recyclability could be a promising material for small to limited scale air pollution treatment units. Copyright © 2016. Published by Elsevier B.V.

  17. Volatile Organic Compounds (VOCs in Conventional and High Performance School Buildings in the U.S.

    Directory of Open Access Journals (Sweden)

    Lexuan Zhong

    2017-01-01

    Full Text Available Exposure to volatile organic compounds (VOCs has been an indoor environmental quality (IEQ concern in schools and other buildings for many years. Newer designs, construction practices and building materials for “green” buildings and the use of “environmentally friendly” products have the promise of lowering chemical exposure. This study examines VOCs and IEQ parameters in 144 classrooms in 37 conventional and high performance elementary schools in the U.S. with the objectives of providing a comprehensive analysis and updating the literature. Tested schools were built or renovated in the past 15 years, and included comparable numbers of conventional, Energy Star, and Leadership in Energy and Environmental Design (LEED-certified buildings. Indoor and outdoor VOC samples were collected and analyzed by thermal desorption, gas chromatography and mass spectroscopy for 94 compounds. Aromatics, alkanes and terpenes were the major compound groups detected. Most VOCs had mean concentrations below 5 µg/m3, and most indoor/outdoor concentration ratios ranged from one to 10. For 16 VOCs, the within-school variance of concentrations exceeded that between schools and, overall, no major differences in VOC concentrations were found between conventional and high performance buildings. While VOC concentrations have declined from levels measured in earlier decades, opportunities remain to improve indoor air quality (IAQ by limiting emissions from building-related sources and by increasing ventilation rates.

  18. Volatile Organic Compounds (VOCs) in Conventional and High Performance School Buildings in the U.S.

    Science.gov (United States)

    Zhong, Lexuan; Su, Feng-Chiao; Batterman, Stuart

    2017-01-01

    Exposure to volatile organic compounds (VOCs) has been an indoor environmental quality (IEQ) concern in schools and other buildings for many years. Newer designs, construction practices and building materials for “green” buildings and the use of “environmentally friendly” products have the promise of lowering chemical exposure. This study examines VOCs and IEQ parameters in 144 classrooms in 37 conventional and high performance elementary schools in the U.S. with the objectives of providing a comprehensive analysis and updating the literature. Tested schools were built or renovated in the past 15 years, and included comparable numbers of conventional, Energy Star, and Leadership in Energy and Environmental Design (LEED)-certified buildings. Indoor and outdoor VOC samples were collected and analyzed by thermal desorption, gas chromatography and mass spectroscopy for 94 compounds. Aromatics, alkanes and terpenes were the major compound groups detected. Most VOCs had mean concentrations below 5 µg/m3, and most indoor/outdoor concentration ratios ranged from one to 10. For 16 VOCs, the within-school variance of concentrations exceeded that between schools and, overall, no major differences in VOC concentrations were found between conventional and high performance buildings. While VOC concentrations have declined from levels measured in earlier decades, opportunities remain to improve indoor air quality (IAQ) by limiting emissions from building-related sources and by increasing ventilation rates. PMID:28117727

  19. Cyclic Organic Peroxides Characterization by Mass Spectrometry and Raman Microscopy

    Science.gov (United States)

    2011-04-01

    organic peroxides,DART, hexa -methylene triperoxide diamine (HMTD), triacetonetriperoxide (TATP), TATP-d18, triacetone triperoxide (TATP), time-of...peroxides, DART, hexa -methylene triperoxide diamine (HMTD), triacetone triperoxide (TATP), , triacetone triperoxide (TATP), time-of-flight–mass...acetone tri-peroxide (TATP) and hexa -methylene triper- oxide diamine (HMTD) are the more commonly used cyclic organic peroxides in terrorist acts

  20. Photolysis pathway of nitroaromatic compounds in aqueous solutions in the UV/H2O2 process

    Institute of Scientific and Technical Information of China (English)

    CHEN Bing; YANG Chun; GOH Ngoh Khang

    2006-01-01

    Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.

  1. Variations in radiation and photolysis rates in the southern midlatitudes due to ozone depletion over the Antarctica

    Science.gov (United States)

    López Comí, Laura; Morgenstern, Olaf; Zeng, Guang; Masters, Sarah L.

    2013-04-01

    Lauder (45° S, 170° E), a research station located on the South Island of New Zealand, is a clean-air atmospheric observatory representative of southern mid-latitudes. Long-term records of various atmospheric chemical compounds have been measured here for up to three decades. We assess observations of selected atmospheric chemical species, including ozone, and their variability throughout the recording period. By utilizing these observational data and a photolysis scheme (FAST-JX) we will address how changes in the total ozone column and in aerosols at Lauder affect radiation and photolysis rates of different species. The results serve as a stepping stone towards constructing a single-column photolysis model for Lauder constrained with profiles of stable species (e.g. ozone, methane, CO, HCHO, halogen compounds, etc) measured at Lauder to derive variations and trends of shorter-lived species. One of our targets will be changes in the tropospheric oxidizing capacity in the Southern Hemisphere.

  2. 国内外 VOCs 排放标准体系研究%Study of Emission Standards System of VOCs at Home and Abroad

    Institute of Scientific and Technical Information of China (English)

    罗斌; 蒋燕; 王斌

    2014-01-01

    It had important significance to develop VOCs emission standards for controlling VOCs emissions, improving air quality, and protecting human health and ecological environment. The characteristics of emission standards system of VOCs at home and abroad were analyzed, and some suggestions on the development of VOCs emission standards were proposed that toxicity and emissions of pollutants, particular pollutants of key industries should be considered when developing standards, and establishing emission standards system of VOCs giving priority to industry standards.%制定VOCs排放标准对于控制VOCs排放量,改善环境空气质量,保护人体健康和生态环境有重要意义。分析了国内外VOCs排放标准体系的特点,提出我国制定VOCs排放标准的几点建议,即标准制定过程中应考虑污染物毒性和排放量大小,考虑控制重点行业的特征污染物,并建立以行业排放标准为主的VOCs排放标准体系。

  3. Photolysis of the antidepressants amisulpride and desipramine in wastewaters: Identification of transformation products formed and their fate

    Energy Technology Data Exchange (ETDEWEB)

    Gros, Meritxell [Commonwealth Scientific and Industrial Research Organization (CSIRO), Land and Water Flagship, Waite Campus, Urrbrae, 5064 Adelaide, SA (Australia); Swedish University of Agricultural Sciences (SLU), Department of Aquatic Sciences and Assessment, Lennart Hjelms väg 9, 75007 Uppsala (Sweden); Williams, Mike, E-mail: Mike.Williams@csiro.au [Commonwealth Scientific and Industrial Research Organization (CSIRO), Land and Water Flagship, Waite Campus, Urrbrae, 5064 Adelaide, SA (Australia); Llorca, Marta; Rodriguez-Mozaz, Sara [Catalan Institute for Water Research (ICRA), Scientific and Technological Park of the University of Girona, C/Emili Grahit, 101 Girona (Spain); Barceló, Damià [Catalan Institute for Water Research (ICRA), Scientific and Technological Park of the University of Girona, C/Emili Grahit, 101 Girona (Spain); Water and Soil Quality Research Group, Department of Environmental IDAEA-CSIC, Jordi Girona 18-26, E-08034 Barcelona (Spain); Kookana, Rai S. [Commonwealth Scientific and Industrial Research Organization (CSIRO), Land and Water Flagship, Waite Campus, Urrbrae, 5064 Adelaide, SA (Australia)

    2015-10-15

    Attenuation of pharmaceuticals due to natural sunlight is expected to be an important removal pathway in wastewater treatment plants using treatment lagoon systems. In this work, the photolysis of two antidepressants, amisulpride and desipramine, has been investigated in both ultrapure water and wastewater under simulated solar irradiation. Results showed that for amisulpride short irradiation times (t{sub 1/2} approximately 3 h in pure water and 4 h in wastewater) were adequate to degrade the parent compound while a longer exposure period was required for desipramine (t{sub 1/2} of approximately 36 h in pure water), although its degradation is enhanced almost three times by indirect photolysis in wastewaters. A significant number of transformation products (TPs) were identified for both pharmaceuticals by high-resolution mass spectrometry. In general, TPs formed are not persistent although acute toxicity tests for desipramine and its TPs showed an increase of the mixture toxicity after solar irradiation, suggesting that some TPs may be more toxic than the parent compound. In wastewaters collected from treatment lagoons, only amisulpride and one of its major TPs, TP 357, were detected. This indicates that long solar exposure times may be necessary for an effective elimination of these substances in lagoon systems or that photolysis may not be the main removal pathway for these particular compounds. - Highlights: • Photolysis of both compounds resulted in several transformation products, some of which were previously unknown. • Short irradiation times may be adequate to degrade amisulpride whereas a longer exposure is required for desipramine. • Transformation of desipramine was enhanced by about three times due to indirect photolysis in wastewaters. • For desipramine, mixture acute toxicity increased after solar irradiation. • Photolysis is unlikely to be the main removal pathway for the two antidepressants during wastewater treatment.

  4. Extended Research on Detection of Deception Using Volatile Organic Compound (VOC) Emissions

    Energy Technology Data Exchange (ETDEWEB)

    Center for Human Reliability Studies

    2006-06-01

    A system that captures and analyzes volatile organic compound (VOC) emissions from skin surfaces may offer a viable alternative method to the polygraph instrument currently in use for detecting deception in U.S. government settings. Like the involuntary autonomic central nervous system response data gathered during polygraph testing, VOC emissions from the skin may provide data that can be used to detect stress caused by deception. Detecting VOCs, then, may present a noninvasive, non-intrusive method for observing, recording, and quantifying evidence of stress or emotional change.

  5. Study on characteristics of double surface VOC emissions from dry flat-plate building materials

    Institute of Scientific and Technical Information of China (English)

    WANG Xinke; ZHANG Yinping; ZHAO Rongyi

    2006-01-01

    This paper sets up an analytic model of double surface emission of volatile organic compound (VOC) from dry, flat-plate building materials. Based on it, the influence of factors including air change rate, loading factor of materials in the room, mass diffusion coefficient, partition coefficient, convective mass transfer coefficient, thickness of materials, asymmetric convective flow and initial VOC concentration distribution in the building material on emission is discussed. The conditions for simplifying double surface emission into single surface emission are also discussed. The model is helpful to assess the double surface VOC emission from flat-plate building materials used in indoor furniture and space partition.

  6. Pressure dependence of the deuterium isotope effect in the photolysis of formaldehyde by ultraviolet light

    Directory of Open Access Journals (Sweden)

    E. J. K. Nilsson

    2010-04-01

    Full Text Available The pressure dependence of the relative photolysis rate of HCHO vs. HCDO has been investigated for the first time, using a photochemical reactor at the University of Copenhagen. The dissociation of HCHO vs. HCDO using a UVA lamp was measured at total bath gas pressures of 50, 200, 400, 600 and 1030 mbar. The products of formaldehyde photodissociation are either H2 + CO (molecular channel or HCO + H (radical channel, and a photolysis lamp was chosen to emit light at wavelengths that greatly favor the molecular channel. The isotope effect in the dissociation, kHCHO/kHCDO, was found to depend strongly on pressure, varying from 1.1 + 0.15/−0.1 at 50 mbar to 1.75±0.10 at 1030 mbar. The results can be corrected for radical channel contribution to yield the kinetic isotope effect for the molecular channel; i.e. the KIE in the production of molecular hydrogen. This is done and the results at 1030 mbar are discussed in relation to previous studies at ambient pressure. In the atmosphere the relative importance of the two product channels changes with altitude as a result of changes in pressure and actinic flux. The study demonstrates that the δD of photochemical hydrogen produced from formaldehyde will increase substantially as pressure decreases.

  7. Photolysis of Caged-GABA Rapidly Terminates Seizures In Vivo: Concentration and Light Intensity Dependence.

    Science.gov (United States)

    Wang, Dan; Yu, Zhixin; Yan, Jiaqing; Xue, Fenqin; Ren, Guoping; Jiang, Chenxi; Wang, Weimin; Piao, Yueshan; Yang, Xiaofeng

    2017-01-01

    The therapy of focal epilepsy remains unsatisfactory for as many as 25% of patients. The photolysis of caged-γ-aminobutyric acid (caged-GABA) represents a novel and alternative option for the treatment of intractable epilepsy. Our previous experimental results have demonstrated that the use of blue light produced by light-emitting diode to uncage ruthenium-bipyridine-triphenylphosphine-c-GABA (RuBi-GABA) can rapidly terminate paroxysmal seizure activity both in vitro and in vivo. However, the optimal concentration of RuBi-GABA, and the intensity of illumination to abort seizures, remains unknown. The aim of this study was to explore the optimal anti-seizure effects of RuBi-GABA by using implantable fibers to introduce blue light into the neocortex of a 4-aminopyridine-induced acute seizure model in rats. We then investigated the effects of different combinations of RuBi-GABA concentrations and light intensity upon seizure. Our results show that the anti-seizure effect of RuBi-GABA has obvious concentration and light intensity dependence. This is the first example of using an implantable device for the photolysis of RuBi-GABA in the therapy of neocortical seizure, and an optimal combination of RuBi-GABA concentration and light intensity was explored. These results provide important experimental data for future clinical translational studies.

  8. Laser flash-photolysis and gas discharge in N2O-containing mixture: kinetic mechanism

    Science.gov (United States)

    Kosarev, Ilya; Popov, Nikolay; Starikovskaia, Svetlana; Starikovskiy, Andrey; mipt Team

    2011-10-01

    The paper is devoted to further experimental and theoretical analysis of ignition by ArF laser flash-photolysis and nanosecond discharge in N2O-containing mixture has been done. Additional experiments have been made to assure that laser emission is distributed uniformly throughout the cross-section. The series of experiments was proposed and carried out to check validity of O(1D) determination in experiments on plasma assisted ignition initiated by flash-photolysis. In these experiments, ozone density in the given mixture (mixture composition and kinetics has been preliminary analyzed) was measured using UV light absorption in Hartley band. Good coincidence between experimental data and results of calculations have been obtained Temporal behavior of energy input, electric field and electric current has been measured and analyzed. These data are considered as initial conditions for numerical modeling of the discharge in O2:N2O:H2:Ar = 0.3:1:3:5 mixture. Ion-molecular reactions and reactions of active species production in Ar:H2:O2:N2O mixture were analyzed. The set of reactions to describe chemical transformation in the system due to the discharge action has been selected.

  9. UV photolysis of diclofenac in water; kinetics, degradation pathway and environmental aspects.

    Science.gov (United States)

    Kovacic, Marin; Juretic Perisic, Daria; Biosic, Martina; Kusic, Hrvoje; Babic, Sandra; Loncaric Bozic, Ana

    2016-08-01

    In this study, the photolysis behavior of commonly used anti-inflammatory drug diclofenac (DCF) was investigated using UV-C and UV-A irradiation. In that purpose, DCF conversion kinetics, mineralization of organic content, biodegradability, and toxicity were monitored and compared. The results showed different kinetics of DCF conversion regarding the type of UV source applied. However, in both cases, the mineralization extent reached upon complete DCF conversion is rather low (≤10 %), suggesting that the majority of DCF was transformed into by-products. Formation/degradation of main degradation by-products was monitored using high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS), whereas different profiles were obtained by UV-C and UV-A photolysis. The results of bioassays revealed that biodegradability of DCF solutions remained low through the applied treatments. The toxicity of irradiated DCF solutions was evaluated using Vibrio fischeri. A significant reduction of toxicity, especially in the case of UV-A radiation, was observed upon complete degradation of DCF. In addition to toxicity reduction, calculated Log K OW values of DCF degradation by-products indicate their low potential for bioaccumulation (Log K OW ≤ 3) in comparison to the parent substance.

  10. Direct measurements of NO{sub 2} photolysis rates for Mexico City

    Energy Technology Data Exchange (ETDEWEB)

    Castro, T.; Ruiz-Suarez, L. G.; Gay, C. [Centro de Ciencias de la Atmosfera, UNAM, Mexico, D.F. (Mexico); Helguera, M. [Centro Nacional de Investigacion y Desarrollo Tecnologico, SEP, Cuernavaca, Mor. (Mexico); Ruiz-Suarez, J. C. [Departamento de Fisica Aplicada, CINVESTAV del IPN, Unidad Merida, Merida, Yucatan, (Mexico)

    1995-07-01

    Direct measurements of the rate of NO{sub 2} photolysis to NO and O({sup 3}P) are reported as photolysis frequencies J (NO{sub 2}) for Mexico City. These frequencies were measured using a flow reactor, where a known concentration of NO{sub 2} was photolysed for different experimental exposure times. Ultraviolet (UV) radiation was measured with an Eppley UV radiometer. Comparisons with calculated values using a radiation transfer model, and Madronich's formula are shown. [Spanish] Se reportan medidas de las constantes de fotolisis del NO{sub 2} a NO y O({sup 3}P) como frecuencias de fotolisis J(NO{sub 2}) para la Ciudad de Mexico. Estas frecuencias se midieron usando un reactor, en donde una concentracion conocida de NO{sub 2} se fotodisocia para diferentes tiempos de exposicion. La radiacion ultravioleta (UV) se midio con un radiometro Eppley. Se muestra una comparacion con valores calculados usando un modelo de transferencia y la formula de Madronich.

  11. Photolysis and Fluorescence in the /delta and /epsilon Bands of Thermospheric NO

    Science.gov (United States)

    Yonker, J. D.; Bailey, S. M.; Paxton, L. J.

    2008-12-01

    Recent measurements of the oscillator strengths (Yoshino et al, 2006) and predissociation rates (Luque and Crosley, 2000) for the δ and ɛ band systems of nitric oxide (NO) suggest a reevaluation of the NO photolysis rate. It is well-known that the dominant contribution throughout the atmosphere is due to dissociation in the δ(0,0) and δ (1,0) bands. However, above 90 km, attenuation of the solar VUV irradiance due to the O2 Schumann-Runge system is diminished and the contribution of the δ(2,0), ɛ(1,0), and ɛ(2,0) bands to the photolysis rate becomes increasingly significant. In this talk it is shown that the contribution from these bands rises from 16% at 100km to 26% above 120 km. As the ratio of the radiative to predissociation rates for the δ(0,0), ɛ(0,0), ɛ(1,0), and ɛ(2,0) bands is sensitive to the rotational level, expected fluorescence from these bands is also presented using data from the Student Nitric Oxide Explorer (SNOE).

  12. Photolysis and cellular toxicities of the organic ultraviolet filter chemical octyl methoxycinnamate and its photoproducts.

    Science.gov (United States)

    Stein, Hannah V; Berg, Courtney J; Maung, Jessica N; O'Connor, Lauren E; Pagano, Alexandra E; MacManus-Spencer, Laura A; Paulick, Margot G

    2017-06-21

    Organic ultraviolet filter chemicals (UVFCs) are the active ingredients used in many sunscreens to protect the skin from UV light; these chemicals have been detected in numerous aquatic environments leading to concerns about how they might affect aquatic organisms and humans. One commonly used organic UVFC is octyl methoxycinnamate (OMC), better known by its commercial name, octinoxate. Upon exposure to UV light, OMC degrades rapidly, forming numerous photoproducts, some of which have been previously identified. In this study, we isolated and completely characterized the major products of OMC photolysis, including the two major stable OMC cyclodimers. One of these cyclodimers is a δ-truxinate, resulting from a head-to-head dimerization of two OMC molecules, and the other cyclodimer is an α-truxillate, resulting from a head-to-tail dimerization of two OMC molecules. Additionally, the cellular toxicities of the individual photoproducts were determined; it was found that the parent UVFC, OMC, 4-methoxybenzaldehyde, and two cyclodimers are significantly toxic to cells. The photoproduct 2-ethylhexanol is not cytotoxic, demonstrating that different components of OMC photolysate contribute differently to its cellular toxicity. This study thus provides an enhanced understanding of OMC photolysis and gives toxicity data that can be used to better evaluate OMC as a sunscreen agent.

  13. Synergistic effect of proanthocyanidin on the bactericidal action of the photolysis of H2O2.

    Science.gov (United States)

    Ikai, Hiroyo; Nakamura, Keisuke; Kanno, Taro; Shirato, Midori; Meirelles, Luiz; Sasaki, Keiichi; Niwano, Yoshimi

    2013-01-01

    The in vitro antibacterial activity of the hydroxyl radical generation system by the photolysis of H2O2 in combination with proanthocyanidin, which refers to a group of polyphenolic compounds, was examined. Bactericidal activity of photo-irradiated H2O2 at 405 nm against Streptococcus mutans, a major pathogen of dental caries, was augmented in the presence of proanthocyanidin, whose bactericidal effect by itself was very poor, in a concentration-dependent manner. This combination was also proven effective against Porphyromonas gingivalis, a major pathogen of periodontitis. It is speculated that H2O2, generated from photo-irradiated proanthocyanidin around the bacterial cells, is photolyzed to the hydroxyl radical, which would in turn affect the membrane structure and function of the bacterial cells, resulting in augmented sensitivity of bacterial cells to the disinfection system utilizing the photolysis of H2O2. The present study suggests that the combination of H2O2 and proanthocyanidin works synergistically to kill bacteria when photo-irradiated.

  14. Selective formation of triplet alkyl nitrenes from photolysis of beta-azido-propiophenone and their reactivity.

    Science.gov (United States)

    Singh, Pradeep N D; Mandel, Sarah M; Sankaranarayanan, Jagadis; Muthukrishnan, Sivaramakrishnan; Chang, Mingxin; Robinson, Rachel M; Lahti, Paul M; Ault, Bruce S; Gudmundsdóttir, Anna D

    2007-12-26

    Photolysis of beta-azido propiophenone derivatives, 1, with built-in sensitizer units, leads to selective formation of triplet alkyl nitrenes 2 that were detected directly with laser flash photolysis (lambdamax = 325 nm, tau = 27 ms) and ESR spectroscopy (|D/hc| = 1.64 cm-1, |E/hc| = 0.004 cm-1). Nitrenes 2 were further characterized with argon matrix isolation, isotope labeling, and molecular modeling. The triplet alkyl nitrenes are persistent intermediates that do not abstract H-atoms from the solvent but do decay by dimerizing with another triplet nitrene to form azo products, rather than reacting with an azide precursor. The azo dimer tautomerizes and rearranges to form heterocyclic compound 3. Nitrene 2a, with an n,pi* configuration as the lowest triplet excited state of the its ketone sensitizer moiety, undergoes intramolecular 1,4-H-atom abstraction to form biradical 6, which was identified by argon matrix isolation, isotope labeling, and molecular modeling. beta-Azido-p-methoxy-propiophenone, with a pi,pi* lowest excited state of its triplet sensitizer moiety, does not undergo any secondary photoreactions but selectively yields only triplet alkyl nitrene intermediates that dimerize to form 3b.

  15. Efficiencies and Physical Principles of Various Solar Energy Conversion Processes Leading to the Photolysis of Water

    Energy Technology Data Exchange (ETDEWEB)

    Bergene, T.

    1995-12-31

    In the application of solar energy, hydrogen is likely to be used as an energy carrier and a storage medium. Production of molecular hydrogen and oxygen from water requires energy input, which may come from solar energy in various ways. This thesis begins with a literature survey of the different conversion processes and the efficiencies, which is an introduction to a series of enclosed papers. These papers are: (1) Trapping of Minority Charge Carriers at Irradiated Semiconductor/Electrolyte Heterojunctions, (2) Model Calculations on Flat-Plate Solar Heat Collector With Integrated Solar Cells, and (3) Efficiencies and Physical Principles of Photolysis of Water By Microalgae. In the papers, The qualitative features of the ``illumination-current``-characteristic curve are deduced. The hypothesis is that trapping originates in some specific cases because of confinement, which leads to charge injections into energy states above that corresponding to the band edge. The quantitative features of certain hybrid photovoltaic/thermal configuration are deduced. An analysis of the theoretical and realizable efficiencies of the photolysis of water by micro algae is given. 151 refs., 18 figs., 1 table

  16. Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

    Science.gov (United States)

    Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

    2016-09-01

    Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

  17. Laser Photolysis and Thermolysis of Organic Selenides and Tellurides for Chemical Gas-phase Deposition of Nanostructured Materials

    Directory of Open Access Journals (Sweden)

    Josef Pola

    2009-03-01

    Full Text Available Laser radiation-induced decomposition of gaseous organic selenides and tellurides resulting in chemical deposition of nanostructured materials on cold surfaces is reviewed with regard to the mechanism of the gas-phase decomposition and properties of the deposited materials. The laser photolysis and laser thermolysis of the Se and Te precursors leading to chalcogen deposition can also serve as a useful approach to nanostructured chalcogen composites and IVA group (Si, Ge, Sn element chalcogenides provided that it is carried out simultaneously with laser photolysis or thermolysis of polymer and IVA group element precursor.

  18. Laser photolysis and thermolysis of organic selenides and tellurides for chemical gas-phase deposition of nanostructured materials.

    Science.gov (United States)

    Pola, Josef; Ouchi, Akihiko

    2009-03-12

    Laser radiation-induced decomposition of gaseous organic selenides and tellurides resulting in chemical deposition of nanostructured materials on cold surfaces is reviewed with regard to the mechanism of the gas-phase decomposition and properties of the deposited materials. The laser photolysis and laser thermolysis of the Se and Te precursors leading to chalcogen deposition can also serve as a useful approach to nanostructured chalcogen composites and IVA group (Si, Ge, Sn) element chalcogenides provided that it is carried out simultaneously with laser photolysis or thermolysis of polymer and IVA group element precursor.

  19. Quantum yields for OH production from 193 and 248 nm photolysis of HNO3 and H2O2

    Science.gov (United States)

    Schiffman, A.; Nelson, D. D., Jr.; Nesbitt, D. J.

    1993-05-01

    Flash kinetic spectroscopy in a flow tube is used to measure at room temperature the absolute yields for OH production from 193 and 248 nm photolysis of HNO3 and H2O2. The OH radicals are produced by excimer laser photolysis and probed via direct absorption of high resolution tunable IR laser light. The results indicate quantum yields for both precursors at both wavelengths which are less than the maximum possible values of 1 for H2O2. The present measurements are discussed in light of contrasting results suggested from other work.

  20. STUDY ON THE PHOTOLYSIS MECHANISM OF POLYESTER FROM SUCCINIC ACID AND N-β-HYDROXYETHYL 2,2,6,6-TETRAMETHYL-4-HYDROXY PIPERIDINE (TINUVIN-622)

    Institute of Scientific and Technical Information of China (English)

    PAN Jiangqing; CUI Song

    1988-01-01

    The photolysis mechanism of polyester of succinic acid with N-β-hydroxyethyl 2,2,6,6-tetramethyl-4-hydroxy piperidine (Tinuvin-622) has been studied by instrumental analysis. The results show that Tinuvin-622 can be easily photolysed. Based on the results of IR, NMR, ESR, GPC, GC, MS, the photolysis mechanism of Tinuvin-622 has been proposed.

  1. An unheated permeation device for calibrating atmospheric VOC measurements

    Directory of Open Access Journals (Sweden)

    J. Brito

    2011-05-01

    Full Text Available The development of an unpowered permeation device for continuous calibration of in-situ instruments measuring atmospheric volatile organic compounds (VOCs is described. Being lightweight and compact, and containing only negligible amounts of chemicals, the device is especially suited for field use such as onboard aircraft. Its speciality is to maintain the permeation process in thermal equilibrium, i.e. the instantaneous permeation rate can be ascribed via a simple temperature measurement. This equilibrium state is maintained by a combination of three features: (i a thin PTFE membrane as permeation medium which guarantees short stabilization times, (ii a water bath as heat buffer, and (iii a vacuum-panel based insulation, in which features (ii and (iii minimize temperature drifts. The uncertainty of the permeation rate due to thermal non-equilibrium is kept below 1 %. An extensive theory part details the major permeation processes of gases through porous polymers, being Fick's diffusion, Knudsen flow, and viscous flow. Both the measured stabilization time and the measured temperature dependence of the permeation rate independently indicate that the permeation can be described by a viscous flow model, where diffusion of the gas molecules in large pores (having a diameter of >0.05 μm dominates.

  2. [Comparison Analysis of Economic and Engineering Control of Industrial VOCs].

    Science.gov (United States)

    Wang, Yu-fei; Liu, Chang-xin; Cheng, Jie; Hao, Zheng-ping; Wang, Zheng

    2015-04-01

    Volatile organic compounds (VOCs) pollutant has become China's major air pollutant in key urban areas like sulfur dioxide, nitrogen oxides and particulate matter. It is mainly produced from industry sectors, and engineering control is one of the most important reduction measures. During the 12th Five-Year Plan, China decides to invest 40 billion RMB to build pollution control projects in key industry sectors with annual emission reduction of 605 000 t x a(-1). It shows that China attaches a great importance to emission reduction by engineering projects and highlights the awareness of engineering reduction technologies. In this paper, a macroeconomic model, namely computable general equilibrium model, (CGE model) was employed to simulate engineering control and economic control (imposing environmental tax). We aim to compare the pros and cons of the two reduction policies. Considering the economic loss of the whole country, the environmental tax has more impacts on the economy system than engineering reduction measures. We suggest that the central government provides 7 500 RMB x t(-1) as subsidy for enterprises in industry sectors to encourage engineering reduction.

  3. An unheated permeation device for calibrating atmospheric VOC measurements

    Directory of Open Access Journals (Sweden)

    J. Brito

    2011-10-01

    Full Text Available The development of an unpowered permeation device for continuous calibration of in-situ instruments measuring atmospheric volatile organic compounds (VOCs is described. Being lightweight and compact, and containing only negligible amounts of chemicals, the device is especially suited for field use such as on board aircraft. Its speciality is to maintain the permeation process in thermal equilibrium, so that the instantaneous permeation rate can be ascribed to a simple temperature measurement. This equilibrium state is maintained by a combination of three features: (i a thin PTFE membrane as permeation medium which guarantees short stabilization times, (ii a water bath as heat buffer, and (iii a vacuum-panel based insulation, in which features (ii and (iii minimize temperature drifts to ~30 mK h−1 per Kelvin temperature difference to the environment. The respective uncertainty of the permeation rate due to thermal non-equilibrium is kept below 1%. An extensive theory part details the major permeation processes of gases through porous polymers, being Fick's diffusion, Knudsen flow, and viscous flow. Both the measured stabilization time and the measured temperature dependence of the permeation rate independently indicate that the permeation can be described by a viscous flow model, where diffusion of the gas molecules in large pores (having a diameter of >0.05 μm dominates.

  4. Measurements of VOCs in Mexico City during the MILAGRO Campaign

    Science.gov (United States)

    Baker, A. K.; Beyersdorf, A. J.; Blake, N. J.; Meinardi, S.; Atlas, E.; Rowland, F.; Blake, D. R.

    2006-12-01

    During March of 2006 we participated in MILAGRO (Megacities Initiative: Local and Global Research Observations), a multi-platform campaign to measure pollutants in and in outflow from the Mexico City metropolitan area. As part of MILAGRO we collected whole air canister samples at two Mexico City ground sites: the Instituto Mexicano del Petroleo, located in the city, northeast of the center, and the Universidad Technologica de Tecamac, a suburban site approximately 50 km northeast of the city center. Samples were also collected in various other locations throughout Mexico City. Over 300 whole air samples were collected and analyzed for a wide range of volatile organic compounds (VOCs) including methane, carbon monoxide, nonmethane hydrocarbons (NMHCs) and halocarbons. Propane was the most abundant NMHC at both the urban and suburban locations, with mixing ratios frequently in excess of 10 parts per billion at both locations. This is likely the result of the widespread use of liquefied petroleum gas (LPG) of which propane is the major component. For most species, median mixing ratios at the urban sites were significantly greater than at the suburban site. Here we compare results from both urban and suburban locations and also examine the influence of transport on the composition of outflow from Mexico City.

  5. Safe handling of potential peroxide forming compounds and their corresponding peroxide yielded derivatives.

    Energy Technology Data Exchange (ETDEWEB)

    Sears, Jeremiah Matthew; Boyle, Timothy J.; Dean, Christopher J.

    2013-06-01

    This report addresses recent developments concerning the identification and handling of potential peroxide forming (PPF) and peroxide yielded derivative (PYD) chemicals. PPF chemicals are described in terms of labeling, shelf lives, and safe handling requirements as required at SNL. The general peroxide chemistry concerning formation, prevention, and identification is cursorily presented to give some perspective to the generation of peroxides. The procedure for determining peroxide concentrations and the proper disposal methods established by the Hazardous Waste Handling Facility are also provided. Techniques such as neutralization and dilution are provided for the safe handling of any PYD chemicals to allow for safe handling. The appendices are a collection of all available SNL documentation pertaining to PPF/PYD chemicals to serve as a single reference.

  6. Reactivity of ambient volatile organic compounds (VOCs) in summer of 2004 in Beijing

    Institute of Scientific and Technical Information of China (English)

    Shan Huang; Min Shao; Sihua Lu; Ying Liu

    2008-01-01

    Ambient volatile organic compounds (VOCs) were sampled at six sites in Beijing in the summer of 2004 and analyzed byGCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates (L<,OH) and ozone formationpotentials (OFPs). Top 15 reactive species, mainly alkenes and aromatics, were identified by these two methods, and accounted formore than 70% of total reactivity of VOCs. In urban areas, isoprene was the most reactive species in term of OH loss rate,contributing 11.4% to the Loft of VOCs. While toluene, accounting for 9.4% of OFPs, appeared to have a long-time role in thephotochemical processes. Tongzhou site is obviously influenced by local chemical industry, but the other five sites showed typicalurban features influenced mainly by vehicular emissions.2008 Min Shao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  7. An analytical solution for VOCs emission from multiple sources/sinks in buildings

    Institute of Scientific and Technical Information of China (English)

    DENG BaoQing; YU Bo; Chang Nyung KIM

    2008-01-01

    An analytical solution is presented to describe the emission/sorption of volatile organic compounds (VOCs) from/on multiple single-layer materials coexisting in buildings. The diffusion of VOCs within each material is described by a transient diffusion equation. All diffusion equations are coupled with each other through the equation of mass conservation in the air. The analytical solution is validated by the experimental data in literature, Compared to the one-material case, the coexistence of multiple materials may decrease the emission rate of VOCs from each material. The smaller the diffusion coef-ficient is, the more the emission rate decreases. Whether a material is a source or a sink in the case of multiple materials coexisting is not affected by the diffusion coefficient. For the case of multiple mate-rials with different partition coefficients, a material with a high partition coefficient may become a sink. This may promote the emission of VOCs from other materials.

  8. EVALUATION AND PERFORMANCE ASSESSMENT OF INNOVATIVE LOW-VOC CONTACT ADHESIVES IN WOOD LAMINATING OPERATIONS

    Science.gov (United States)

    The report gives results of an evaluation and assessment of the perfor-mance, economics, and emission reduction potential upon application of low-volatile organic compound (VOC) waterborne contact adhesive formulations specifically ina manual laminating operation for assembling s...

  9. VocMat projekt - uudsed e-õppe võimalused turismiasjalistele / Heli Tooman

    Index Scriptorium Estoniae

    Tooman, Heli, 1949-

    2008-01-01

    Turismivaldkonna spetsialistidele mõeldud koolitusprojektist VocMat (Vocational Management Training for the Tourism Industry). Projekti partneriteks Eestis on Ettevõtluse Arendamise Sihtasutuse Turismiarenduskeskus ja Tartu Ülikooli Pärnu kolledzh. Lisa: Kokkuvõte

  10. VocMat projekt - uudsed e-õppe võimalused turismiasjalistele / Heli Tooman

    Index Scriptorium Estoniae

    Tooman, Heli, 1949-

    2008-01-01

    Turismivaldkonna spetsialistidele mõeldud koolitusprojektist VocMat (Vocational Management Training for the Tourism Industry). Projekti partneriteks Eestis on Ettevõtluse Arendamise Sihtasutuse Turismiarenduskeskus ja Tartu Ülikooli Pärnu kolledzh. Lisa: Kokkuvõte

  11. Phytic Acid Inhibits Lipid Peroxidation In Vitro

    Directory of Open Access Journals (Sweden)

    Alicja Zajdel

    2013-01-01

    Full Text Available Phytic acid (PA has been recognized as a potent antioxidant and inhibitor of iron-catalyzed hydroxyl radical formation under in vitro and in vivo conditions. Therefore, the aim of the present study was to investigate, with the use of HPLC/MS/MS, whether PA is capable of inhibiting linoleic acid autoxidation and Fe(II/ascorbate-induced peroxidation, as well as Fe(II/ascorbate-induced lipid peroxidation in human colonic epithelial cells. PA at 100 μM and 500 μM effectively inhibited the decay of linoleic acid, both in the absence and presence of Fe(II/ascorbate. The observed inhibitory effect of PA on Fe(II/ascorbate-induced lipid peroxidation was lower (10–20% compared to that of autoxidation. PA did not change linoleic acid hydroperoxides concentration levels after 24 hours of Fe(II/ascorbate-induced peroxidation. In the absence of Fe(II/ascorbate, PA at 100 μM and 500 μM significantly suppressed decomposition of linoleic acid hydroperoxides. Moreover, PA at the tested nontoxic concentrations (100 μM and 500 μM significantly decreased 4-hydroxyalkenal levels in Caco-2 cells which structurally and functionally resemble the small intestinal epithelium. It is concluded that PA inhibits linoleic acid oxidation and reduces the formation of 4-hydroxyalkenals. Acting as an antioxidant it may help to prevent intestinal diseases induced by oxygen radicals and lipid peroxidation products.

  12. Phytic acid inhibits lipid peroxidation in vitro.

    Science.gov (United States)

    Zajdel, Alicja; Wilczok, Adam; Węglarz, Ludmiła; Dzierżewicz, Zofia

    2013-01-01

    Phytic acid (PA) has been recognized as a potent antioxidant and inhibitor of iron-catalyzed hydroxyl radical formation under in vitro and in vivo conditions. Therefore, the aim of the present study was to investigate, with the use of HPLC/MS/MS, whether PA is capable of inhibiting linoleic acid autoxidation and Fe(II)/ascorbate-induced peroxidation, as well as Fe(II)/ascorbate-induced lipid peroxidation in human colonic epithelial cells. PA at 100 μM and 500 μM effectively inhibited the decay of linoleic acid, both in the absence and presence of Fe(II)/ascorbate. The observed inhibitory effect of PA on Fe(II)/ascorbate-induced lipid peroxidation was lower (10-20%) compared to that of autoxidation. PA did not change linoleic acid hydroperoxides concentration levels after 24 hours of Fe(II)/ascorbate-induced peroxidation. In the absence of Fe(II)/ascorbate, PA at 100 μM and 500 μM significantly suppressed decomposition of linoleic acid hydroperoxides. Moreover, PA at the tested nontoxic concentrations (100 μM and 500 μM) significantly decreased 4-hydroxyalkenal levels in Caco-2 cells which structurally and functionally resemble the small intestinal epithelium. It is concluded that PA inhibits linoleic acid oxidation and reduces the formation of 4-hydroxyalkenals. Acting as an antioxidant it may help to prevent intestinal diseases induced by oxygen radicals and lipid peroxidation products.

  13. Electronic structure and bonding in crystalline peroxides

    Science.gov (United States)

    Königstein, Markus; Sokol, Alexei A.; Catlow, C. Richard A.

    1999-08-01

    Hartree-Fock and density-functional PW91 theories as realized in the CRYSTAL95 code have been applied to investigate the structural and electronic properties of Ba, Sr, and Ca peroxide materials with the calcium carbide crystal structure, results for which are compared with those for the corresponding oxides. Special attention is paid to the stabilization of the peroxide molecular ion O2-2 in the ionic environment provided by the lattice, and to chemical bonding effects. In order to describe the covalent bonding within the O2-2 ion and the polarization of the O- ion in the crystal electrostatic field, it is essential to include an account of the effects of electron correlation. The PW91 density functional has allowed us to reproduce the crystallographic parameters within a 3% error. The chemical bonding within the peroxide molecular ion has a complex nature with a balance between the weak covalent bond of σz type and the strong electrostatic repulsion of the closed-shell electron groups occupying O 2s and O 2px and 2py states. Compression of the peroxide ion in the ionic crystals gives rise to an excessive overlap of the O 2s closed shells of the two O- ions of a peroxide molecular ion O2-2, which in turn determines the antibonding character of the interaction and chemical bonding in the O2-2 molecular ion.

  14. Leaf level VOC emissions of single plants from Amazonian and Mediterranean ecosystems: Ontogeny and flooding as stress factor for VOC emissions

    OpenAIRE

    Bracho Nunez, Araceli

    2010-01-01

    Die Vegetation ist die wichtigste Quelle von organischen flüchtigen Verbindungen (auf Englisch volatile organic compounds,VOCs), die einen bemerkenswerten Einfluss auf der Chemie und Physik der Atmosphäre haben. VOCs beeinflussen die oxidative Kapazität der Atmosphäre und tragen zu der Bildung und zum Wachstum von sekundären organischen Aerosolen bei, welche einerseits eine Streuung und Reflektierung der Energie verursachen und andererseits sich an der Bildung und Entwicklung von Wolken betei...

  15. Quantitative assessment of industrial VOC emissions in China: Historical trend, spatial distribution, uncertainties, and projection

    Science.gov (United States)

    Zheng, Chenghang; Shen, Jiali; Zhang, Yongxin; Huang, Weiwei; Zhu, Xinbo; Wu, Xuecheng; Chen, Linghong; Gao, Xiang; Cen, Kefa

    2017-02-01

    The temporal trends of industrial volatile organic compound (VOC) emissions was comprehensively summarized for the 2011 to 2013 period, and the projections for 2020 to 2050 for China were set. The results demonstrate that industrial VOC emissions in China increased from 15.3 Tg in 2011 to 29.4 Tg in 2013 at an annual average growth rate of 38.3%. Guangdong (3.45 Tg), Shandong (2.85 Tg), and Jiangsu (2.62 Tg) were the three largest contributors collectively accounting for 30.4% of the national total emissions in 2013. The top three average industrial VOC emissions per square kilometer were Shanghai (247.2 ton/km2), Tianjin (62.8 ton/km2), and Beijing (38.4 ton/km2), which were 12-80 times of the average level in China. The data from the inventory indicate that the use of VOC-containing products, as well as the production and use of VOCs as raw materials, as well as for storage and transportation contributed 75.4%, 10.3%, 9.1%, and 5.2% of the total emissions, respectively. ArcGIS was used to display the remarkable spatial distribution variation by allocating the emission into 1 km × 1 km grid cells with a population as surrogate indexes. Combined with future economic development and population change, as well as implementation of policy and upgrade of control technologies, three scenarios (scenarios A, B, and C) were set to project industrial VOC emissions for the years 2020, 2030, and 2050, which present the industrial VOC emissions in different scenarios and the potential of reducing emissions. Finally, the result shows that the collaborative control policies considerably influenced industrial VOC emissions.

  16. VOC emissions during outdoor ship painting and health-risk assessment

    Science.gov (United States)

    Malherbe, Laure; Mandin, Corinne

    Painting of ship external surfaces in building or repair shipyards generates significant emissions of volatile organic compounds (VOC) to the atmosphere. Such emissions have not been specifically regulated so far. The purpose of our study is therefore to evaluate the quantities and as far as possible the nature of the emitted VOC, to characterize the dispersion of these chemicals in the atmosphere and to assess the exposure and resulting health risks for surrounding populations. This study is focused on VOC emitted during outdoor work involving use of paints and solvents. VOC emissions are diffuse, since they come from the whole painted surfaces. A methodology for quantifying them is developed and tested, using information provided by ALSTOM—Chantiers de l'Atlantique and data found in paint technical sheets. Its reliability is checked against emission values established by ALSTOM or found in literature. Then, for two particular situations, construction on one hand, repair on the other hand, atmospheric dispersion of total VOC is simulated to assess the long-term impact (characterized by the plume extension and the annual mean concentrations) of these compounds. Finally, a health-risk assessment based on the estimates is carried out to evaluate the risks by inhalation for people living near the site. Considering the presumed composition of paints and the available reference toxicological values, total VOC are entirely assimilated to toluene. In both examples (construction and repair) and in the current state of knowledge, the calculated risk is not of health concern. Several ways for taking this study further are proposed: a more exhaustive collection of data relative to VOC and other substances contained in paints, on-site measurement of VOC in the ambient air, characterization of diffuse emissions related to other activities, such as purging or welding, and other pollutants, like particles.

  17. Volatile Organic Compound (VOC) Testing at Building 348, Kelly AFB, Texas.

    Science.gov (United States)

    1987-11-01

    At the request of HQ AFLC/ SGB , the USAFOEHL conducted a stack sampling survey to determine total volatile organic compounds (VOC) being emitted from...Occupational and Environmental Health Laboratory (USAFOEHL/ECQ). The survey was requested by HQ AFLC/ SGB .to estimate VOC emissions through each of...stardards. 2. Range and Sensitivity 2.1 This method was validated over the range of 1417-5940 mg/M at an atmospheric temperature and pressure of 24 0C

  18. Direct UV photolysis of selected pharmaceuticals, personal care products and endocrine disruptors in aqueous solution.

    Science.gov (United States)

    Carlson, Jules C; Stefan, Mihaela I; Parnis, J Mark; Metcalfe, Chris D

    2015-11-01

    Pharmaceuticals and personal care products (PPCPs), and endocrine disrupting compounds (EDCs) are micropollutants of emerging concern that have been detected in the aquatic environment and in some cases, in drinking water at nanogram per liter levels. The goal of this study was to evaluate the removal of 15 model PPCPs and EDCs from water by direct UV photolysis, using either low (LP)-or medium (MP) -pressure mercury vapor arc lamps. Some of the model compounds are either weak bases or weak acids, and therefore, the pKa values were determined or confirmed for those compounds using spectrophotometric titrations. The molar absorption coefficients of ionized and non-ionized forms were also determined. The quantum yields at 253.7 nm in phosphate buffer solutions of pH 7.2 were determined to be 0.033 ± 0.004 for sulfamethoxazole, 0.0035 ± 0.0008 for sulfachloropyridazine, 0.006 ± 0.002 for acetaminophen, 0.34 ± 0.07 for triclosan, 0.35 ± 0.14 for estrone, 0.08 ± 0.05 for 17α-ethinylestradiol, 0.086 ± 0.012 for ibuprofen. The quantum yield for 4-n-nonylphenol photolysis at 253.7 nm varied with the initial concentration from 0.32 ± 0.08 at 23 μg/L to 0.092 ± 0.006 at 230 μg/L. The pseudo-first order rate constants determined for direct photolysis at 253.7 nm of the studied micropollutants followed the order: triclosan ≈ sulfamethoxazole > 4-n-nonylphenol ≈ sulfachloropyridazine ≈ estrone > acetaminophen ≈ 17α-ethinylestradiol ≈ ibuprofen. In contrast to the results observed for the monochromatic radiation (LP lamp), all 15 model compounds photolyzed under exposure to the broadband radiation emitted by the MP lamp. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Nitrate ion photolysis in thin water films in the presence of bromide ions.

    Science.gov (United States)

    Richards, Nicole K; Wingen, Lisa M; Callahan, Karen M; Nishino, Noriko; Kleinman, Michael T; Tobias, Douglas J; Finlayson-Pitts, Barbara J

    2011-06-16

    Nitrate ions commonly coexist with halide ions in aged sea salt particles, as well as in the Arctic snowpack, where NO(3)(-) photochemistry is believed to be an important source of NO(y) (NO + NO(2) + HONO + ...). The effects of bromide ions on nitrate ion photochemistry were investigated at 298 ± 2 K in air using 311 nm photolysis lamps. Reactions were carried out using NaBr/NaNO(3) and KBr/KNO(3) deposited on the walls of a Teflon chamber. Gas phase halogen products and NO(2) were measured as a function of photolysis time using long path FTIR, NO(y) chemiluminescence and atmospheric pressure ionization mass spectrometry (API-MS). Irradiated NaBr/NaNO(3) mixtures show an enhancement in the rates of production of NO(2) and Br(2) as the bromide mole fraction (χ(NaBr)) increased. However, this was not the case for KBr/KNO(3) mixtures where the rates of production of NO(2) and Br(2) remained constant over all values of χ(KBr). Molecular dynamics (MD) simulations show that the presence of bromide in the NaBr solutions pulls sodium toward the solution surface, which in turn attracts nitrate to the interfacial region, allowing for more efficient escape of NO(2) than in the absence of halides. However, in the case of KBr/KNO(3), bromide ions do not appreciably affect the distribution of nitrate ions at the interface. Clustering of Br(-) with NO(3)(-) and H(2)O predicted by MD simulations for sodium salts may facilitate a direct intermolecular reaction, which could also contribute to higher rates of NO(2) production. Enhanced photochemistry in the presence of halide ions may be important for oxides of nitrogen production in field studies such as in polar snowpacks where the use of quantum yields from laboratory studies in the absence of halide ions would lead to a significant underestimate of the photolysis rates of nitrate ions.

  20. Investigation on Using SBS and Active Carbon Filler to Reduce the VOC Emission from Bituminous Materials

    Directory of Open Access Journals (Sweden)

    Peiqiang Cui

    2014-08-01

    Full Text Available Bituminous materials are playing a vital role in pavement design and the roofing industry because of outstanding properties. Unfortunately, bituminous materials will release volatile organic compounds (VOC, making them non-environmentally friendly. Therefore, technologies that can be used to decrease the VOC emission are urgently required. In this research, the VOC emission and material behaviors were analyzed and compared to investigate the possibility of adding styrene butadiene styrene (SBS and active carbon filler into bituminous materials to develop environmentally-friendly materials. Thermal gravimetric analysis-mass spectrometry (TG-MS and ultraviolet-visible spectroscopy testing (UV-Vis were employed to characterize the VOC emission process. Temperature sweep testing and frequency sweep testing were conducted to evaluate the rheological properties of bituminous materials. Research results indicated that the combined introduction of 4 wt% styrene butadiene styrene (SBS and 4 wt% active carbon filler cannot only significantly lower the VOC emission speed and amount, but also improve the deformation resistance behavior at a higher temperature. SBS and active carbon filler can be used to reduce the VOC emission form bituminous materials.

  1. Plant volatile organic compounds (VOCs) in ozone (O3) polluted atmospheres: the ecological effects.

    Science.gov (United States)

    Pinto, Delia M; Blande, James D; Souza, Silvia R; Nerg, Anne-Marja; Holopainen, Jarmo K

    2010-01-01

    Tropospheric ozone (O3) is an important secondary air pollutant formed as a result of photochemical reactions between primary pollutants, such as nitrogen oxides (NOx), and volatile organic compounds (VOCs). O3 concentrations in the lower atmosphere (troposphere) are predicted to continue increasing as a result of anthropogenic activity, which will impact strongly on wild and cultivated plants. O3 affects photosynthesis and induces the development of visible foliar injuries, which are the result of genetically controlled programmed cell death. It also activates many plant defense responses, including the emission of phytogenic VOCs. Plant emitted VOCs play a role in many eco-physiological functions. Besides protecting the plant from abiotic stresses (high temperatures and oxidative stress) and biotic stressors (competing plants, micro- and macroorganisms), they drive multitrophic interactions between plants, herbivores and their natural enemies e.g., predators and parasitoids as well as interactions between plants (plant-to-plant communication). In addition, VOCs have an important role in atmospheric chemistry. They are O3 precursors, but at the same time are readily oxidized by O3, thus resulting in a series of new compounds that include secondary organic aerosols (SOAs). Here, we review the effects of O3 on plants and their VOC emissions. We also review the state of current knowledge on the effects of ozone on ecological interactions based on VOC signaling, and propose further research directions.

  2. Photolysis of alpha-xylyl chlorides: an efficient deep-UV photoinitiating system for radical and cationic polymerization.

    Science.gov (United States)

    Ponce, Patricia; Catalani, Luiz Henrique

    2004-07-01

    Photoacid generators (PAG) are chemical systems where light absorption renders strong acid formation, typically with quantum yields greater than one. Many compounds bearing halogen atoms are reported to produce hydrogen halides upon photolysis. Here, alpha-chloroxylene derivatives (ortho, meta and para) were subject of a photolysis study in order to: (i) determine the operative mechanism, (ii) identify the products formed and (iii) quantify the amount of HCl formed. Product structure and quantum yields of HCl formation where determined for the photolysis of alpha-chloro-o-xylene (1), alpha-chloro-m-xylene (2), alpha-chloro-p-xylene (3), alpha, alpha'-dichloro-o-xylene (4), alpha, alpha'-dichloro-m-xylene (5) and alpha, alpha'-dichloro-p-xylene (6) in apolar (benzene, cumene, ethylbenzene, toluene and isooctane) and polar (methanol, n-propanol, isopropyl alcohol) solvents. Some of these compounds were analysed by laser flash photolysis in argon-purged isooctane as solvent to examine the possible reaction intermediates involved. The observed products are derived from typical radical reactions like recombination, dimerization and hydrogen abstraction from the starting compound or from solvents. The formation of HCl is expected as the result of C-Cl homolysis followed by hydrogen abstraction by chlorine atom. The results showed yields ranging from 1.2 to 18, depending on the conditions used. These numbers indicate the potential use of these compounds as PAG systems for the deep UV region.

  3. Photolysis of Low-Brominated Diphenyl Ethers and Their Reactive Oxygen Species-Related Reaction Mechanisms in an Aqueous System.

    Science.gov (United States)

    Wang, Mei; Wang, Huili; Zhang, Rongbo; Ma, Meiping; Mei, Kun; Fang, Fang; Wang, Xuedong

    2015-01-01

    To date, no report was concerned with participation of reactive oxygen species in waters during photolysis of low-brominated diphenyl ethers (LBDEs). Herein, we found that electron spin resonance (ESR) signals rapidly increased with increasing irradiation time in the solution of LBDEs and 4-oxo-TMP solutions. But this phenomenon did not occur in the presence of NaN3 (1O2 quencher) demonstrating generation of 1O2 in process of LBDEs photolysis. The indirect photolytic contribution rate for BDE-47 and BDE-28 was 18.8% and 17.3% via 1O2, and 4.9% and 6.6% via ·OH, respectively. Both D2O and NaN3 experiments proved that the indirect photolysis of LBDEs was primarily attributable to 1O2. The bimolecular reaction rate constants of 1O2 with BDE-47 and BDE-28 were 3.12 and 3.64 × 106 M-1 s-1, respectively. The rate constants for BDE-47 and BDE-28 (9.01 and 17.52 × 10-3 min-1), added to isopropyl alcohol, were very close to those (9.65 and 18.42 × 10-3 min-1) in water, proving the less indirect photolytic contribution of ·OH in water. This is the first comprehensive investigation examining the indirect photolysis of LBDEs in aqueous solution.

  4. Experimental investigation of incremental reactivity of di-tert-butyl peroxide

    Institute of Scientific and Technical Information of China (English)

    DU Lin; XU YongFu; GE MaoFa; JIA Long; YAO Li

    2007-01-01

    Large quantities of di-tert-butyl peroxide(DTBP)have been emitted into the troposphere due to human activities.Its role in the atmospheric photochemical reaction has not been understood.This study presents the results of the photochemical reactions of DTBP and NOx,which have been simulated in a self-made smog chamber under the temperature of(29±1)℃.Both the wall decays of ozone and NO2 could be neglected,compared to the results in simulative experiments.The effective intensity of UV light used in the experiments was 1.28x10-3s-1,which was expressed by the rate constant of NO2 photolysis in purified air.The reaction mechanism was proposed according to our results and reports of other researchers.The maximum values of incremental reactivity(IR)in the three simulative experiments were 9.53x10-2,5.23x10-2 and 3.78x10-2,respectively.The incremental reactivity decreased with the increase of initial concentrations of DTBP.The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.

  5. Hydrogen peroxide decomposition kinetics in aquaculture water

    DEFF Research Database (Denmark)

    Arvin, Erik; Pedersen, Lars-Flemming

    2015-01-01

    Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish...... facilitated by microbial enzyme activity. The model describes how the hydrogen peroxide removal declines and eventually stops at relatively low chemical oxygen demand (COD) concentrations. It is hypothesized that this is due to an enzyme deficit because it is destructed due to the reactive radicals created...

  6. Lipid peroxidation in adrenal and testicular microsomes.

    OpenAIRE

    1981-01-01

    Studies were carried out to determine the actions of and interactions between ascorbate, NADPH, Fe2+, and Fe3+ on lipid peroxidation in adrenal and testicular microsomes. Ascorbate-induced malonaldehyde production was maximal in adrenal and testicular microsomes at an ascorbate concentration of 1 X 10(-4)M. Fe2+, at levels between 10(-6) and 10(-3)M, produced concentration-dependent increases in lipid peroxidation in adrenal and testicular microsomes; Fe2+ had a far greater effect than Fe3+ i...

  7. Phytic Acid Inhibits Lipid Peroxidation In Vitro

    OpenAIRE

    Alicja Zajdel; Adam Wilczok; Ludmiła Węglarz; Zofia Dzierżewicz

    2013-01-01

    Phytic acid (PA) has been recognized as a potent antioxidant and inhibitor of iron-catalyzed hydroxyl radical formation under in vitro and in vivo conditions. Therefore, the aim of the present study was to investigate, with the use of HPLC/MS/MS, whether PA is capable of inhibiting linoleic acid autoxidation and Fe(II)/ascorbate-induced peroxidation, as well as Fe(II)/ascorbate-induced lipid peroxidation in human colonic epithelial cells. PA at 100 μM and 500 μM effectively inhibited the deca...

  8. Quantification of Methane and VOC Emissions from Natural Gas Production in Two Basins with High Ozone Events

    Science.gov (United States)

    Edie, R.; Robertson, A.; Snare, D.; Soltis, J.; Field, R. A.; Murphy, S. M.

    2015-12-01

    Since 2005, the Uintah Basin of Utah and the Upper Green River Basin of Wyoming frequently exceeded the EPA 8-hour allowable ozone level of 75 ppb, spurring interest in volatile organic compounds (VOCs) emitted during oil and gas production. Debate continues over which stage of production (drilling, flowback, normal production, transmission, etc.) is the most prevalent VOC source. In this study, we quantify emissions from normal production on well pads by using the EPA-developed Other Test Method 33a. This methodology combines ground-based measurements of fugitive emissions with 3-D wind data to calculate the methane and VOC emission fluxes from a point source. VOC fluxes are traditionally estimated by gathering a canister of air during a methane flux measurement. The methane:VOC ratio of this canister is determined at a later time in the laboratory, and applied to the known methane flux. The University of Wyoming Mobile Laboratory platform is equipped with a Picarro methane analyzer and an Ionicon Proton Transfer Reaction-Time of Flight-Mass Spectrometer, which provide real-time methane and VOC data for each well pad. This independent measurement of methane and VOCs in situ reveals multiple emission sources on one well pad, with varying methane:VOC ratios. Well pad emission estimates of methane, benzene, toluene and xylene for the two basins will be presented. The different emission source VOC profiles and the limitations of real-time and traditional VOC measurement methods will also be discussed.

  9. Reactive Oxygen Species, Lipid Peroxidation and Antioxidative Defense Mechanism

    Directory of Open Access Journals (Sweden)

    Hossam S. EL-BELTAGI

    2013-05-01

    Full Text Available Lipid peroxidation can be defined as the oxidative deterioration of lipids containing any number of carbon-carbon double bonds. Lipid peroxidation is a well-established mechanism of cellular injury in both plants and animals, and is used as an indicator of oxidative stress in cells and tissues. Lipid peroxides are unstable and decompose to form a complex series of compounds including reactive carbonyl compounds. The oxidation of linoleates and cholesterol is discussed in some detail. Analytical methods for studying lipid peroxidation were mentioned. Various kinds of antioxidants with different functions inhibit lipid peroxidation and the deleterious effects caused by the lipid peroxidation products.

  10. Involvement of lipid peroxidation and organic peroxides in UVA-induced matrix metalloproteinase-1 expression.

    Science.gov (United States)

    Polte, Tobias; Tyrrell, Rex M

    2004-06-15

    Ultraviolet A (UVA) irradiation causes human skin aging and skin cancer at least partially through the activation of matrix metalloproteinases (MMPs). MMP-1, the interstitial collagenase, is responsible for the degradation of collagen and is involved in tumor progression in human skin. The present study uses human skin fibroblast cells (FEK4) to investigate the involvement of lipid peroxidation and the role of peroxides as possible mediators in MMP-1 activation by UVA. Preincubation with the antioxidants butylated hydroxytoluene and Trolox reduced UVA-dependent MMP-1 upregulation, suggesting that peroxidation of membrane lipids is involved. Blocking the iron-driven generation of lipid peroxides and hydroxyl radicals by different iron chelators led to a decrease in UVA-induced MMP-1 mRNA accumulation. Moreover, modulation of glutathione peroxidase activity by use of the specific inhibitor mercaptosuccinate (MS) or by the depletion of glutathione (using buthionine-S, R-sulfoximine, BSO), enhanced the UVA-dependent MMP-1 response. Finally, UVA irradiation generated a significant increase in intracellular peroxide levels which is augmented by pretreatment of the cells with BSO or MS. Our results demonstrate that lipid peroxidation and the production of peroxides are important events in the signalling pathway of MMP-1 activation by UVA.

  11. Characterization of the transient species generated by the photoionization of Berberine: A laser flash photolysis study

    Science.gov (United States)

    Cheng, Ling-Li; Wang, Mei; Zhu, Hui; Li, Kun; Zhu, Rong-Rong; Sun, Xiao-Yu; Yao, Si-De; Wu, Qing-Sheng; Wang, Shi-Long

    2009-09-01

    Using 266 nm laser flash photolysis it has been demonstrated that Berberine (BBR) in aqueous solution is ionized via a mono-photonic process giving a hydrated electron, anion radical that formed by hydrated electron react with steady state of BBR, and neutral radical that formed from rapid deprotonation of the radical cation of BBR. The quantum yield of photoionization is determined to be 0.03 at room temperature with KI solution used as a reference. Furthermore utilizing pH changing method and the SO 4rad - radical oxidation method, the assignment of radical cation of BBR was further confirmed, the p Ka value of it was calculated, and the related set up rate constant was also determined.

  12. Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

    DEFF Research Database (Denmark)

    Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

    2014-01-01

    with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with results from previous studies. Similarly to what was previously shown for k(H2CO)/k(HDCO), the isotope effect decreased as pressure decreased. In addition, a model was constructed using RRKM theory to calculate the lifetime of excited formaldehyde on the S0 surface, to investigate its...

  13. Clay and Soil Photolysis of the Pesticides Mesotrione and Metsulfuron Methyl

    Directory of Open Access Journals (Sweden)

    Marie Siampiringue

    2014-01-01

    Full Text Available Photolysis may represent an important degradation process of pollutants at the surface of soil. In the present work, we report a detailed study on the degradation of two pesticides: mesotrione and metsulfuron methyl using a sunlight simulator. In a first step, we studied the photochemical behaviour at the surface of clays from the kinetic as well as from the analytical point of view. In both cases, the quantum yields were found to be higher when compared to those obtained in aqueous solutions. The effect of iron(III, water, and humic substances contents was studied. In the former cases, an increase of the degradation rate was observed while an inhibition was observed with the latter owing to a filter effect phenomenon. In a second step, we studied the photodegradation at the surface of natural soil and identified the generated byproducts. They appear to mainly arise from photohydrolysis process.

  14. Oxidation of polystyrene aerosols by VUV-photolysis and/or ozone.

    Science.gov (United States)

    Vicente, José Salas; Gejo, Juan López; Rothenbacher, Sonja; Sarojiniamma, Sumalekshmy; Gogritchiani, Eliso; Wörner, Michael; Kasper, Gerhard; Braun, André M

    2009-07-01

    Aerosols of submicron polystyrene particles were oxidized by either vacuum-ultraviolet (VUV) irradiation in the presence of molecular oxygen (O(2)) and/or by ozone (O(3)). Different degrees of oxidation and oxidative degradation were reached by VUV-photolysis depending on radiant energy, O(2) and H(2)O concentrations in the bulk gas mixture as well as on particle diameter. The same functionalization was obtained by exposing the aerosol to O(3), however, oxidation, in particular oxidative degradation, was less efficient. The evolution of hydroxyl and carbonyl functions introduced was quantified by ATR-FTIR spectroscopy of filtered particles, and oxidative degradation of the polymer particles was confirmed by determining size and number of aerosol particles before and after oxidation. Efficiency analyses are based on the results of an O(3) actinometry and on an evaluation of the rate of absorbed photons by the aerosol particles in function of their size.

  15. Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides.

    Science.gov (United States)

    Wentrup, Curt; Bibas, Hervé; Kuhn, Arvid; Mitschke, Ullrich; McMills, Mark C

    2013-11-01

    Matrix photolysis of N,N-dialkyldiazoacetamides 1a-d at 7-10 K results in either the formation of C-H insertion products (in case of N,N-dimethyl and N,N-diethyl diazoamides) or almost exclusive Wolff rearrangement to ketenes (in the case of the cyclic diazoamides N-(diazoacetyl)azetidine and N-(diazoacetyl)pyrrolidine). This can be ascribed to higher activation barriers for the approach of the singlet carbene p orbital in 5 (or of the diazo carbon in an excited state of 1) to the stronger and "tied back" nature of the C-H bonds in the cyclic substituents. In contrast, flash vacuum thermolysis (FVT) of diazoamides 1a-d, in which reactions of excited states are excluded, gives rise to clean C-H insertion with only minor Wolff rearrangement to ketenes.

  16. Studies on degradation of glyphosate by several oxidative chemical processes: ozonation, photolysis and heterogeneous photocatalysis.

    Science.gov (United States)

    Assalin, Marcia R; De Moraes, Sandra G; Queiroz, Sonia C N; Ferracini, Vera L; Duran, Nelson

    2010-01-01

    Several different Advanced Oxidation Processes (AOPs) including ozonation at pH 6.5 and 10, photolysis and heterogeneous photocatalysis using TiO(2) as semiconductor and dissolved oxygen as electron acceptor were applied to study the degradation of glyphosate (N-phosphonomethyl glycine) in water. The degree of glyphosate degradation, the reactions kinetic and the formation of the major metabolite, aminomethyl phosphonic acid (AMPA), were evaluated. Ozonation at pH 10 resulted in the maximum mineralization of glyphosate. It was observed that under the experimental conditions used in this study the degradation of glyphosate followed the first-order kinetics. The half-life obtained for glyphosate degradation in the O(3)/pH 10 process was 1.8 minutes.

  17. Synthesis and Evaluation of Porous Semiconductor Hexaniobate Nanotubes for Photolysis of Organic Dyes in Wastewater

    Directory of Open Access Journals (Sweden)

    Maryam Zarei-Chaleshtori

    2014-10-01

    Full Text Available We present the chemical synthesis of hexaniobate nanotubes using two routes, (1 starting material K4Nb6O17 and (2 parent material of H4Nb6O17 via ion exchange. The as-synthesized materials were exfoliated by adjusting the pH to 9–10 using tetra-n-butylammonioum hydroxide (TBA+OH−, leading to a formation of hexaniobate nanotubes. In order to understand morphology a full characterization was conducted using SEM, HRTEM, BET and powder-XRD. The photocatalytic activity was evaluated using photolysis method using Bromocresol Green (BG and Methyl Orange (MO as model contaminants. Results indicate a nanotube porous oxide with large porous and surface area; the photocatalytic activity is about 95% efficient when comparing with commercial TiO2.

  18. Nanosecond flash photolysis of unsymmetrical phenol-substituted calix[4]arene in cyclohexane

    Energy Technology Data Exchange (ETDEWEB)

    Feng Wen; Yuan Lihua [Sichuan Univ., Chengdu (China); Yao Side; Wang Wenfeng [Academia Sinica, Shanghai Institute of Nuclear Research, Shanghai (China)

    2000-03-01

    In the present paper the laser flash photolysis study of an unsymmetrical hindered phenol-substituted calix[4]arene(UPCA[4]OH) at 248 nm was carried out in cyclohexane at room temperature. The transient absorption spectra of UPCA[4]OH displayed two main absorption maxima at ca.330 nm and 520 nm with different grow and decay kinetics, and initial peak at 520 nm was assigned to the triplet state of the solute and the other peak at 330 nm was due to unsymmetrical phenol-substituted calix[4]aryloxyl radical. According to the kinetic analysis, the mechanism of the formation of the triplet and the calix[4]aryloxyl radical has been proposed. (author)

  19. Theoretical Study on the Tripletsensitized Photolysis of 2,5-Dimethylfuran

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    In the present work, the triplet-sensitized photolysis of 2,5-dimethylfuran has been investigated with the complete active space SCF (CASSCF) molecular orbital method. Two different reaction routes through diradical and carbene intermediates respectively have been systematically studied, and the reaction via carbene intermediate is the major part well compatible with experiment. Geometries of minima and transition states on SoT1 surface were fully optimized at the CAS level with a 6-31 G* basis set. A multireference MP2 algorithm that has been implemented in Gaussian was used to correct the energetics for dynamic correlation. Four intersystem crossing points have been located and discussed, and two of them are efficient. Our computation indicates that the reaction must occur on the triplet-excited state.

  20. (Fundamental studies in oxidation-reduction in relation to water photolysis)

    Energy Technology Data Exchange (ETDEWEB)

    Hurst, J.K.

    1991-01-01

    Our research has been directed at understanding three elementary processes that are central to developing membrane-based integrated chemical systems for water photolysis. These are: (1) the role of interfaces in charge separation/recombination reactions, (2) pathways for transmembrane charge separation, and (3) mechanisms of water oxidation catalyzed by transition metal coordination complexes. Historically, the chemical dynamics of each of these processes has been poorly understood, with numerous unresolved issues and conflicting viewpoints appearing in the literature. Our experimental systems comprise primarily unilamellar vesicles that have been doped with amphiphilic viologens which function as transmembrane charge relays. These systems are experimentally highly tractable and versatile, are conceptually simple, and have been widely used in a variety of organized microphase media and prototypic devices. As such, they are ideal for identifying basic principles governing reactivity.

  1. Sulfur Isotope Fractionation Due to SO2 Photolysis in the Atmosphere

    Science.gov (United States)

    Lyons, J. R.; Blackie, D.; Stark, G.; Pickering, J.

    2012-12-01

    The discovery of unusual (i.e. mass-independent) sulfur isotope fractionation (or MIF) in Archean and Paleoproterozoic sedimentary rocks has promised to yield insights into the rise of O2 and the nature of the sulfur cycle on ancient Earth [1], but interpretation has been hampered by the lack of a clear mechanism for the sulfur isotope signature. Proposed MIF mechanisms include SO2 photolysis [1-4], atmospheric S3 (thiozone) formation, and thermal sulfate reduction in sediments [5]. Studies focusing only on SO2 photolysis, including measurements of isotopic cross sections [6], have yielded results differing greatly from theory [4], and have resulted in improbable interpretations [7]. In addition to ancient rocks, there are sulfur isotope MIF signatures in polar ice core sulfates associated with massive Plinian eruptions over the past ~1000 years (e.g., [8]). The ice core MIF signatures differ significantly from the ancient Earth MIF signatures, suggesting a different source mechanism. SO2 photolysis can generate sulfur isotope MIF signatures in two ways: 1) self-shielding by an optically-thick column of SO2, and 2) isotope-dependent differences in absorption line intensities and widths, which are espcially important for optically-thin conditions. The MIF signatures in ice core sulfates appear to be consistent with self-shielding in an optically-thick plume, but the Archean MIF clearly is not. To address the optically-thin case, we've made high-resolution ultraviolet cross section measurements of the sulfur isotopologues of SO2 made with the UV FTS at Imperial College. We measured cross sections at 1 cm-1 spectral resolution for 32SO2, 33SO2, 34SO2 and for a 36SO2/34SO2 mixture. Incorporating these cross sections into a simple atmospheric photochemical model with a solar UV flux, we find sulfur MIF signatures for SO and S that.are consistent with the Archean pyrites. We also find that additional mass-dependent fractionation during self-shielding by 32SO2 places an

  2. Effect of mineral dust aerosols on the photolysis rates in the clean and polluted marine environments

    Science.gov (United States)

    Jeong, Gill-Ran; Sokolik, Irina N.

    2007-11-01

    This study examines the importance of spectral optical properties of mineral dust in calculations of photolysis rates in clean and polluted marine environments. A set of optical characteristics was computed with Mie theory using data on the size distribution and composition of mineral dust from recent experimental and modeling studies. These models were incorporated into the National Center for Atmospheric Research tropospheric ultraviolet-visible radiation transfer code. The 13 analyzed photolysis reactions were classified into three groups according to their photolytic wavelengths and the vertical profile of J values in the aerosol-free atmosphere. The photolysis reactions of O3(O1D), NO2, and NO3(NO) were selected as representative of groups I, II, and III, respectively. We find that depending on its properties, dust causes either a decrease or an increase in the spectral actinic fluxes relative to the aerosol-free condition. The wavelength range in which the changes in actinic fluxes are negative becomes broader as the amount of dust load increases, a dust size distribution is shifted to coarse size mode, and the iron oxide content in dust aggregates increases. Changes in actinic fluxes also depend on the sun position (time of the day) and an altitude considered. As a result, dust exerts the differing impact on J values of the three photolytic groups. The diurnal cycle of dust-affected J values of a given group is similar among the differing size distribution and dust compositions, but changes in J values vary by a factor of 1.5-2. For a given content of iron oxide, the largest changes are caused by the size distributions that are shifted to the fine size mode. A change in J values of groups I and II caused by the varying amount of iron oxide in dust aggregates (from 1% to 10%) is negative in and below the dust layer. In contrast, J values of group III increase in the presence of low absorbing dust (with 1% of iron oxide), but they decrease with increasing dust

  3. Development of new VOC exposure metrics and their relationship to ''Sick Building Syndrome'' symptoms

    Energy Technology Data Exchange (ETDEWEB)

    Ten Brinke, JoAnn [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States)

    1995-08-01

    Volatile organic compounds (VOCs) are suspected to contribute significantly to ''Sick Building Syndrome'' (SBS), a complex of subchronic symptoms that occurs during and in general decreases away from occupancy of the building in question. A new approach takes into account individual VOC potencies, as well as the highly correlated nature of the complex VOC mixtures found indoors. The new VOC metrics are statistically significant predictors of symptom outcomes from the California Healthy Buildings Study data. Multivariate logistic regression analyses were used to test the hypothesis that a summary measure of the VOC mixture, other risk factors, and covariates for each worker will lead to better prediction of symptom outcome. VOC metrics based on animal irritancy measures and principal component analysis had the most influence in the prediction of eye, dermal, and nasal symptoms. After adjustment, a water-based paints and solvents source was found to be associated with dermal and eye irritation. The more typical VOC exposure metrics used in prior analyses were not useful in symptom prediction in the adjusted model (total VOC (TVOC), or sum of individually identified VOCsVOCi)). Also not useful were three other VOC metrics that took into account potency, but did not adjust for the highly correlated nature of the data set, or the presence of VOCs that were not measured. High TVOC values (2--7 mg m-3) due to the presence of liquid-process photocopiers observed in several study spaces significantly influenced symptoms. Analyses without the high TVOC values reduced, but did not eliminate the ability of the VOC exposure metric based on irritancy and principal component analysis to explain symptom outcome.

  4. Development of new VOC exposure metrics and their relationship to ''Sick Building Syndrome'' symptoms

    Energy Technology Data Exchange (ETDEWEB)

    None

    1995-08-01

    Volatile organic compounds (VOCs) are suspected to contribute significantly to ''Sick Building Syndrome'' (SBS), a complex of subchronic symptoms that occurs during and in general decreases away from occupancy of the building in question. A new approach takes into account individual VOC potencies, as well as the highly correlated nature of the complex VOC mixtures found indoors. The new VOC metrics are statistically significant predictors of symptom outcomes from the California Healthy Buildings Study data. Multivariate logistic regression analyses were used to test the hypothesis that a summary measure of the VOC mixture, other risk factors, and covariates for each worker will lead to better prediction of symptom outcome. VOC metrics based on animal irritancy measures and principal component analysis had the most influence in the prediction of eye, dermal, and nasal symptoms. After adjustment, a water-based paints and solvents source was found to be associated with dermal and eye irritation. The more typical VOC exposure metrics used in prior analyses were not useful in symptom prediction in the adjusted model (total VOC (TVOC), or sum of individually identified VOCs ({Sigma}VOC{sub i})). Also not useful were three other VOC metrics that took into account potency, but did not adjust for the highly correlated nature of the data set, or the presence of VOCs that were not measured. High TVOC values (2--7 mg m{sup {minus}3}) due to the presence of liquid-process photocopiers observed in several study spaces significantly influenced symptoms. Analyses without the high TVOC values reduced, but did not eliminate the ability of the VOC exposure metric based on irritancy and principal component analysis to explain symptom outcome.

  5. Belowground communication: impacts of volatile organic compounds (VOCs) from soil fungi on other soil-inhabiting organisms.

    Science.gov (United States)

    Werner, Stephanie; Polle, Andrea; Brinkmann, Nicole

    2016-10-01

    We reviewed the impact of fungal volatile organic compounds (VOCs) on soil-inhabiting organisms and their physiological and molecular consequences for their targets. Because fungi can only move by growth to distinct directions, a main mechanism to protect themselves from enemies or to manipulate their surroundings is the secretion of exudates or VOCs. The importance of VOCs in this regard has been significantly underestimated. VOCs not only can be means of communication, but also signals that are able to specifically manipulate the recipient. VOCs can reprogram root architecture of symbiotic partner plants or increase plant growth leading to enlarged colonization surfaces. VOCs are also able to enhance plant resistance against pathogens by activating phytohormone-dependent signaling pathways. In some cases, they were phytotoxic. Because the response was specific to distinct species, fungal VOCs may contribute to regulate the competition of plant communities. Additionally, VOCs are used by the producing fungus to attack rivaling fungi or bacteria, thereby protecting the emitter or its nutrient sources. In addition, animals, like springtails, nematodes, and earthworms, which are important components of the soil food web, respond to fungal VOCs. Some VOCs are effective repellents for nematodes and, therefore, have applications as biocontrol agents. In conclusion, this review shows that fungal VOCs have a huge impact on soil fauna and flora, but the underlying mechanisms, how VOCs are perceived by the recipients, how they manipulate their targets and the resulting ecological consequences of VOCs in inter-kingdom signaling is only partly understood. These knowledge gaps are left to be filled by future studies.

  6. A High Performance Biofilter for VOC Emission Control.

    Science.gov (United States)

    Wu, G; Conti, B; Leroux, A; Brzezinski, R; Viel, G; Heitz, M

    1999-02-01

    Biofiltration is a cleaning technique for waste air contaminated with some organic compounds. The advantages of the conventional biofilter over other biological systems are a high-superficial area best suited for the treatment of some compounds with poor water solubility, ease of operation, and low operating costs. It has crucial disadvantages, however; for example, it is not suitable to treat waste gases with high VOC concentrations and it has poor control of reaction conditions. To improve on these problems and to build a high-performance biofilter, three structured peat media and two trickling systems have been introduced in this study. The influences of media size and composition have been investigated experimentally. Peat bead blended with 30% (w/w) certain mineral material with a good binding capacity has advantages over other packing materials, for example, suitable size to prevent blockage due to microbial growth, strong buffering capacity to neutralize acidic substances in the system, and a pH range of 7.0-7.2 suitable for the growth of bacteria. Dropwise trickling system offers an effective measure to easily control the moisture content of the bed and the reaction conditions (pH, nutrient) and to partially remove excess biomass produced during the metabolic processes of microorganisms. The influence of nutrient supplementation has also been investigated in this study, which has revealed that the biological system was in a condition of nutrient limitation instead of carbon limitation. The biofilters built in our laboratory were used to treat waste gas contaminated with toluene in a concentration range of 1 to 3.2 g/m(3) and at the specific gas flow rate of 24 to120 m(3)/m(2).hr. Under the conditions employed, a high elimination capacity (135 g/m(3).hr) was obtained in the biofilter packed with peat beads (blended with 30% of the mineral material), and no blockage problem was observed in an experimental period of 2-3 months.

  7. Atmospheric chemistry of 2,3-pentanedione: photolysis and reaction with OH radicals.

    Science.gov (United States)

    Szabó, Emese; Djehiche, Mokhtar; Riva, Matthieu; Fittschen, Christa; Coddeville, Patrice; Sarzyński, Dariusz; Tomas, Alexandre; Dóbé, Sándor

    2011-08-25

    The kinetics of the overall reaction between OH radicals and 2,3-pentanedione (1) were studied using both direct and relative kinetic methods at laboratory temperature. The low pressure fast discharge flow experiments coupled with resonance fluorescence detection of OH provided the direct rate coefficient of (2.25 ± 0.44) × 10(-12) cm(3) molecule(-1) s(-1). The relative-rate experiments were carried out both in a collapsible Teflon chamber and a Pyrex reactor in two laboratories using different reference reactions to provide the rate coefficients of 1.95 ± 0.27, 1.95 ± 0.34, and 2.06 ± 0.34, all given in 10(-12) cm(3) molecule(-1) s(-1). The recommended value is the nonweighted average of the four determinations: k(1) (300 K) = (2.09 ± 0.38) × 10(-12) cm(3) molecule(-1) s(-1), given with 2σ accuracy. Absorption cross sections for 2,3-pentanedione were determined: the spectrum is characterized by two wide absorption bands between 220 and 450 nm. Pulsed laser photolysis at 351 nm was used and the depletion of 2,3-pentanedione (2) was measured by GC to determine the photolysis quantum yield of Φ(2) = 0.11 ± 0.02(2σ) at 300 K and 1000 mbar synthetic air. An upper limit was estimated for the effective quantum yield of 2,3-pentanedione applying fluorescent lamps with peak wavelength of 312 nm. Relationships between molecular structure and OH reactivity, as well as the atmospheric fate of 2,3-pentanedione, have been discussed.

  8. Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis

    Directory of Open Access Journals (Sweden)

    Forbes A

    2012-06-01

    Full Text Available Steven S Nkosi,1,2 Bonex W Mwakikunga,4 Elias Sideras-Haddad,2 Andrew Forbes1,31CSIR National Laser Centre, Pretoria, South Africa; 2DST/NRF Centre for Excellence in Strong Materials and School of Physics, University of the Witwatersrand, Johannesburg, 3School of Physics, University of KwaZulu-Natal, Durban, South Africa; 4DST/CSIR National Centre for Nano-Structured Materials, Pretoria, South AfricaAbstract: Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III acetylacetonate and Pt(II acetylacetonate. Fe(II and Pt(I acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001 diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence.Keywords: nanostructures, iron, platinum, nanoparticles, laser liquid photolysis, composition

  9. Non-invasive bleaching of the human lens by femtosecond laser photolysis.

    Directory of Open Access Journals (Sweden)

    Line Kessel

    Full Text Available BACKGROUND: Globally, cataract is the leading cause of blindness and impaired vision. Cataract surgery is an attractive treatment option but it remains unavailable in sufficient quantity for the vast majority of the world population living in areas without access to specialized health care. Reducing blindness from cataract requires solutions that can be applied outside operating theatres. Cataract is a protein conformational disease characterized by accumulation of light absorbing, fluorescent and scattering protein aggregates. The aim of the study was to investigate whether these compounds were susceptible to photobleaching by a non-invasive procedure and whether this would lead to optical rejuvenation of the lens. METHODOLOGY/PRINCIPAL FINDINGS: Nine human donor lenses were treated with an 800 nm infra-red femtosecond pulsed laser in a treatment zone measuring 1x1x0.52 mm. After laser treatment the age-induced yellow discoloration of the lens was markedly reduced and the transmission of light was increased corresponding to an optical rejuvenation of 3 to 7 years. CONCLUSIONS/SIGNIFICANCE: The results demonstrate that the age-induced yellowing of the human lens can be bleached by a non-invasive procedure based on femtosecond laser photolysis. Cataract is a disease associated with old age. At the current technological stage, lens aging is delayed but with a treatment covering the entire lens volume complete optical rejuvenation is expected. Thus, femtosecond photolysis has the potential clinical value of replacing invasive cataract surgery by a non-invasive treatment modality that can be placed in mobile units, thus breaking down many of the barriers impeding access to treatment in remote and poor regions of the world.

  10. Self-assembly of uranyl-peroxide nanocapsules in basic peroxidic environments

    Energy Technology Data Exchange (ETDEWEB)

    Miro, Pere; Vlaisavljevich, Bess [Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, MN (United States); Gil, Adria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona (Spain); Burns, Peter C. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, South Bend, IN (United States); Nyman, May [Materials Science of Actinides, Department of Chemistry, Oregon State University, Corvallis, OR (United States); Bo, Carles [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona (Spain); Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, Campus Sescelades, Tarragona (Spain)

    2016-06-13

    A wide range of uranyl-peroxide nanocapsules have been synthesized using very simple reactants in basic media; however, little is known about the process to form these species. We have performed a density functional theory study of the speciation of the uranyl ions under different experimental conditions and explored the formation of dimeric species via a ligand exchange mechanism. We shed some light onto the importance of the excess of peroxide and alkali counterions as a thermodynamic driving force towards the formation of larger uranyl-peroxide species. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. A kinetic and ESR investigation of iron(II) oxalate oxidation by hydrogen peroxide and dioxygen as a source of hydroxyl radicals

    DEFF Research Database (Denmark)

    Park, J S; Wood, P M; Davies, Michael Jonathan

    1997-01-01

    The reaction of Fe(II) oxalate with hydrogen peroxide and dioxygen was studied for oxalate concentrations up to 20 mM and pH 2-5, under which conditions mono- and bis-oxalate complexes (Fe[II](ox) and Fe[II](ox)2[2-]) and uncomplexed Fe2+ must be considered. The reaction of Fe(II) oxalate...... with hydrogen peroxide (Fe2+ + H2O2 --> Fe3+ + .OH + OH-) was monitored in continuous flow by ESR with t-butanol as a radical trap. The reaction is much faster than for uncomplexed Fe2+ and a rate constant, k = 1 x 10(4) M(-1) s(-1) is deduced for Fe(II)(ox). The reaction of Fe(II) oxalate with dioxygen...... by oxalate. Further ESR studies with DMPO as spin trap reveal that reaction of Fe(II) oxalate with hydrogen peroxide can also lead to formation of the carboxylate radical anion (CO2-), an assignment confirmed by photolysis of Fe(II) oxalate in the presence of DMPO....

  12. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    Science.gov (United States)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    unsaturated aldehydes were detected and a reaction pathway, initiated by a H-abstraction of the surfactant by the excited HA*, has been proposed. This mechanism infers that the presence of the surface microlayer will enhance protonation and self-reactions, leading to the formation of dimers as suggested in [6]. These products could explain the formation of the unsaturated products observed. To confirm the hypothesis of an initiative step of H-abstraction, the system was simplified using OH radicals, generated by the photolysis of H2O2, in presence of an artificial organic layer of nonanoic acid. The VOCs produced, monitored by PTR/SRI-TOF-MS in NO+ and H3O+ ionization mode, were less abundant compared to the system with HA, but the same classes of products could be observed, including oxidation products such as aldehydes but also unsatured products like dienes. The underlying water was sampled before and after the experiment and analysed by HR-ESI-MS, showing mostly enrichment of oxidative products, such as hydroxy- and keto-acids immediately derived from the photochemical oxidation of the nonanoic acid layer. These products, showing lower volatility and higher polarity, partition preferentially to the bulk water. The results of this simplified system confirm the reaction mechanism proposed and the role an organic layer can play in the photochemical formation of VOCs, which could influence the marine boundary layer chemistry. 1. Peter S. Liss, R.A.D., ed. Sea Surface and Global Change. 1997, Cambridge University Press: Cambridge. 509. 2. Griffith, E.C. and V. Vaida, In situ observation of peptide bond formation at the water-air interface. Proceedings of the National Academy of Sciences, 2012. 109(39): p. 15697-15701. 3. Sinreich, R., et al., Ship-based detection of glyoxal over the remote tropical Pacific Ocean. Atmospheric Chemistry and Physics, 2010. 10(23): p. 11359-11371. 4. Kieber, R.J., X.L. Zhou, and K. Mopper, Formation of carbonyl-compounds from uv

  13. Virucidal efficacy of hydrogen peroxide vapour disinfection

    NARCIS (Netherlands)

    Tuladhar, E.; Terpstra, P.; Koopmans, M.; Duizer, E.

    2012-01-01

    Background: Viral contamination of surfaces is thought to be important in transmission. Chemical disinfection can be an effective means of intervention, but little is known about the virucidal efficacy of hydrogen peroxide vapour (HPV) against enteric and respiratory viruses. Aim: To measure the

  14. Virucidal efficacy of hydrogen peroxide vapour disinfection

    NARCIS (Netherlands)

    Tuladhar, E.; Terpstra, P.; Koopmans, M.; Duizer, E.

    2012-01-01

    Background: Viral contamination of surfaces is thought to be important in transmission. Chemical disinfection can be an effective means of intervention, but little is known about the virucidal efficacy of hydrogen peroxide vapour (HPV) against enteric and respiratory viruses. Aim: To measure the vir

  15. Assessment of Exposure to VOCs among Pregnant Women in the National Children’s Study

    Directory of Open Access Journals (Sweden)

    Elizabeth Barksdale Boyle

    2016-03-01

    Full Text Available Epidemiologic studies can measure exposure to volatile organic compounds (VOCs using environmental samples, biomarkers, questionnaires, or observations. These different exposure assessment approaches each have advantages and disadvantages; thus, evaluating relationships is an important consideration. In the National Children’s Vanguard Study from 2009 to 2010, participants completed questionnaires and data collectors observed VOC exposure sources and collected urine samples from 488 third trimester pregnant women at in-person study visits. From urine, we simultaneously quantified 28 VOC metabolites of exposure to acrolein, acrylamide, acrylonitrile, benzene, 1-bromopropane, 1,3-butadiene, carbon disulfide, crotonaldehyde, cyanide, N,N-dimethylformamide, ethylbenzene, ethylene oxide, propylene oxide, styrene, tetrachloroethylene, toluene, trichloroethylene, vinyl chloride, and xylene exposures using ultra high performance liquid chromatography coupled with an electrospray ionization tandem mass spectrometry (UPLC-ESI/MSMS method. Urinary thiocyanate was measured using an ion chromatography coupled with an electrospray ionization tandem mass spectrometry method (IC-ESI/MSMS. We modeled the relationship between urinary VOC metabolite concentrations and sources of VOC exposure. Sources of exposure were assessed by participant report via questionnaire (use of air fresheners, aerosols, paint or varnish, organic solvents, and passive/active smoking and by observations by a trained data collector (presence of scented products in homes. We found several significant (p < 0.01 relationships between the urinary metabolites of VOCs and sources of VOC exposure. Smoking was positively associated with metabolites of the tobacco constituents acrolein, acrylamide, acrylonitrile, 1,3-butadiene, crotonaldehyde, cyanide, ethylene oxide, N,N-dimethylformamide, propylene oxide, styrene, and xylene. Study location was negatively associated with the toluene metabolite

  16. Optimizing the emission inventory of volatile organic compounds (VOCs) based on network observations

    Science.gov (United States)

    Chen, Sheng-Po; Liu, Wen-Tzu; Ou-Yang, Chang-Feng; Chang, Julius S.; Wang, Jia-Lin

    2014-02-01

    Hourly observations of 56 non-methane hydrocarbons (NMHCs) performed by a network of photochemical assessment monitoring stations (PAMS) at 11 locations across Taiwan were used to evaluate 56 speciated emissions and the resulting simulations of an air quality model. Based on the PAMS observations at two urban sites, emission modification was made for the 56 PAMS species in the model. To further test the applicability of this emission correction approach, the same modified emissions were subject to seven different meteorological conditions and comparison with observations of all the 11 PAMS sites. Originally there was a minimum of only 8 of 56 species showed agreement with observations for the worst of the 11 PAMS sites and 28 of 56 species for the best site. With modified emissions, the number increased to 13-52 species across the 11 PAMS sites, demonstrating that the simple urban based correction procedure has broad applicability. When applying this modification of PAMS emissions to the simulations of other air quality gases, SO2 and NOx showed small changes compared with observations (-0.27% and -2.51%, respectively), while total VOC concentrations showed significant changes (+15.28%) as a result of the adjustment in VOC emissions (+26.7%). Although VOCs are the precursor of ozone, the relatively large changes in VOC did not seem to affect ozone formation to the similar extent, only resulting in the changes of average O3 by 2.9 ppb (+9.41%). It shows that although the emission modification improves individual VOC simulations, the performance in oxidant simulation is still largely unaltered. Although the original U.S. VOC emission profiles can capture the general features of ambient VOCs, further optimization of emissions may still be needed by referencing extensive observations, so that emissions can better fit domestic conditions and accuracy in model simulations can be improved.

  17. Assessment of Exposure to VOCs among Pregnant Women in the National Children’s Study

    Science.gov (United States)

    Boyle, Elizabeth Barksdale; Viet, Susan M.; Wright, David J.; Merrill, Lori S.; Alwis, K. Udeni; Blount, Benjamin C.; Mortensen, Mary E.; Moye, John; Dellarco, Michael

    2016-01-01

    Epidemiologic studies can measure exposure to volatile organic compounds (VOCs) using environmental samples, biomarkers, questionnaires, or observations. These different exposure assessment approaches each have advantages and disadvantages; thus, evaluating relationships is an important consideration. In the National Children’s Vanguard Study from 2009 to 2010, participants completed questionnaires and data collectors observed VOC exposure sources and collected urine samples from 488 third trimester pregnant women at in-person study visits. From urine, we simultaneously quantified 28 VOC metabolites of exposure to acrolein, acrylamide, acrylonitrile, benzene, 1-bromopropane, 1,3-butadiene, carbon disulfide, crotonaldehyde, cyanide, N,N-dimethylformamide, ethylbenzene, ethylene oxide, propylene oxide, styrene, tetrachloroethylene, toluene, trichloroethylene, vinyl chloride, and xylene exposures using ultra high performance liquid chromatography coupled with an electrospray ionization tandem mass spectrometry (UPLC-ESI/MSMS) method. Urinary thiocyanate was measured using an ion chromatography coupled with an electrospray ionization tandem mass spectrometry method (IC-ESI/MSMS). We modeled the relationship between urinary VOC metabolite concentrations and sources of VOC exposure. Sources of exposure were assessed by participant report via questionnaire (use of air fresheners, aerosols, paint or varnish, organic solvents, and passive/active smoking) and by observations by a trained data collector (presence of scented products in homes). We found several significant (p < 0.01) relationships between the urinary metabolites of VOCs and sources of VOC exposure. Smoking was positively associated with metabolites of the tobacco constituents acrolein, acrylamide, acrylonitrile, 1,3-butadiene, crotonaldehyde, cyanide, ethylene oxide, N,N-dimethylformamide, propylene oxide, styrene, and xylene. Study location was negatively associated with the toluene metabolite N

  18. A comparative study of fungal and bacterial biofiltration treating a VOC mixture

    Energy Technology Data Exchange (ETDEWEB)

    Estrada, José M. [Departamento de Procesos y Tecnología, Universidad Autónoma Metropolitana-Cuajimalpa, Artificios 40, Col. Miguel Hidalgo, Delegación Álvaro Obregón (Mexico); Departamento de Ingeniería Química y Tecnología del Medio Ambiente – Universidad de Valladolid, Valladolid (Spain); Hernández, Sergio [Departmento de Procesos e Hidráulica – Universidad Autónoma Metropolitana – Iztapalapa Mexico D.F. Mexico (Mexico); Muñoz, Raúl [Departamento de Ingeniería Química y Tecnología del Medio Ambiente – Universidad de Valladolid, Valladolid (Spain); Revah, Sergio, E-mail: srevah@xanum.uam.mx [Departamento de Procesos y Tecnología, Universidad Autónoma Metropolitana-Cuajimalpa, Artificios 40, Col. Miguel Hidalgo, Delegación Álvaro Obregón (Mexico)

    2013-04-15

    Highlights: ► Bacterial biofilter showed better EC and ΔP than fungal biofilter. ► The preferential biodegradation order was: propanal > hexanol > MIBK > toluene. ► Propanal partially inhibited the biodegradation of the rest of VOCs. ► The two-stage biofilter showed a higher stability than the individual units. -- Abstract: Bacterial biofilters usually exhibit a high microbial diversity and robustness, while fungal biofilters have been claimed to better withstand low moisture contents and pH values, and to be more efficient coping with hydrophobic volatile organic compounds (VOCs). However, there are only few systematic evaluations of both biofiltration technologies. The present study compared fungal and bacterial biofiltration for the treatment of a VOC mixture (propanal, methyl isobutyl ketone-MIBK, toluene and hexanol) under the same operating conditions. Overall, fungal biofiltration supported lower elimination capacities than its bacterial counterpart (27.7 ± 8.9 vs 40.2 ± 5.4 g C m{sup −3} reactor h{sup −1}), which exhibited a final pressure drop 60% higher than that of the bacterial biofilter due to mycelial growth. The VOC mineralization ratio was also higher in the bacterial bed (≈63% vs ≈43%). However, the substrate biodegradation preference order was similar for both biofilters (propanal > hexanol > MIBK > toluene) with propanal partially inhibiting the consumption of the rest of the VOCs. Both systems supported an excellent robustness versus 24 h VOC starvation episodes. The implementation of a fungal/bacterial coupled system did not significantly improve the VOC removal performance compared to the individual biofilter performances.

  19. Fluorimetric analysis of hydrogen peroxide with automated measurement.

    NARCIS (Netherlands)

    Beurden, W.J.C van; Bosch, M.J. van den; Janssen, W.C.; Smeenk, F.W.; Dekhuijzen, P.N.R.; Harff, G.A.

    2003-01-01

    In the pathophysiology of chronic obstructive pulmonary disease (COPD) oxidative stress plays an important role, which can be determined by measuring hydrogen peroxide. Hydrogen peroxide can be measured fluorimetrically in exhaled breath condensate (EBC), however, not standardized. The objective of

  20. Drinking Peroxide as 'Natural' Cure Leads to Dangerous Blood Clots

    Science.gov (United States)

    ... https://medlineplus.gov/news/fullstory_163513.html Drinking Peroxide as 'Natural' Cure Leads to Dangerous Blood Clots ... 9, 2017 (HealthDay News) -- Ingesting high-concentration hydrogen peroxide as a "natural cure" or cleansing agent may ...

  1. Systems and methods for generation of hydrogen peroxide vapor

    Science.gov (United States)

    Love, Adam H; Eckels, Joel Del; Vu, Alexander K; Alcaraz, Armando; Reynolds, John G

    2014-12-02

    A system according to one embodiment includes a moisture trap for drying air; at least one of a first container and a second container; and a mechanism for at least one of: bubbling dried air from the moisture trap through a hydrogen peroxide solution in the first container for producing a hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above a hydrogen peroxide solution in the second container for producing a hydrogen peroxide vapor. A method according one embodiment includes at least one of bubbling dried air through a hydrogen peroxide solution in a container for producing a first hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above the hydrogen peroxide solution in a container for producing a second hydrogen peroxide vapor. Additional systems and methods are also presented.

  2. Microsomal lipid peroxidation as a mechanism of cellular damage. [Dissertation

    Energy Technology Data Exchange (ETDEWEB)

    Kornbrust, D.J.

    1979-01-01

    The NADPH/iron-dependent peroxidation of lipids in rat liver microsomes was found to be dependent on the presence of free ferrous ion and maintains iron in the reduced Fe/sup 2 +/ state. Chelation of iron by EDTA inhibited peroxidation. Addition of iron, after preincubation of microsomes in the absence of iron, did not enhance the rate of peroxidation suggesting that iron acts by initiating peroxidative decomposition of membrane lipids rather than by catalyzing the breakdown of pre-formed hydroperoxides. Liposomes also underwent peroxidation in the presence of ferrous iron at a rate comparable to intact microsomes and was stimulated by ascorbate. Carbon tetrachloride initiated lipid peroxidation in the absence of free metal ions. Rates of in vitro lipid peroxidation of microsomes and homogenates were found to vary widely between different tissues and species. The effects of paraquat on lipid peroxidation was also studied. (DC)

  3. Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell

    OpenAIRE

    Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.

    2012-01-01

    This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O2-reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the ...

  4. Expanding the crystal chemistry of uranyl peroxides: four hybrid uranyl-peroxide structures containing EDTA.

    Science.gov (United States)

    Qiu, Jie; Ling, Jie; Sieradzki, Claire; Nguyen, Kevin; Wylie, Ernest M; Szymanowski, Jennifer E S; Burns, Peter C

    2014-11-17

    The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO2(4-). The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA(4-). In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA(4-) or EDTAO2(4-) results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO2(4-) to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA(4-) in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

  5. VOC emission into the atmosphere by trees and leaf litter in Polish forests

    Science.gov (United States)

    Isidorov, V.; Smolewska, M.; Tyszkiewicz, Z.

    2009-04-01

    It is generally recognized at present that the vegetation of continents is the principal source of reactive volatile organic compounds (VOC) of the atmosphere. The upper limit of the evaluation of global phytogenic VOC is 1100-1500 Tg/yr (Isidorov, 1990; Guenther et al., 1995). Although these global evaluations showing the place of phytogenic emission among of other VOC sources are important, evaluations for individual countries are also very important. This poster represents the results of the estimation of VOC emission from Polish forests. Calculations took into account the composition and age of forests. According to our estimation, the total VOC emission by the arboreal vegetation differs from 190 to 750 kt/yr, depending of weather conditions in different years. There are only few studies conducted on decaying plant material as a source of atmospheric VOCs, but still they are able to give evidence of the importance of this source. For Polish forests, the litter mass is estimated to be (16-19)106 t/yr. These organic materials undergo decomposition by mesofauna and microorganisms. In these processes volatile organic compounds (VOC) stored in the litter and secondary metabolites of litter-destroying fungi are emitted into the atmosphere. The scale of the phenomenon makes leaf litter an important VOC source in the atmosphere. The filling of numerous gaps in researches of VOC emissions from decomposing leaf litter demands carrying out of long term field experiments in various climatic conditions. In this communication we report also the results of 3.5-year experiment on qualitative and quantitative GC-MS investigations of VOC emitted into the gas phase from leaves litter of some species of deciduous and coniferous trees of Polish forests. Apart from terpenes and their oxygenated derivatives, which are usual in plant tissues, leaf litter intensively emits vast amounts of lower alcohols and carbonyl compounds. We suppose that these volatile substances are products

  6. Pilot-scale testing of renewable biocatalyst for swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions

    Science.gov (United States)

    Maurer, Devin L.; Koziel, Jacek A.; Bruning, Kelsey; Parker, David B.

    2017-02-01

    Comprehensive control of odors, hydrogen sulfide (H2S), ammonia (NH3), and greenhouse gas (GHG) emissions associated with swine production is a critical need. A pilot-scale experiment was conducted to evaluate surface-applied soybean peroxidase (SBP) and calcium peroxide (CaO2) as a manure additive to mitigate emissions of odorous volatile organic compounds (VOC) including dimethyl disulfide/methanethiol (DMDS/MT), dimethyl trisulfide, n-butyric acid, valeric acid, isovaleric acid, p-cresol, indole, and skatole. The secondary impact on emissions of NH3, H2S, and GHG was also measured. The SBP was tested at four treatments (2.28-45.7 kg/m2 manure) with CaO2 (4.2% by weight of SBP) over 137 days. Significant reductions in VOC emissions were observed: DMDS/MT (36.2%-84.7%), p-cresol (53.1%-89.5%), and skatole (63.2%-92.5%). There was a corresponding significant reduction in NH3 (14.6%-67.6%), and significant increases in the greenhouse gases CH4 (32.7%-232%) and CO2 (20.8%-124%). The remaining emissions (including N2O) were not statistically different. At a cost relative to 0.8% of a marketed hog it appears that SBP/CaO2 treatment could be a promising option at the lowest (2.28 kg/m2) treatment rate for reducing odorous gas and NH3 emissions at swine operations, and field-scale testing is warranted.

  7. Volatile Organic Compound (VOC) Emissions from Dairy Cows and Their Waste

    Science.gov (United States)

    Shaw, S.; Holzinger, R.; Mitloehner, F.; Goldstein, A.

    2005-12-01

    Biogenic VOCs are typically defined as those directly emitted from plants, but approximately 6% of global net primary production is consumed by cattle that carry out enteric fermentation and then emit VOCs that could also be considered biogenic. Current regulatory estimates suggest that dairy cattle in central California emit VOCs at rates comparable to those from passenger vehicles in the region, and thus contribute significantly to the extreme non-attainment of ozone standards there. We report PTR-MS measurements of ammonia and VOCs, and cavity-enhanced-absorption gas analyzer (Los Gatos Research, Inc.) measurements of CH4, emitted from dairy cattle in various stages of pregnancy/lactation and their waste. Experiments were conducted in chambers at UC Davis that simulate freestall cow housing conditions. CH4 fluxes ranged from 125-374 lb/cow/year. The compounds with the highest fluxes from '3 cows+waste' treatments were: ammonia (1-18), methanol (0-2.3), acetone+propanal (0.2-0.7), dimethylsulfide (0-0.4), and mass 109 (likely ID = p-cresol; 0-0.3) in lb/cow/year. Mass 60 (likely ID = trimethylamine) and acetic acid were also abundant. There were 10s of additional compounds with detectable, but small, emissions. A few compounds that were likely emitted (i.e. ethanol, formaldehyde, and dimethylamine) were not quantified by the PTR-MS. The total flux for all measured organic gases (TOG = CH4 + PTR-MS VOCs(including acetone+propanal)) averaged 246±45 lb/cow/year for '3 cows+waste' treatments, and was dominated by methane (>98%). TOG flux for 'waste only' treatments averaged 1.1±0.1 lb/cow/year, and was instead dominated by VOC (>84%). The PTR-MS VOCs as a percent of TOG (0.6±0.2%) emitted from '3 cows+waste' treatments in chamber conditions was a factor of 10 smaller than that currently estimated by the California Air Resources Board. In addition, the ozone forming potentials of the most abundant VOCs are only about 10% those of typical combustion or plant

  8. 49 CFR 172.552 - ORGANIC PEROXIDE placard.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false ORGANIC PEROXIDE placard. 172.552 Section 172.552... SECURITY PLANS Placarding § 172.552 ORGANIC PEROXIDE placard. (a) Except for size and color, the ORGANIC... background on the ORGANIC PEROXIDE placard must be red in the top half and yellow in the lower half. The...

  9. 49 CFR 172.427 - ORGANIC PEROXIDE label.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false ORGANIC PEROXIDE label. 172.427 Section 172.427... SECURITY PLANS Labeling § 172.427 ORGANIC PEROXIDE label. (a) Except for size and color, the ORGANIC... on the ORGANIC PEROXIDE label must be red in the top half and yellow in the lower half....

  10. 21 CFR 178.1005 - Hydrogen peroxide solution.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Hydrogen peroxide solution. 178.1005 Section 178... SANITIZERS Substances Utilized To Control the Growth of Microorganisms § 178.1005 Hydrogen peroxide solution. Hydrogen peroxide solution identified in this section may be safely used to sterilize polymeric...

  11. An extended baseline examination of indoor VOCs in a city of low ambient pollution: Perth, Western Australia

    Science.gov (United States)

    Maisey, S. J.; Saunders, S. M.; West, N.; Franklin, P. J.

    2013-12-01

    This study of indoor air quality reports VOC concentrations in 386 suburban homes located in Perth Western Australia, a city of low ambient pollution and temperate climate. Details of indoor VOC concentrations, temperature, relative humidity, and information on house characteristics and occupant activities were collected during the sampling periods. The concentration of VOCs observed in typical homes was low and individual compounds rarely exceeded 5 μg m-3. Median individual VOC concentrations ranged from 0.06 μg m-3 for 1,1,1 trichloroethane and butyl ether to 26.6 μg m-3 for cis/trans 2-butene. Recently renovated homes had higher concentrations of VOCs than non renovated homes, including ∑VOCs (p = 0.026), ∑BTEX (p = 0.03), ∑xylene (p = 0.013), toluene (p = 0.05), cyclohexane (p = 0.039), and propyl benzene (p = 0.039). Statistical analyses showed house age and attached garages were not significant factors for any of the VOCs tested. The concentrations of indoor VOCs in Perth were lower than overseas observations and those reported in recent Australian studies, with inferences made to differences in the climate and the occupant behaviour. The results are a baseline profile of indoor VOCs over the period 2006-2011, in an Australian city of low population density and of generally low ambient pollution.

  12. Volatile organic compounds (VOCs) in urban air: How chemistry affects the interpretation of positive matrix factorization (PMF) analysis

    Science.gov (United States)

    Yuan, Bin; Shao, Min; de Gouw, Joost; Parrish, David D.; Lu, Sihua; Wang, Ming; Zeng, Limin; Zhang, Qian; Song, Yu; Zhang, Jianbo; Hu, Min

    2012-12-01

    Volatile organic compounds (VOCs) were measured online at an urban site in Beijing in August-September 2010. Diurnal variations of various VOC species indicate that VOCs concentrations were influenced by photochemical removal with OH radicals for reactive species and secondary formation for oxygenated VOCs (OVOCs). A photochemical age-based parameterization method was applied to characterize VOCs chemistry. A large part of the variability in concentrations of both hydrocarbons and OVOCs was explained by this method. The determined emission ratios of hydrocarbons to acetylene agreed within a factor of two between 2005 and 2010 measurements. However, large differences were found for emission ratios of some alkanes and C8 aromatics between Beijing and northeastern United States secondary formation from anthropogenic VOCs generally contributed higher percentages to concentrations of reactive aldehydes than those of inert ketones and alcohols. Anthropogenic primary emissions accounted for the majority of ketones and alcohols concentrations. Positive matrix factorization (PMF) was also used to identify emission sources from this VOCs data set. The four resolved factors were three anthropogenic factors and a biogenic factor. However, the anthropogenic factors are attributed here to a common source at different stages of photochemical processing rather than three independent sources. Anthropogenic and biogenic sources of VOCs concentrations were not separated completely in PMF. This study indicates that photochemistry of VOCs in the atmosphere complicates the information about separated sources that can be extracted from PMF and the influence of photochemical processing must be carefully considered in the interpretation of source apportionment studies based upon PMF.

  13. Development of a portable instrument for the continuous analysis of volatile organic compounds (VOCs) and its application to environmental monitoring.

    Science.gov (United States)

    Yamada, Etsu; Matsushita, Kazumasa; Nakamura, Mitsuaki; Fuse, Yasuro; Miki, Sadao; Fujimoto, Kiyoomi; Morita, Hiroyoshi; Shimada, Osamu

    2006-01-01

    A small, time efficient and sensitive instrument for the continuous analysis of very volatile organic compounds (VOCs) with a boiling point lower than 100 degrees C in addition to the analysis of VOCs with a boiling point in the range of 100-150 degrees C was developed and applied to the measurement of VOCs in the course of university research and environmental monitoring. VOCs, such as n-hexane, acetone, ethyl acetate, alcohols, benzene, toluene and xylene, were continuously measured once every 30 min. The detection limits of hexane, ethyl acetate, benzene and toluene at a preconcentration time of 10 min were 0.41 microg/m(3) (0.12 ppb), 0.67 microg/m(3) (0.19 ppb), 0.22 microg/m(3) (0.07 ppb) and 0.22 microg/m(3) (0.06 ppb), respectively. The relative standard deviations of VOCs were less than 5%. The sensitivities of the present method VOCs were higher than those of the conventional method. The temporal changes in VOC concentrations in several laboratories and at a plant for the disposal of organic liquid wastes were measured, and the behavior of VOCs was analyzed. All the VOC concentrations, except that of ethyl acetate, determined using the portable instrument were slightly lower than those determined using a passive sampler. The portable instrument developed in the course of this study can be used for the risk assessment and management of chemicals.

  14. A High Sensitivity and Wide Dynamic Range Fiber-Optic Sensor for Low-Concentration VOC Gas Detection

    Directory of Open Access Journals (Sweden)

    Md. Rajibur Rahaman Khan

    2014-12-01

    Full Text Available In this paper, we propose a volatile organic compound (VOC gas sensing system with high sensitivity and a wide dynamic range that is based on the principle of the heterodyne frequency modulation method. According to this method, the time period of the sensing signal shift when Nile Red containing a VOC-sensitive membrane of a fiber-optic sensing element comes into contact with a VOC. This sensing membrane produces strong, fast and reversible signals when exposed to VOC gases. The response and recovery times of the proposed sensing system were less than 35 s, and good reproducibility and accuracy were obtained.

  15. A High Sensitivity and Wide Dynamic Range Fiber-Optic Sensor for Low-Concentration VOC Gas Detection

    Science.gov (United States)

    Khan, Md. Rajibur Rahaman; Kang, Shin-Won

    2014-01-01

    In this paper, we propose a volatile organic compound (VOC) gas sensing system with high sensitivity and a wide dynamic range that is based on the principle of the heterodyne frequency modulation method. According to this method, the time period of the sensing signal shift when Nile Red containing a VOC-sensitive membrane of a fiber-optic sensing element comes into contact with a VOC. This sensing membrane produces strong, fast and reversible signals when exposed to VOC gases. The response and recovery times of the proposed sensing system were less than 35 s, and good reproducibility and accuracy were obtained. PMID:25490592

  16. Low VOC drying of lumber and wood panel products. Progress report number 6

    Energy Technology Data Exchange (ETDEWEB)

    Yan, H.; Wild, M.P.; Hooda, U.; Banerjee, S. [Institute of Paper Science and Technology, Inc., Atlanta, GA (United States); Shmulsky, R.; Thompson, A.; Ingram, L.; Conners, T. [Mississippi State Univ., MS (United States)

    1998-01-01

    Twenty five Southern pine boards were machined into 2 x 4 inch pieces. Next, the 8 foot boards were cut in half into matched pairs. One of the two was irradiated with RF, while the other served as a control. Both sets were dried under a conventional temperature-time based schedule. Results and conclusions are: RF pretreatment of lumber does not affect strength; the amount of pinene lost into the headspace during low-VOC RF-treatment of wood approximately corresponds to the amount of material lost from the wood; virtually all the pinene can be removed from the low-VOC reactor with steam, suggesting that pinene can be collected when the small amount of steam released during low-headspace treatment is condensed; temperature and moisture loss profiles for particle at 105 C has been modeled using experimental data at 130 C and 160 C; the VOC-temperature curve from dried particle shows a break at about 156 C, the boiling point of {alpha}-pinene, demonstrating that pinene boil-off occurs beyond this threshold; VOC release from dry particle has been successfully modeled; the transport of VOC from sapwood to the atmosphere for pine is faster than the corresponding movement from heartwood to sapwood; and seasonal variations in pine extractives are small.

  17. Comparing the VOC emissions between air-dried and heat-treated Scots pine wood

    Science.gov (United States)

    Manninen, Anne-Marja; Pasanen, Pertti; Holopainen, Jarmo K.

    The emissions of volatile organic compounds (VOCs) from air-dried Scots pine wood and from heat-treated Scots pine wood were compared with GC-MS analysis. Air-dried wood blocks released about 8 times more total VOCs than heat-treated (24 h at 230°C) ones. Terpenes were clearly the main compound group in the air-dried wood samples, whereas aldehydes and carboxylic acids and their esters dominated in the heat-treated wood samples. Only 14 compounds out of 41 identified individual compounds were found in both wood samples indicating considerable changes in VOC emission profile during heat-treatment process. Of individual compounds α-pinene, 3-carene and hexanal were the most abundant ones in the air-dried wood. By contrast, in the heat-treated wood 2-furancarboxaldehyde, acetic acid and 2-propanone were the major compounds of VOC emission. Current emission results reveal that significant chemical changes have occurred, and volatile monoterpenes and other low-molecular-weight compounds have evaporated from the wood during the heat-treatment process when compared to air-dried wood. Major chemical changes detected in VOC emissions are explained by the thermal degradation and oxidation of main constituents in wood. The results suggest that if heat-treated wood is used in interior carpentry, emissions of monoterpenes are reduced compared to air-dried wood, but some irritating compounds might be released into indoor air.

  18. VOC emission rates and emission factors for a sheetfed offset printing shop.

    Science.gov (United States)

    Wadden, R A; Scheff, P A; Franke, J E; Conroy, L M; Javor, M; Keil, C B; Milz, S A

    1995-04-01

    Emission rates were determined during production for a sheetfed offset printing shop by combining the measured concentrations and ventilation rates with mass balance models that characterized the printing space. Air samples were collected simultaneously on charcoal tubes for 12 separate 1-hour periods at 6 locations. Air samples and cleaning solvents were analyzed by gas chromatography for total volatile organic compounds (VOC) and 13 hydrocarbons. The average VOC emission rate was 470 g/hr with a range of 160-1100 g/hr. These values were in good agreement with the amounts of VOC, hexane, toluene, and aromatic C9s determined from estimated solvent usage and measured solvent compositions. Comparison of the emission rates with source activities indicated an emission factor of 30-51 g VOC/press cleaning. Based on the test observations it was estimated that this typical small printing facility was likely to release 1-2 T VOC/year. The methodology also may be useful for the surface coating industry, as emission rates in this study were determined without recourse to a temporary total enclosure and without interfering with worker activities, increasing worker exposure, or increasing safety and explosion hazards.

  19. Release of VOCs and particles during use of nanofilm spray products.

    Science.gov (United States)

    Nørgaard, Asger W; Jensen, Keld A; Janfelt, Christian; Lauritsen, Frants R; Clausen, Per A; Wolkoff, Peder

    2009-10-15

    Here, we present emission data on VOCs and particles emitted during simulated use of four commercial nanofilm spray products (NFPs) used for making easy-to-clean or self-cleaning surfaces on floors, ceramic tiles, and windows. The aim was to characterize the emitted VOCs and to provide specific source strength data for VOCs and particles released to the airduring use of the products. Containers with NFP were mounted on a spray-stand inside a closed stainless steel chamber with no air exchange. NFPs were sprayed in amounts corresponding to 1 m2 surface toward a target plate at a distance of 35 cm. Released VOCs were measured by a combination of air sampling on Tenax TA adsorbent followed by thermal desorption GC/MS and GC/FID analysis and real time measurements using a miniature membrane inlet mass spectrometer. Particles were measured using a fast mobility particle sizer and an aerosol particle sizer. A number of VOCs were identified, including small alcohols, ketones and ethers, chlorinated acetones, a perfluorinated silane, limonene, and cyclic siloxanes. The number of generated particles was on the order of 3 x 10(8) to 2 x 10(10) particles/m3 per g sprayed NFP and were dominated by nanosize particles.

  20. Photolysis frequency measurement techniques: results of a comparison within the ACCENT project

    Directory of Open Access Journals (Sweden)

    K. C. Clemitshaw

    2008-09-01

    Full Text Available An intercomparison of different radiometric techniques measuring atmospheric photolysis frequencies j(NO2, j(HCHO and j(O1D was carried out in a two-week field campaign in June 2005 at Jülich, Germany. Three double-monochromator based spectroradiometers (DM-SR, three single-monochromator based spectroradiometers with diode-array detectors (SM-SR and seventeen filter radiometers (FR (ten j(NO2-FR, seven j(O1D-FR took part in this comparison. For j(NO2, all spectroradiometer results agreed within ±3%. For j(HCHO, agreement was slightly poorer between −8% and +4% of the DM-SR reference result. For the SM-SR deviations were explained by poorer spectral resolutions and lower accuracies caused by decreased sensitivities of the photodiode arrays in a wavelength range below 350 nm. For j(O1D, the results were more complex within +8% and −4% with increasing deviations towards larger solar zenith angles for the SM-SR. The direction and the magnitude of the deviations were dependent on the technique of background determination. All j(NO2-FR showed good linearity with single calibration factors being sufficient to convert from output voltages to j(NO2. Measurements were feasible until sunset and comparison with previous calibrations showed good long-term stability. For the j(O1D-FR, conversion from output voltages to j(O1D needed calibration factors and correction functions considering the influences of total ozone column and elevation of the sun. All instruments showed good linearity at photolysis frequencies exceeding about 10% of maximum values. At larger solar zenith angles, the agreement was non-uniform with deviations explainable by insufficient correction functions. Comparison with previous calibrations for some j(O1D-FR indicated

  1. Synthesis of 2,2'-Biflavanones from Flavone via Electroreduction and Photolysis

    Institute of Scientific and Technical Information of China (English)

    Chen Arh-Hwang; Cheng Chieh-Yuan; Kuo Wei-Bao; Chen Chia-Wen

    2004-01-01

    Biflavonoids, widely distributed in natural plants, had strong biological activities including spasmolysis, peripheral vasodilatation, antibradykinin activity and antispasmogenic action against prostaglandin PGE1, inhibition of cyclic GMP and cyclic AMP phosphodiesterase and inhibition of hepatoma cells. Recently, some bifiavonoids were demonstrated to enhance suppersion of lymphocyte proliferation, inhibition of phospholipaseCrl, anti-inflammatory activity, anti-HIV activity, anticomplementatory activity, antiviral activity and chemoprevention of hepatotoxicity.Several synthetic methods including Ullmann coupling, Baker-Venkataraman rearrangement and cyclization, cyclization from bichalcone, oxidative coupling, reductive coupling, Pd-cathode reduction and photoinduced electron transfer reaction were used for preparations of some bifiavonoids. In this paper, we report synthesis of 2,2'-biflavanones from flavone via electrolytic reductive coupling and photolysis.In the electrochemical reduction, flavone was reduced to give two hydrodimers of rac-2,2'-biflavanone and meso-2,2'-biflavanone and one reductive product of flavanone. The yields were dependent on the nature of electrodes, the kinds of supporting electrolytes and the reaction temperature. It was found to afford higher yields of rac-2,2'-biflavanone and meso-2,2'-biflavanone( 32.4% and 24.8%, 35.8% and 13.4%, respectively,) in the reaction conditions of Pb(-)/C(+)-H2SO4-7F/mol and C(-)/C(+)-H2SOn-5F/mol.In the photolysis with the electron-donating amines including triethylamine or 2-(N,N-dimethylamino)ethanol in acetonitrile, benzene or methylene dichloride, flavone also afford two hydrodimers of rac-2,2'-biflavanone and meso-2,2'-biflavanone and one reductive product of flavanone. Their yields were dependent on the molar ratios of substrate to amine, the kinds of amines,the solvents used and the irradiation sources. Higher yields were afforded rac-2,2'-biflavanone,meso-2,2'-biflavanone and flavanone(30

  2. Acetone photolysis at 248 nm revisited: pressure dependence of the CO and CO2 quantum yields.

    Science.gov (United States)

    Somnitz, H; Ufer, T; Zellner, R

    2009-10-14

    Pressure dependent CO and CO2 quantum yields in the laser pulse photolysis of acetone at 248 nm and T = 298 K have been measured directly using quantitative infrared diode laser absorption. The experiments cover the pressure range from 50 to 900 mbar. It is found that the quantum yields show a significant dependence on total pressure, with Phi(CO) decreasing from around 0.5 at 20 mbar to approximately 0.3 at 900 mbar. The corresponding CO2 yields as observed when O2 exists in the reaction mixture, exhibit exactly the opposite behaviour. For the sum of both a value of 1.05(-0.05)(+0.02) independent of pressure is obtained, showing that the sum of (Phi(CO) + Phi(CO2)) is a measure for the primary quantum yield in the photolysis of acetone. In addition, CO quantum yields and corresponding pressure dependences were measured in experiments using different bath gases including He, Ar, Kr, SF6, and O2 as third body colliders. The theoretical framework in which we discuss these data is based on our previous findings that the pressure dependence of the CO yield is a consequence of a stepwise fragmentation mechanism during which acetone decomposes initially into methyl and a vibrationally 'hot' acetyl radical, with the latter being able to decompose promptly into methyl plus CO. The pressure dependence of the CO yield then originates from the second step and is modelled quantitatively via statistical dynamical calculations using a combination of RRKM theory with a time-dependent master equation (ME) approach. From a comparison of experiment with theory the amount of excess energy in the vibrationally hot acetyl radicals (E* approximately 65 kJ mol(-1)) as well as the characteristic collision parameters for interaction of acetyl with the different bath gases were derived. Values of 90, 280, 310, 545, 550 and 1800 cm(-1) for the average energy transferred per downward collision for the bath gases He, Ar, Kr, O2, N2, and SF6, respectively, are obtained. The calculations also

  3. Clinical validation and calibration of in vitro peroxide tooth whitening.

    Science.gov (United States)

    Putt, Mark S; Moore, Michael H; Milleman, Jeffery L; Milleman, Kimberly R; Thong, Stephen H; Vorwerk, Linda M; Charig, Andrew J; Nelson, Bruce J; Winston, Anthony E

    2009-01-01

    The purpose of this study was to validate and calibrate an in vitro test method for screening the performance of peroxide-containing toothpastes against actual clinical whitening performance. An additional objective was to estimate the whitening performance of a new peroxide-additive gel using the in vitro methodology. A one-month longitudinal clinical study was performed to provide a benchmark for the in vivo intrinsic whitening performance of a peroxide-containing fluoride toothpaste. An in vitro study was then conducted, using freshly prepared slurries of the same peroxide-containing toothpaste in artificial saliva, to repeatedly treat extracted human teeth with natural intrinsic stain. The effect of cumulative treatment time on whiteness was determined using objective chromometer whiteness measurements (L*, a*, and b*), and more subjective Vita Shade guide (Vitapan) comparisons, and the results were correlated. A non-peroxide fluoride toothpaste was used as a negative control. The peroxide gel additive, combined in a 1:1 ratio with each of two non-peroxide toothpastes and diluted in artificial saliva, was evaluated using the same instrumental and subjective measures for in vitro whitening efficacy. The previously evaluated peroxide toothpaste and one of the non-peroxide toothpastes were used as positive and negative controls, respectively. In the clinical study, the peroxide-containing toothpaste produced a linear increase in tooth whiteness with time, achieving an approximately two Vita Shade guide improvement in whiteness at the end of four weeks. The same peroxide toothpaste in vitro produced a curvilinear increase in tooth whiteness versus cumulative treatment time, with a two-shade increase being achieved in 116 minutes. The non-peroxide control toothpaste produced less than half a shade guide increase in whiteness within the first 30 minutes, and none thereafter. Both the clinical and in vitro studies indicated that further whitening can be obtained with

  4. [Evaluation and selection of VOCs treatment technologies in packaging and printing industry].

    Science.gov (United States)

    Wang, Hai-Lin; Wang, Jun-Hui; Zhu, Chun-Lei; Nie, Lei; Hao, Zheng-Ping

    2014-07-01

    Volatile organic compounds (VOCs) play an important role in urban air pollution. Activities of industries including the packaging and printing industries are regarded as the major sources. How to select the suitable treating techniques is the major problem for emission control. In this article, based on the VOCs emission characteristics of the packaging and printing industry and the existing treatment technologies, using the analytic hierarchy process (AHP) model, an evaluation system for VOCs selection was established and all the technologies used for treatment were assessed. It showed that the priority selection was in the following order: Carbon Fiber Adsorption-Desorption > Granular Carbon Adsorption-Desorption > Thermal Combustion > Regenerative Combustion > Catalytic combustion > Rotary adsorption-concentration and combustion > Granular Carbon adsorption-concentration and combustion. Carbon Fiber Adsorption-Desorption was selected as the best available technology due to its highest weight among those technologies.

  5. Energy recovery efficiency and cost analysis of VOC thermal oxidation pollution control technology.

    Science.gov (United States)

    Warahena, Aruna S K; Chuah, Yew Khoy

    2009-08-01

    Thermal oxidation of VOC is extremely energy intensive, and necessitates high efficiency heat recovery from the exhaust heat. In this paper, two independent parameters heat recovery factor (HRF) and equipment cost factor (ECF) are introduced. HRF and ECF can be used to evaluate separately the merits of energy efficiency and cost effectiveness of VOC oxidation systems. Another parameter equipment cost against heat recovery (ECHR) which is a function of HRF and ECF is introduced to evaluate the merit of different systems for the thermal oxidation of VOC. Respective cost models were derived for recuperative thermal oxidizer (TO) and regenerative thermal oxidizer (RTO). Application examples are presented to show the use and the importance of these parameters. An application examples show that TO has a lower ECF while RTO has a higher HRF. However when analyzed using ECHR, RTO would be of advantage economically in longer periods of use. The analytical models presented can be applied in similar environmental protection systems.

  6. VOC removal by plasma-photocatalyst combination : comparison between a low and an atmospheric pressure plasma.

    Science.gov (United States)

    Rousseau, Antoine; Guaitella, Olivier; Gatilova, Lina; Thevenet, Frederic; Guillard, Chantal; Hannemann, Mario; Roepcke, Jurgen

    2004-09-01

    The combination of a non thermal plasma with a photo-catalyst is promising for VOC and odour abatement at room temperature and at a very low energy cost. In classical photocatalysis, UV photons generate an electron hole pair on the surface of the photo-catalyst (TiO2), which generates primary radicals responsible of VOC oxidation. In plasma-photocatalysis combination, activation mechanisms of the photocatalytic surface are not clearly identified to the day. Our strategy is to compare a pulsed DBD at atmospheric pressure containing TiO2 pellets, with a pulsed low pressure DC discharge in contact with a porous TiO2 surface. These two discharge are characterized electrically and the efficiency of VOC removal is performed using infrared laser absorption spectroscopy and gas chromatography.

  7. Control of VOC emissions from a flexographic printing facility using an industrial biotrickling filter.

    Science.gov (United States)

    Sempere, F; Martínez-Soria, V; Penya-Roja, J M; Waalkens, A; Gabaldón, C

    2012-01-01

    The study of an industrial unit of biotrickling filter for the treatment of the exhaust gases of a flexographic facility was investigated over a 2-year period with the objective to meet the volatile organic compound (VOC) regulatory emission limits. Increasing the water flow rate from 2 to 40 m(3) h(-1) improved the performance of the process, meeting the VOC regulation when 40 m(3) h(-1) were used. An empty bed residence time (EBRT) of 36 s was used when the inlet air temperature was 18.7 °C, and an EBRT as low as 26 s was set when the inlet temperature was 26.8 °C. During this long-term operation, the pressure drop over the column of the bioreactor was completely controlled avoiding clogging problems and the system could perfectly handle the non-working periods without VOC emission, demonstrating its robustness and feasibility to treat the emission of the flexographic sector.

  8. A Review of Photocatalysts Prepared by Sol-Gel Method for VOCs Removal

    Directory of Open Access Journals (Sweden)

    Ting Ke Tseng

    2010-05-01

    Full Text Available The sol-gel process is a wet-chemical technique (chemical solution deposition, which has been widely used in the fields of materials science, ceramic engineering, and especially in the preparation of photocatalysts. Volatile organic compounds (VOCs are prevalent components of indoor air pollution. Among the approaches to remove VOCs from indoor air, photocatalytic oxidation (PCO is regarded as a promising method. This paper is a review of the status of research on the sol-gel method for photocatalyst preparation and for the PCO purification of VOCs. The review and discussion will focus on the preparation and coating of various photocatalysts, operational parameters, and will provide an overview of general PCO models described in the literature.

  9. Bubble-Facilitated VOC Transport from LNAPL Smear Zones and Its Potential Effect on Vapor Intrusion.

    Science.gov (United States)

    Soucy, Nicole C; Mumford, Kevin G

    2017-02-10

    Most conceptual and mathematical models of soil vapor intrusion assume that the transport of volatile organic compounds (VOCs) from a source toward a building is limited by diffusion through the soil gas. Under conditions where advection occurs, transport rates are higher and can lead to higher indoor air concentrations. Advection-dominated conditions can be created by gas bubble flow in the saturated zone. A series of laboratory column experiments were conducted to measure mass flux due to bubble-facilitated VOC transport from light nonaqueous phase liquid (LNAPL) smear zones. Smear zones that contained both LNAPL residual and trapped gas, as well as those that contained only LNAPL residual, were investigated. Results showed that the VOC mass flux due to bubble-facilitated transport was orders-of-magnitude higher than under diffusion-limited conditions. Results also showed that the mass flux due to bubble-facilitated transport was intermittent, and increased with an increased supply of dissolved gases.

  10. Electronic nose system combined with membrane interface probe for detection of VOCs in water

    Science.gov (United States)

    Cho, Junghwan; Howard, Zachary; Kurup, Pradeep

    2011-09-01

    This paper describes a novel electronic nose system combined with a membrane interface probe (MIP) for detecting volatile organic compounds (VOCs) in water. The MIP is an in situ tool that allows the detection of certain VOCs in the soil via a pushed or driven probe. The MIP was combined with a sensor array consisting of four different tin-oxide gas sensors known as an electronic nose (e-nose). The designed e-nose system was calibrated in aqueous media spiked with benzene, toluene, ethylbenzene, and p-xylene (BTEX) at concentrations of 100, 250, and 500 ppm. Since the experiment was conducted utilizing five repetitions for each analyte, a data set of 60 measurements was prepared for principal components analysis (PCA). The results of the PCA showed that two principal components contain more than 99% variance information and each VOC is separable and detectable by the e-nose.

  11. X-ray structural analysis of the photolysis products of glycinate and. beta. -alaninate cobalt(III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Polynova, T.N.; Chuklanova, E.B.; Kramarenko, F.G.; Porai-Koshits, M.A.; Poznyak, A.L.; Pavlovskii, V.I.; Stel-mashok, V.E.

    1987-04-01

    The authors were recently able to isolate in crystalline form the intermediate products in the photolysis of various mixed glycinate Co(III) complexes, and have also lately isolated the intermediate products of the photolysis of analogous complexes containing longer chain anions, such as of amino-3-propionate and amino-4-butyrate. In order to determine the structures of these products it is necessary to analyze them by x-ray crystallography. In this paper they describe the structures of two compounds which contain cationic complexes isolated from UV irradiation (lambda = 254 nm) of aqueous solutions of (Coen/sub 2/(..beta..-ala))/sup 2 +/ and Codipy/sub 2/(gly))/sup 2 +/, respectively (en = ethylenediamine, dipy = 2,2'-dipyridine, gly = glycinate, and ..beta..-ala = alaninate). In both cases, the coordinates of all of the atoms, including hydrogen atoms, were determined.

  12. Investigating ion channel distribution using a combination of spatially limited photolysis, Ca(2+) imaging, and patch clamp recording.

    Science.gov (United States)

    Almassy, Janos; Yule, David I

    2013-01-01

    The production of saliva by parotid acinar cells is stimulated by Ca(2+) activation of Cl(-) and K(+) channels located in the apical plasma membrane of these polarized cells. Here, we utilize a combination of spatially limited flash photolysis, Ca(2+) imaging, and electrophysiological recording to investigate the distinct distribution of Ca(2+)-dependent ion channels in the plasma membrane (PM) of enzymatically isolated murine parotid acinar cells. In these experiments, the aim of photolysis is to selectively target and modify the activity of ion channels, thereby revealing membrane-domain-specific differences in distribution. Specifically, the relative distribution of channels to either apical or basal PM can be investigated. Since there is substantial evidence that Ca(2+)-dependent Cl(-) channels are exclusively localized to the apical membrane of acinar cells, this provides an important electrophysiological verification that a particular membrane has been specifically targeted.

  13. Kinetics and product studies of the reaction ClO + BrO using flash photolysis-ultraviolet absorption

    Science.gov (United States)

    Sander, Stanley P.; Friedl, Randall R.

    1989-01-01

    The reaction between BrO and ClO was studied over the pressure range 50-700 torr and temperature range 220-400 K, using the flash photolysis-ultraviolet absorption method described by Watson et al. (1979). In order to investigate the mechanism of the BrO + ClO reaction, the product branch reactions Br + Cl2O yielding ClO + BrCl and Cl2O + h(nu) yielding products were examined. The rate constant for the overall reaction and the Arrhenius expression for the Br + Cl2O reaction are given, as well as the quantum yield for the production of atomic oxygen from the Cl2O photolysis.

  14. Materials Compatibility in High Test Hydrogen Peroxide

    Science.gov (United States)

    Gostowski, Rudy

    1999-01-01

    Previous ratings of the compatibility of high test hydrogen peroxide (HTP) with materials are not adequate for current needs. The goal of this work was to develop a new scheme of evaluation of compatibility of HTP with various materials. Procedures were developed to enrich commercially available hydrogen peroxide to 90% concentration and to assay the product. Reactivity testing, accelerated aging of materials and calorimetry studies were done on HTP with representative metallic and non-metallic materials. It was found that accelerated aging followed by concentration determination using refractive index effectively discriminated between different Class 2 metallic materials. Preliminary experiments using Differential Scanning Calorimetry (DSC) suggest that a calorimetry experiment is the most sensitive means to assay the compatibility of HTP with materials.

  15. Functionalized Palladium Nanoparticles for Hydrogen Peroxide Biosensor

    Directory of Open Access Journals (Sweden)

    H. Baccar

    2011-01-01

    Full Text Available We present a comparison between two biosensors for hydrogen peroxide (H2O2 detection. The first biosensor was developed by the immobilization of Horseradish Peroxidase (HRP enzyme on thiol-modified gold electrode. The second biosensor was developed by the immobilization of cysteamine functionalizing palladium nanoparticles on modified gold surface. The amino groups can be activated with glutaraldehyde for horseradish peroxidase immobilization. The detection of hydrogen peroxide was successfully observed in PBS for both biosensors using the cyclic voltammetry and the chronoamperometry techniques. The results show that the limit detection depends on the large surface-to-volume ratio attained with palladium nanoparticles. The second biosensor presents a better detection limit of 7.5 μM in comparison with the first one which is equal to 75 μM.

  16. The lipid peroxidation in breast cancer patients.

    Science.gov (United States)

    Kedzierska, Magdalena; Olas, Beata; Wachowicz, Barbara; Jeziorski, Arkadiusz; Piekarski, Janusz

    2010-06-01

    The aim of our study was to estimate oxidative stress (by using different biomarkers of lipid peroxidation--isoprostanes and thiobarbituric acid reactive substances (TBARS)) in patients with invasive breast cancer, patients with benign breast diseases and in a control group. We observed a statistically increased level of TBARS in plasma and isoprostanes in urine of patients with invasive breast cancer in comparison with a control group. The concentration of tested biomarkers in plasma or urine from patients with invasive breast cancer was also higher than in patients with benign breast diseases. Moreover, the levels of tested markers in patients with benign breast diseases and in a control group did not differ. Considering the data presented in this study, we suggest that free radicals induce peroxidation of unsaturated fatty acid in patients with breast cancer.

  17. Comparison of the Decomposition VOC Profile during Winter and Summer in a Moist, Mid-Latitude (Cfb) Climate

    Science.gov (United States)

    Forbes, Shari L.; Perrault, Katelynn A.; Stefanuto, Pierre-Hugues; Nizio, Katie D.; Focant, Jean-François

    2014-01-01

    The investigation of volatile organic compounds (VOCs) associated with decomposition is an emerging field in forensic taphonomy due to their importance in locating human remains using biological detectors such as insects and canines. A consistent decomposition VOC profile has not yet been elucidated due to the intrinsic impact of the environment on the decomposition process in different climatic zones. The study of decomposition VOCs has typically occurred during the warmer months to enable chemical profiling of all decomposition stages. The present study investigated the decomposition VOC profile in air during both warmer and cooler months in a moist, mid-latitude (Cfb) climate as decomposition occurs year-round in this environment. Pig carcasses (Sus scrofa domesticus L.) were placed on a soil surface to decompose naturally and their VOC profile was monitored during the winter and summer months. Corresponding control sites were also monitored to determine the natural VOC profile of the surrounding soil and vegetation. VOC samples were collected onto sorbent tubes and analyzed using comprehensive two-dimensional gas chromatography – time-of-flight mass spectrometry (GC×GC-TOFMS). The summer months were characterized by higher temperatures and solar radiation, greater rainfall accumulation, and comparable humidity when compared to the winter months. The rate of decomposition was faster and the number and abundance of VOCs was proportionally higher in summer. However, a similar trend was observed in winter and summer demonstrating a rapid increase in VOC abundance during active decay with a second increase in abundance occurring later in the decomposition process. Sulfur-containing compounds, alcohols and ketones represented the most abundant classes of compounds in both seasons, although almost all 10 compound classes identified contributed to discriminating the stages of decomposition throughout both seasons. The advantages of GC×GC-TOFMS were demonstrated for

  18. Effects of VOCs on herbaceous plants in an open-top chamber experiment

    Energy Technology Data Exchange (ETDEWEB)

    Cape, J.N.; Leith, I.D.; Binnie, J.; Content, J.; Donkin, M.; Skewes, M.; Price, D.N.; Brown, A.R.; Sharpe, A.D

    2003-07-01

    Birdsfoot trefoil and broad-leaved dock were affected by VOCs. - A selection of herbaceous plants representing the ground flora around a typical chemical installation in the UK was exposed continuously for 7 weeks to a mixture of six VOCs (acetone, acetonitrile, dichloromethane, ethanol, methyl t-butyl ether and toluene) in open-top chambers. Exposure concentrations were based on predictions of atmospheric dispersion from a single source, at a distance of approximately 2 km. The effects of continuous exposure, representing a worst-case, were measured in terms of uncontrolled water loss from leaves, leaf wettability, chlorophyll content and fluorescence, dry matter production and detailed observations of changes in plant growth and phenology. There were significant effects of VOC exposure on seed production, leaf water content and photosynthetic efficiency in some plant species. Such effects may be detectable in vegetation close to major industrial point sources of VOCs, or as a result of an accidental release of material during manufacture or transport. Some of the species tested e.g. birdsfoot trefoil (Lotus corniculatus L.) seem to be promising as potential bioindicators for VOCs, but there may be other even more sensitive species waiting to be discovered. However, the most obvious and conveniently measured response to VOC exposure in the birdsfoot trefoil (premature senescence i.e. advanced timing of seed pod production) could easily be confused in the field with climatic influences. It is also uncertain at this stage whether any of the effects observed would lead to longer term ecological changes in natural plant communities, through biased competition between sensitive and more tolerant species.

  19. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    Science.gov (United States)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  20. Influence of way of finishing furniture segments on amount emissions VOCs

    Directory of Open Access Journals (Sweden)

    Petr Čech

    2010-01-01

    Full Text Available The study deals with the influence of way of finishing furniture segments on amount emissions VOCs (volatile organic compounds. The so-called Volatile Organic Compounds (VOC are among the largest pollution sources of both the internal and external environments.VOC is defined as emission of any organic compound or a mixture thereof, with the exception of methane, whereby the compound exerts the pressure of 0.01 kPa or more at the temperature of 20 °C (293.15 K and reaches the corresponding volatility under the specific conditions of its use and can undergo photochemical reactions with nitrogen oxides when exposed to solar radiation. The effects of VOC upon environment can be described by equation: VOC + NOx + UV radiation + heat = tropospheric ozone (O3In this work there were tested MDF (medium density fibreboard coated by resin impregnated paper was used for the furniture components’ production. Next were tested compressed wood, which was used as a second material of furniture components. These both chosen materials was covered by resin impregnated paper and than sequentially finished by regular coat of finish.An attention of this study is especially put on mentioned factors and on quantity of instant and long-term VOCs emissions emitted from furniture components.The amount of emissions from furniture components, in different phases of the preparation including the resin impregnated paper coating finish, was monitored within the time intervals of 24 hours and 720 hours starting after the time of the finish preparation.The MDF (medium density fibreboard coated by resin impregnated paper was used for the furniture components´ production.A compressed wood was used as a second material of furniture components. This alternative material was covered by resin impregnated paper and than sequentially finished by regular coat of finish.

  1. Arid sites stakeholder participation in evaluating innovative technologies: VOC-Arid Site Integrated Demonstration

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, T.S.; McCabe, G.H.; Brockbank, B.R. [and others

    1995-05-01

    Developing and deploying innovative environmental cleanup technologies is an important goal for the U.S. Department of Energy (DOE), which faces challenging remediation problems at contaminated sites throughout the United States. Achieving meaningful, constructive stakeholder involvement in cleanup programs, with the aim of ultimate acceptance of remediation decisions, is critical to meeting those challenges. DOE`s Office of Technology Development sponsors research and demonstration of new technologies, including, in the past, the Volatile Organic Compounds Arid Site Integrated Demonstration (VOC-Arid ID), hosted at the Hanford Site in Washington State. The purpose of the VOC-Arid ID has been to develop and demonstrate new technologies for remediating carbon tetrachloride and other VOC contamination in soils and ground water. In October 1994 the VOC-Arid ID became a part of the Contaminant Plume Containment and Remediation Focus Area (Plume Focus Area). The VOC Arid ID`s purpose of involving stakeholders in evaluating innovative technologies will now be carried on in the Plume Focus Area in cooperation with Site Technology Coordination Groups and Site Specific Advisory Boards. DOE`s goal is to demonstrate promising technologies once and deploy those that are successful across the DOE complex. Achieving that goal requires that the technologies be acceptable to the groups and individuals with a stake in DOE facility cleanup. Such stakeholders include groups and individuals with an interest in cleanup, including regulatory agencies, Native American tribes, environmental and civic interest groups, public officials, environmental technology users, and private citizens. This report documents the results of the stakeholder involvement program, which is an integral part of the VOC-Arid ID.

  2. Catalyst screening for the VOC decomposition using adsorption and oxygen plasma

    Energy Technology Data Exchange (ETDEWEB)

    Kim, H.H.; Ogata, A. [National Inst. of Advanced Industrial Science and Technology, Tokyo (Japan)

    2010-07-01

    Emissions of volatile organic compounds (VOCs) are directly related to the formation of photochemical smog and the secondary aerosol formation, particularly in urban areas. As such, VOC pollution control is a high priority in air quality management. Non-thermal plasmas (NTPs) have been considered for the abatement of VOCs, but 3 key factors must be addressed, notably improve the energy efficiency, have less NOx formation and acceptable material balance. A recent trend in the use of NTP for air pollution control is the combination of NTP with a catalyst. This combined process is subdivided into single-stage and two-stage depending on the position of the catalyst. Ozone-assisted catalysis is the two-stage system. This study focused on the decomposition of VOCs using a single-stage plasma-driven catalysis (PDC) system, and demonstrated the effectiveness of the PDC in terms of energy efficiency, product selectivity and carbon balance. The PDC reactor has a strong dependence on the oxygen content in the oxidation of VOCs. The potentials of various catalysts for cycled system were evaluated in terms of adsorption capability of VOC and enhancement factor (EF). The study focused on zeolites with a large surface area. Nanometer-sized active metals were also loaded on the zeolite surfaces, and their catalytic activity was tested. The metal nanoparticles supported on zeolites enhanced the catalytic activities considerably. ICCD camera observation of the discharge plasma on the surface of catalyst provided an important insight into the understanding of discharge plasma and catalyst. The area of discharge plasma expanded over a wide range by the metal nanoparticles. This physical influence was found to be closely related to the enhanced performance of the plasma-driven catalyst process. 15 refs., 5 figs.

  3. Hydrogen Peroxide Propulsion for Smaller Satellites

    OpenAIRE

    Whitehead, John

    1998-01-01

    As satellite designs shrink, providing maneuvering and control capability falls outside the realm of available propulsion technology. While cold gas has been used on the smallest satellites, hydrogen peroxide propellant is suggested as the next step in performance and cost before hydrazine. Minimal toxicity and a small scale enable bench top propellant preparation and development testing. Progress toward low-cost thrusters and self-pressurizing tank systems is described.

  4. Photolysis and thermolysis of bis(imino)pyridine cobalt azides: C-H activation from putative cobalt nitrido complexes.

    Science.gov (United States)

    Hojilla Atienza, Crisita Carmen; Bowman, Amanda C; Lobkovsky, Emil; Chirik, Paul J

    2010-11-24

    A series of planar aryl-substituted bis(imino)pyridine cobalt azide complexes were prepared and evaluated as synthetic precursors for the corresponding cobalt nitrido compounds. Thermolysis or photolysis of two examples resulted in intramolecular C-H activation of the benzylic positions of the aryl substituents. For the mesityl-substituted compound, C-H activation by the putative nitride resulted in formation of a neutral imine ligand and modification of the chelate by hydrogen transfer to the imine carbon.

  5. The role of direct photolysis and indirect photochemistry in the environmental fate of ethylhexyl methoxy cinnamate (EHMC) in surface waters.

    Science.gov (United States)

    Vione, D; Calza, P; Galli, F; Fabbri, D; Santoro, V; Medana, C

    2015-12-15

    The aquatic environmental fate of ethylhexyl methoxy cinnamate (EHMC), one of the most used UVB filters worldwide, was studied by assessing its environmental persistence and photoinduced transformations. The role of direct and indirect photolysis was evaluated. Direct photolysis was shown to play a key role, and this process is expected to be the main attenuation route of EHMC in sunlit surface waters. In contrast, the reaction with OH radicals would be negligible and that with (3)CDOM* would at most be a secondary process. The measurement of the quantum yield of direct photolysis and of the rate constants of reaction with photogenerated transient species (or, sometimes, the use of reasonable values for the latter) allowed the prediction of the EHMC half-life time in surface waters, by means of a validated photochemical model. The predicted EHMC lifetime is of the order of hours to a few days in fair-weather summertime, and the main factors controlling the EHMC phototransformation in sunlit surface waters would be the water depth and the dissolved organic carbon (DOC) content. The formation of transformation products (TPs) was followed as well via HPLC/HRMS. Three TPs were detected in the samples exposed to UVA radiation, while one additional TP was detected in the samples exposed to UVB radiation. The detected TPs comprised 4-methoxybenzaldehyde, a hydroxylated derivative and dimeric species. Through the use of heterogeneous photocatalysis with TiO2, seven additional TPs were identified, most of them resulting from the further degradation of primary TPs formed through direct photolysis and that might be detected in aquatic systems as well. The photodegradation of EHMC in the presence of TiO2 yielded more toxic TPs than the parent compound (as determined with the Vibrio fischeri Microtox assay). The increased toxicity is partially accounted for by the formation of 4-methoxybenzaldehyde.

  6. Photolysis quantum yield measurements in the near-UV; a critical analysis of 1-(2-nitrophenyl)ethyl photochemistry.

    Science.gov (United States)

    Corrie, John E T; Kaplan, Jack H; Forbush, Biff; Ogden, David C; Trentham, David R

    2016-05-11

    The photolysis quantum yield, Qp, of 1-(2-nitrophenyl)ethyl phosphate (caged Pi) measured in the near-UV (342 nm peak with 60 nm half-bandwidth) is 0.53 and is based on results reported in 1978 (Biochemistry, 17, 1929-1935). This article amplifies methodology for determining that Qp in view of different recent estimates. Some general principles together with other examples relating to measurement of Qp values are discussed together with their relevance to biological research.

  7. Inactivation of human myeloperoxidase by hydrogen peroxide.

    Science.gov (United States)

    Paumann-Page, Martina; Furtmüller, Paul G; Hofbauer, Stefan; Paton, Louise N; Obinger, Christian; Kettle, Anthony J

    2013-11-01

    Human myeloperoxidase (MPO) uses hydrogen peroxide generated by the oxidative burst of neutrophils to produce an array of antimicrobial oxidants. During this process MPO is irreversibly inactivated. This study focused on the unknown role of hydrogen peroxide in this process. When treated with low concentrations of H2O2 in the absence of reducing substrates, there was a rapid loss of up to 35% of its peroxidase activity. Inactivation is proposed to occur via oxidation reactions of Compound I with the prosthetic group or amino acid residues. At higher concentrations hydrogen peroxide acts as a suicide substrate with a rate constant of inactivation of 3.9 × 10(-3) s(-1). Treatment of MPO with high H2O2 concentrations resulted in complete inactivation, Compound III formation, destruction of the heme groups, release of their iron, and detachment of the small polypeptide chain of MPO. Ten of the protein's methionine residues were oxidized and the thermal stability of the protein decreased. Inactivation by high concentrations of H2O2 is proposed to occur via the generation of reactive oxidants when H2O2 reacts with Compound III. These mechanisms of inactivation may occur inside neutrophil phagosomes when reducing substrates for MPO become limiting and could be exploited when designing pharmacological inhibitors.

  8. Comparison of different real time VOC measurement techniques in a ponderosa pine forest

    Science.gov (United States)

    Kaser, L.; Karl, T.; Schnitzhofer, R.; Graus, M.; Herdlinger-Blatt, I. S.; DiGangi, J. P.; Sive, B.; Turnipseed, A.; Hornbrook, R. S.; Zheng, W.; Flocke, F. M.; Guenther, A.; Keutsch, F. N.; Apel, E.; Hansel, A.

    2013-03-01

    Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20-25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and

  9. On-road emission characteristics of VOCs from light-duty gasoline vehicles in Beijing, China

    Science.gov (United States)

    Cao, Xinyue; Yao, Zhiliang; Shen, Xianbao; Ye, Yu; Jiang, Xi

    2016-01-01

    This study is the third in a series of three papers aimed at characterizing the VOC emissions of vehicles in Beijing. In this study, 30 light-duty vehicles fueled with gasoline were evaluated using a portable emission measurement system (PEMS) as they were driven on a predesigned, fixed test route. All of the tested vehicles were rented from private vehicle owners and spanned regulatory compliance guidelines ranging from Pre-China I to China IV. Alkanes, alkenes, aromatics and some additional species in the exhaust were collected in Tedlar bags and analyzed using gas chromatography/mass spectrometry (GC-MS). Carbonyls were collected on 2,4-dinitrophenyhydrazine (DNPH) cartridges and analyzed using high-performance liquid chromatography (HPLC). Overall, 74 VOC species were detected from the tested vehicles, including 22 alkanes, 6 alkenes, 1 alkyne, 16 aromatics, 3 cyclanes, 10 halohydrocarbons, 12 carbonyls and 4 other compounds. Alkanes, aromatics and carbonyls were the dominant VOCs with weight percentages of approximately 36.4%, 33.1% and 17.4%, respectively. The average VOC emission factors and standard deviations of the Pre-China I, China I, China II, China III and China IV vehicles were 469.3 ± 200.1, 80.7 ± 46.1, 56.8 ± 37.4, 25.6 ± 11.7 and 14.9 ± 8.2 mg/km, respectively, which indicated that the VOC emissions significantly decreased under stricter vehicular emission standards. Driving cycles also influenced the VOC emissions from the tested vehicles. The average VOC emission factors based on the travel distances of the tested vehicles under urban driving cycles were greater than those under highway driving cycles. In addition, we calculated the ozone formation potential (OFP) using the maximum incremental reactivity (MIR) method. The results of this study will be helpful for understanding the true emission levels of light-duty gasoline vehicles and will provide information for controlling VOC emissions from vehicles in Beijing, China.

  10. VOC emissions, evolutions and contributions to SOA formation at a receptor site in Eastern China

    Directory of Open Access Journals (Sweden)

    B. Yuan

    2013-03-01

    Full Text Available Volatile organic compounds (VOCs were measured by two online instruments (GC-FID/MS and PTR-MS at a receptor site on Changdao Island (37.99° N, 120.70° E in eastern China. Reaction with OH radical dominated the chemical loss of most VOC species during the Changdao campaign. A photochemical age based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory, but the emission ratios of oxygenated VOCs (OVOCs are significantly lower than those from emission inventory. The photochemical age based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of OA to CO are determined to be 14.9 μg m−3 ppm−1 and SOA are produced at an enhancement ratio of 18.8 μg m−3 ppm−1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m−3 ppm−1 CO and low-NOx condition (6.5 μg m−3 ppm−1 CO. Polycyclic aromatic hydrocarbons (PAHs and higher alkanes (>C10 account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs may be a large contributor to SOA formation during the Changdao campaign. SOA formation potential of primary VOC emissions determined from both field campaigns and emission inventory in China are lower than the measured SOA levels reported in Beijing and Pearl River Delta (PRD, indicating SOA formation cannot be explained by VOC oxidation in this regions. SOA budget in China is estimated to be 5.0–13.7 Tg yr−1, with a fraction of at least 2.7 Tg yr−1 from anthropogenic emissions, which are much higher than the previous estimates from regional models.

  11. Comparison of the substrate effect on VOC emissions from water based varnish and latex paint.

    Science.gov (United States)

    Silva, Gabriela V; Vasconcelos, M Teresa S D; Santos, Armando M; Fernandes, Eduardo O

    2003-01-01

    The building materials are recognised to be major contributors to indoor air contamination by volatile organic compounds (VOCs). The improvement of the quality of the environment within buildings is a topic of increasing research and public interest. Legislation in preparation by the European Commission may induce, in the near future, European Union Member States to solicit the industries of paints, varnishes and flooring materials for taking measures, in order to reduce the VOC emissions resulting from the use of their products. Therefore, product characterisation and information about the influence of environmental parameters on the VOC emissions are fundamental for providing the basic scientific information required to allow architects, engineers, builders, and building owners to provide a healthy environment for building occupants. On the other hand, the producers of coating building materials require this information to introduce technological alterations, when necessary, in order to improve the ecological quality of their products, and to make them more competitive. Studies of VOC emissions from wet materials, like paints and varnishes, have usually been conducted after applying the material on inert substrates, due to its non-adsorption and non-porosity properties. However, in real indoor environments, these materials are applied on substrates of a different nature. One aim of this work was to study, for the first time, the VOC emissions from a latex paint applied on concrete. The influence of the substrate (uncoated cork parquet, eucalyptus parquet without finishing and pine parquet with finishing) on the emissions of VOC from a water-based varnish was also studied. For comparison purposes, polyester film (an inert substrate) was used for both wet materials. The specific emission rates of the major VOCs were monitored for the first 72 h of material exposure in the atmosphere of a standardized test chamber. The air samples were collected on Tenax TA and

  12. [Pollution characteristics and health risk assessment of atmospheric VOCs in the downtown area of Guangzhou, China].

    Science.gov (United States)

    Li, Lei; Li, Hong; Wang, Xue-Zhong; Zhang, Xin-Min; Wen, Chong

    2013-12-01

    The measurements of 31 kinds of VOCs in the ambient air of a site were carried out in the downtown of Guangzhou by online method from November 5, 2009 to November 9, 2009. The ambient level and composition characteristics, temporal variation characteristics, sources identification, and chemical reactivity of VOCs were studied, and the health risk of VOCs in the ambient air in the study area was assessed by using the international recognized health risk assessment method. Results showed that the mean and the range of the mass concentrations of 31 VOCs were 114.51 microg x m(-3) and 29.42-546.06 microg x m(-3), respectively. The mass concentrations of 31 VOCs, and those of alkanes, alkenes, and aromatics all showed a changing trend of higher in the morning and in the evening, and lower at noontime. Vehicular exhaust, gasoline and liquefied petroleum gas evaporates were the main sources of VOCs with the volatilization of paints and solvents being important emission sources. Toluene, trans-2-butene, m/p-xylene, i-butane, and 1,3,5-trimethylbenzene were the key reactive species among the 31 VOCs. Vehicular exhaust and gasoline evaporation were the main sources of VOCs leading to the formation of ozone. Health risk assessment showed that n-hexane, 1,3-butadiene, benzene, toluene, ethylbenzene, m/p-xylene and o-xylene had no appreciable risk of adverse non-cancer health effect on the exposed population, but 1, 3-butadiene and benzene had potential cancer risk. By comparing the corresponding data about health risk assessment of benzene compounds in some cities in China, it is concluded that benzene can impose relatively high cancer risk to the exposed populations in the ambient air of some cities in China. Therefore, strict countermeasures should be taken to further control the pollution of benzene in the ambient air of cities, and it is imperative to start the related studies and develop the atmospheric environmental health criteria and national ambient air quality

  13. Comparison of different real time VOC measurement techniques in a ponderosa pine forest

    Directory of Open Access Journals (Sweden)

    L. Kaser

    2012-10-01

    Full Text Available Volatile organic compound (VOC mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS, a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS, a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA, a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS and a Fiber Laser-Induced Fluorescence Instrument (FILIF. The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK+MAC using PTR-(TOF-MS at this site. A study-average relative contribution of 85% for MVK+MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the

  14. Comparison of different real time VOC measurement techniques in a ponderosa pine forest

    Directory of Open Access Journals (Sweden)

    L. Kaser

    2013-03-01

    Full Text Available Volatile organic compound (VOC mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS, a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS, a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA, a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS and a Fiber Laser-Induced Fluorescence Instrument (FILIF. The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC using PTR-(TOF-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study

  15. VOCs Speciation From Steam Boiler Stacks of Industries Located in Naucalpan

    Science.gov (United States)

    Mejia, G. M.; Tejeda, D. D.; Bremauntz, M. P.; Valdez, A.; Montufar, P. C.; Martinez, M. A.; Sierra, M. J.; Gonzalez, C. A.

    2007-05-01

    Results of VOCs speciation from industrial steam boiler stacks located in Naucalpan are presented and discussed. This municipality is located north of the Metropolitan Zone of the Valley of Mexico (MZVM). Speciation of VOCs is important to generate information about sources of pollution, to update emission inventories, to study the dynamics of pollutants in the atmosphere, and to estimate possible risks of population exposure. This information is valuable for decision making on air pollution control strategies. Samples from 35 steam boilers form industries burning Diesel, LPG, or CNG were taken using the US-EPA Method 18. Selected samples from the use of different fuels were analyzed using gas chromatography and flame ionization detection (GC-FID) according to US-EPA protocol TO-14. The VOCs analyzed included alkanes of 9 carbons or less, alkenes of 7 carbons or less and aromatics (families of benzene). The results show consistency on the VOCs detected on Diesel samples. The main compounds found were 1- Butene+iButylene, m/p-Xylene, Ethane, Propene, Propane, Acetylene, 2Me-1Butene, and Toluene. The average concentrations of these compounds were in the range of 130 to 385 ppbC. The results of LPG samples did not show a definite pattern of VOCs, although light components predominate and, in some samples, Toluene and Xylene. These last components were not expected for industries reporting the use of LPG, perhaps due to the use of a combination of fuels and mistakes in the reports of fuel used at the time of sampling. The analysis of CNG samples show predominance of light VOCs, in the range of 90 to 300 ppbC. As in the case of LPG, some aromatics showed high concentrations in some samples analyzed perhaps due to the use of different fuels in the boiler. The results of this study are the first results of VOCs speciation obtained form exhaust gases from stacks of Mexican industries. The data reported are valuable to analyze emission inventories of VOCs and to better

  16. A significant role for nitrate and peroxide groups on indoor secondary organic aerosol.

    Science.gov (United States)

    Carslaw, Nicola; Mota, Tiago; Jenkin, Michael E; Barley, Mark H; McFiggans, Gordon

    2012-09-04

    This paper reports indoor secondary organic aerosol, SOA, composition based on the results from an improved model for indoor air chemistry. The model uses a detailed chemical mechanism that is near-explicit to describe the gas-phase degradation of relevant indoor VOC species. In addition, gas-to-particle partitioning is included for oxygenated products formed from the degradation of limonene, the most ubiquitous terpenoid species in the indoor environment. The detail inherent in the chemical mechanism permits the indoor SOA composition to be reported in greater detail than currently possible using experimental techniques. For typical indoor conditions in the suburban UK, SOA concentrations are ~1 μg m(-3) and dominated by nitrated material (~85%), with smaller contributions from peroxide (12%), carbonyl (3%), and acidic (1%) material. During cleaning activities, SOA concentrations can reach 20 μg m(-3) with the composition dominated by peroxide material (73%), with a smaller contribution from nitrated material (21%). The relative importance of these different moieties depends crucially (in order) on the outdoor concentration of O(3), the deposition rates employed and the scaling factor value applied to the partitioning coefficient. There are currently few studies that report observation of aerosol composition indoors, and most of these have been carried out under conditions that are not directly relevant. This study highlights the need to investigate SOA composition in real indoor environments. Further, there is a need to measure deposition rates for key indoor air species on relevant indoor surfaces and to reduce the uncertainties that still exist in gas-to-particle phase parametrization for both indoor and outdoor air chemistry models.

  17. Evaluation of photolysis and hydrolysis of atrazine and its first degradation products in the presence of humic acids

    Energy Technology Data Exchange (ETDEWEB)

    Prosen, Helena [University of Ljubljana, Faculty of Chemistry and Chemical Technology, Askerceva 5, SI-1000 Ljubljana (Slovenia)]. E-mail: helena.prosen@uni-lj.si; Zupancic-Kralj, Lucija [University of Ljubljana, Faculty of Chemistry and Chemical Technology, Askerceva 5, SI-1000 Ljubljana (Slovenia)

    2005-02-01

    Relative importance of hydrolysis and photolysis of atrazine and its degradation products in aqueous solutions with dissolved humic acids (HA) has been assessed under exposure to sunlight and under UV irradiation. Quantum yield for direct photolysis of atrazine at 254 nm was 0.037 mol photon{sup -1}, the reaction order was 0.8. Atrazine, desethylatrazine and desisopropylatrazine converted to their 2-hydroxy analogs with rate constants 0.02-0.08 min{sup -1} in clear solutions, while addition of HA (300 mg L{sup -1}) caused a 10-fold increase in rate constants. Hydroxyatrazine was not degraded. No evidence of photo-Fenton reaction was found. Under exposure to solar light, atrazine, desethylatrazine and desisopropylatrazine were converted to 2-hydroxy analogs only at pH 2 because of acid hydrolysis and possible contribution of photolysis. At lower HA concentration, only their light-shielding effect was noticed, while at higher concentrations, HA-catalysed hydrolysis prevailed. Hydroxyatrazine concentration diminished at all pH values in solutions without HA exposed to sunlight. - Different humic acid-influenced degradation processes influence atrazine and its degradation products.

  18. Investigations of UV photolysis of PVP-capped silver nanoparticles in the presence and absence of dissolved organic carbon

    Energy Technology Data Exchange (ETDEWEB)

    Poda, Aimee R., E-mail: aimee.r.poda@usace.army.mil; Kennedy, Alan J.; Cuddy, Michael F., E-mail: michael.cuddy@usace.army.mil; Bednar, Anthony J. [U.S. Army Engineer Research and Development Center, Environmental Laboratory (United States)

    2013-05-15

    This study investigated the effect of UV irradiation on the characteristics and toxicity of 50 nm (nominal diameter) polyvinylpyrrolidone-capped silver nanoparticles (AgNPs) in the presence and absence of dissolved organic carbon (DOC). The photolysis resulted in a decrease in average particle size as measured by field flow fractionation interfaced with inductively coupled plasma mass spectrometry. The decrease in size was attributed to the photo-induced oxidation of the PVP and dissolution of metallic silver. Moreover, photolysis of the AgNPs in solutions containing DOC appeared to give rise to small nanoparticles ({approx}5 nm) formed via reduction of dissolved silver ions. These results were consistent with photolysis of AgNO{sub 3} solutions initially devoid of nanoparticles. Thus, the carbon-containing constituents of DOC serve as reducing agents for Ag{sup +}, primarily under conditions of UV irradiation. The standard zooplankton model, Daphnia magna, indicated that the toxicity of nanosilver was significantly reduced when the AgNPs have been exposed to UV light. Observed toxicity was further reduced when AgNPs in DOC-containing solutions were exposed to UV. These results suggest that environmentally relevant conditions such as DOC and UV light are important mitigating factors that mediate the aquatic toxicity of AgNPs.

  19. Photolysis of the antidepressants amisulpride and desipramine in wastewaters: Identification of transformation products formed and their fate.

    Science.gov (United States)

    Gros, Meritxell; Williams, Mike; Llorca, Marta; Rodriguez-Mozaz, Sara; Barceló, Damià; Kookana, Rai S

    2015-10-15

    Attenuation of pharmaceuticals due to natural sunlight is expected to be an important removal pathway in wastewater treatment plants using treatment lagoon systems. In this work, the photolysis of two antidepressants, amisulpride and desipramine, has been investigated in both ultrapure water and wastewater under simulated solar irradiation. Results showed that for amisulpride short irradiation times (t1/2 approximately 3h in pure water and 4h in wastewater) were adequate to degrade the parent compound while a longer exposure period was required for desipramine (t1/2 of approximately 36 h in pure water), although its degradation is enhanced almost three times by indirect photolysis in wastewaters. A significant number of transformation products (TPs) were identified for both pharmaceuticals by high-resolution mass spectrometry. In general, TPs formed are not persistent although acute toxicity tests for desipramine and its TPs showed an increase of the mixture toxicity after solar irradiation, suggesting that some TPs may be more toxic than the parent compound. In wastewaters collected from treatment lagoons, only amisulpride and one of its major TPs, TP 357, were detected. This indicates that long solar exposure times may be necessary for an effective elimination of these substances in lagoon systems or that photolysis may not be the main removal pathway for these particular compounds.

  20. On the photochemistry of IONO2: absorption cross section (240-370 nm) and photolysis product yields at 248 nm.

    Science.gov (United States)

    Joseph, D M; Ashworth, S H; Plane, J M C

    2007-11-01

    The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) iodine oxides, but the formation and subsequent photolysis of IONO(2) is very inefficient as an ozone-depleting cycle.

  1. Synthesis of binary iron-carbon nanoparticles by UV laser photolysis of Fe(CO)5 with various hydrocarbons

    Science.gov (United States)

    Eremin, A. V.; Gurentsov, E. V.; Musikhin, S. A.

    2016-10-01

    In this study the laser photolysis of the mixtures containing vapors of various hydrocarbons and iron pentacarbonyl was implemented to nanoparticle formation. The radiation source used for photo-dissociation of precursors was a pulsed Nd:Yag laser operated at a wavelength of 266 nm. Under UV radiation the molecules of Fe(CO)5 decomposed, forming atomic iron vapor and unsaturated carbonyls at well-known and readily controllable parameters. The subsequent condensation of supersaturated metal vapor resulted in small iron clusters and nanoparticles formation. The growth process of the nanoparticles was observed by a method of laser light extinction. Laser induced incandescence technique was applied for particle sizing during the process of their formation. Additionally nanoparticle samples were investigated by a transmission electron microscope. The particle size distribution was measured by statistical treatment of microphotographs. The elemental analysis by energy-dispersive x-ray spectroscopy and electron diffraction pattern gave the composition and structure of nanoparticles. The core-shell iron-carbon nanoparticles were synthesized by joint laser photolysis of iron pentacarbonyl with benzene and acetylene. The photolysis of the mixtures of toluene, butanol and methane with iron pentacarbonyl revealed in a pure iron particles formation which fast oxidized in air when were extracted out of the reactor.

  2. Unexpected photolysis of the sunscreen octinoxate in the presence of the sunscreen avobenzone.

    Science.gov (United States)

    Sayre, Robert M; Dowdy, John C; Gerwig, Andre J; Shields, William J; Lloyd, Roger V

    2005-01-01

    A major concern raised about photostability studies of sunscreen products is that the photodegradation of sunscreens does not readily translate into changes in product performance. This study examines the correlation between photochemical degradation of sunscreen agents and changes in protection provided by sunscreen films. Films of a commercial sunscreen product containing avobenzone, oxybenzone and octinoxate were irradiated using a fluorescent UV-A phototherapy lamp with additional UV-B blocking filter. Periodically, during irradiation the transmittances of the films were measured and samples collected for chemical analysis of the sunscreen agents using high-performance liquid chromatography techniques. The results show that UV-induced changes in UV transmittance of sunscreen films correlate with changes in concentration of sunscreen agents. In a parallel experiment, we also irradiated a thin film of the same product in the cavity of an electron spin resonance (ESR) spectrometer. We report the concomitant photolysis of avobenzone and octinoxate that predominates over expected E/Z photoisomerization and that irradiation of a film of this product produced free radicals detected by ESR spectroscopy that persisted even after exposure had ended.

  3. Photo-assisted electrochemical degradation of simulated textile effluent coupled with simultaneous chlorine photolysis.

    Science.gov (United States)

    de Mello Florêncio, Thaíla; de Araújo, Karla Santos; Antonelli, Raissa; de Toledo Fornazari, Ana Luiza; da Cunha, Paula Cordeiro Rodrigues; da Silva Bontempo, Letícia Helena; de Jesus Motheo, Artur; Granato, Ana Claudia; Malpass, Geoffroy Roger Pointer

    2016-10-01

    The influence of chloride ion concentration during the photo-assisted electrochemical degradation of simulated textile effluent, using a commercial Ti/Ru0.3Ti0.7O2 anode, was evaluated. Initially, the effect of applied current and supporting electrolyte concentration on the conversion of chloride ions to form reactive chlorine species in 90 min of experiment was analyzed in order to determine the maximum production of reactive chlorine species. The optimum conditions encountered (1.5 A and 0.3 mol dm(-3) NaCl) were subsequently employed for the degradation of simulated textile effluent. The efficiency of the process was determined through the analysis of chemical oxygen demand (COD), total organic carbon (TOC), of the presence of organochlorine products and phytotoxicity. Photo-assisted electrochemical degradation was more efficient for COD and TOC removal than the electrochemical technique alone. With simultaneous UV irradiation, a reduced quantity of reactive chlorine was produced, indicating that photolysis of the chlorine species led to the formation of hydroxyl radicals. This fact turns a simple electrochemical process into an advanced oxidation process.

  4. Economic and simple system to combine single-spot photolysis and whole-field fluorescence imaging

    Science.gov (United States)

    Jaafari, Nadia; Henson, Mark; Graham, Jeremy; Canepari, Marco

    2013-06-01

    In recent years, the use of light emitting diodes (LEDs) has become commonplace in fluorescence microscopy. LEDs are economical and easy to couple to commercial microscopes, and they provide powerful and stable light that can be triggered by transistor-transistor logic pulses in the range of tens of microseconds or shorter. LEDs are usually installed on the epifluorescence port of the microscope to obtain whole-field illumination, which is ideal for fluorescence imaging. In contrast, photolysis or channelrhodopsin stimulation often requires localized illumination, typically achieved using lasers. Here we show that insertion of a long-pass (>411 nm) filter with an appropriately sized pinhole in the epifluorescence pathway, combined with dual UV/visible illumination, can produce efficient whole-field visible illumination and spot UV illumination of 15 to 20 μm. We tested our system by performing calcium imaging experiments combined with L-glutamate or N-methyl-D-aspartic acid (NMDA) photorelease in hippocampal neurons from brain slices or dissociated cultures, demonstrating the ability to obtain local activation of NMDA receptors exclusively in the illuminated spot. The very inexpensive and simple system that we report here will allow many laboratories with limited budgets to run similar experiments in a variety of physiological applications.

  5. Degradation of 4-chloro 2-aminophenol using combined strategies based on ultrasound, photolysis and ozone.

    Science.gov (United States)

    Barik, Arati J; Gogate, Parag R

    2016-01-01

    The present work investigates the degradation of 4-chloro 2-aminophenol (4C2AP), a highly toxic organic compound, using ultrasonic reactors and combination of ultrasound with photolysis and ozonation for the first time. Two types of ultrasonic reactors viz. ultrasonic horn and ultrasonic bath operating at frequency of 20 kHz and 36 kHz respectively have been used in the work. The effect of initial pH, temperature and power dissipation of the ultrasonic horn on the degradation rate has been investigated. The established optimum parameters of initial pH as 6 (natural pH of the aqueous solution) and temperature as 30 ± 2°C were then used in the degradation studies using the combined approaches. Kinetic study revealed that degradation of 4C2AP followed first order kinetics for all the treatment approaches investigated in the present work. It has been established that US+UV+O3 combined process was the most promising method giving maximum degradation of 4C2AP in both ultrasonic horn (complete removal) and bath (89.9%) with synergistic index as 1.98 and 1.29 respectively. The cavitational yield of ultrasonic bath was found to be eighteen times higher as compared to ultrasonic horn implying that configurations with higher overall areas of transducers would be better selection for large scale treatment. Overall, the work has clearly demonstrated that combined approaches could synergistically remove the toxic pollutant (4C2AP).

  6. Photolysis and thermolysis of pyridyl carbonyl azide monolayers on single-crystal platinum.

    Science.gov (United States)

    Adkinson, Dana K; Magri, David C; Pitters, Jason L; Griffiths, Keith; Norton, Peter R; Workentin, Mark S

    2013-01-01

    The photochemical and thermal reactivity of a number of acyl azide-substituted pyridine compounds, namely nicotinyl azide, isonicotinyl azide, picolinyl azide and dinicotinyl azide with investigated as saturated monolayers on a single-crystal Pt(111) surface in an ultrahigh vacuum chamber. Multilayers of the substrates exhibited a maximum rate of desorption at 270 K, above which, stable saturated monolayers formed as characterized by reflection-absorption infrared spectroscopy by observation of C=O and N3 bands at 1700 cm(-1), and 2100 and 1300 cm(-1) respectively. The monolayers were stable up to 400 K. Photolysis of the monolayer (or heating above 400 K) results in the formation of the respective isocyanate intermediate after loss of nitrogen as evidenced by the appearance of a new infrared band at 2260 cm(-1) with concomitant loss of the azide bands. The resulting isocyanate saturated monolayer is stable in absence of nucleophiles, but can be quenched with appropriate nucleophiles. © 2013 The American Society of Photobiology.

  7. Direct and indirect photolysis of triclocarban in the presence of dissolved organic matter

    Directory of Open Access Journals (Sweden)

    Tamara D. Trouts

    2015-05-01

    Full Text Available Abstract Photolysis is an important attenuation pathway for the removal of wastewater effluent organic micropollutants from surface waters. In this work, direct and indirect processes leading to the degradation of the disinfectant, triclocarban were studied. Photo-irradiation experiments were conducted in water collected from Old Woman Creek (OWC a tributary of Lake Erie near Huron, OH, USA and in solutions of fulvic acids isolated from the Suwannee River, Georgia, USA (SRFA, Old Woman Creek (OWCFA and Pony Lake, Antarctica (PLFA. Photodegradation of triclocarban proceeded faster in the presence of all three fulvic acids relative to deionized water. PLFA, an autochthonous dissolved organic matter (DOM was found to be more reactive than the other fulvic acids, while the mostly allochthonous SRFA exhibited the lowest reactivity toward triclocarban. The later observation can be in part explained by anti-oxidant moieties present in SRFA. Photosensitized triclocarban degradation in whole water DOM from OWC was entirely attributable to the fulvic acid fraction and suggests that this component is the most photo-reactive fraction of the DOM. Anoxic and methanol-quenched experiments revealed unexpected results whereby the former suggests oxidation through reaction with triplet DOM, while the later is indicative of reaction with photo-generated hydroxyl radicals. It is possible that methanol can quench excited DOM species, which would shut down the triplet oxidation pathway. Finally, we observed no enhancement of triclocarban-photosensitized degradation through the addition of iron.

  8. Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

    1993-01-01

    Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

  9. Combined photolysis and catalytic ozonation of dimethyl phthalate in a high-gravity rotating packed bed.

    Science.gov (United States)

    Chang, Chia-Chi; Chiu, Chun-Yu; Chang, Ching-Yuan; Chang, Chiung-Fen; Chen, Yi-Hung; Ji, Dar-Ren; Yu, Yue-Hwa; Chiang, Pen-Chi

    2009-01-15

    In this study, a high-gravity rotating packed bed (HGRPB) was used as a catalytic ozonation reactor to decompose dimethyl phthalate (DMP), an endocrine disrupting chemical commonly encountered. The HGRPB is an effective gas-liquid mixing equipment which can enhance the ozone mass transfer coefficient. Platinum-containing catalyst (Pt/-Al2O3) of Dash 220N and ultra violet (UV) lamp were combined in the high-gravity ozonation (HG-OZ) system to enhance the self-decomposition of molecular ozone in liquid to form highly reactive radical species. Different combinations of HG-OZ with Dash 220N and UV for the degradation of DMP were tested. These include HG-OZ, HG catalytic OZ (HG-Pt-OZ), HG photolysis OZ (HG-UV-OZ) and HG-UV-Pt-OZ. The result indicated that all the above four ozonation processes result in significant decomposition of DMP and mineralization of total organic carbon (TOC) at the applied ozone dosage per volume of liquid sample of 1.2gL(-1). The UV and Pt/gamma-Al2O3 combined in HG-OZ can enhance the TOC mineralization efficiency (eta(TOC)) to 56% (via HG-UV-OZ) and 57% (via HG-Pt-OZ), respectively, while only 45% with ozone only. The process of HG-UV-Pt-OZ offers the highest eta(TOC) of about 68%.

  10. [Effect of ionic liquid [bmim][PF6] on the transient photolysis behavior of xanthone].

    Science.gov (United States)

    Fu, Hai-Ying; Cao, Xi-Yan; Xing, Zhao-Guo; Wu, Guo-Zhong

    2013-07-01

    The transient photochemical behavior of xanthone (XAN) in 1-butyl-3-methyl imidazolium hexafluoride phosphate ionic liquid ([bmim][PF6]) or binary mixed solution with acetonitrile (MeCN) was investigated by nano-second laser photolysis techniques. The spectral blue shift of 3XAN* was observed in the neat [bmim][PF6] or IL/MeCN mixture solution compared to MeCN solution. And the yield was also increased. Moreover, the energy transfer rate constant of XAN and naphthalene (NAP) was affected by the concentrations of ionic liquid. The values decreased rapidly with increasing VIL. For example, the values were 1.2 x 10(10) mol x L(-1) x s(-1) in MeCN, and 1.1 x 10(8) mol x L(-1) x s(-1) in [bmim][PF6], respectively. The photo-induced electron transfer between XAN and N,N-dimethylaniline was also investigated by changing the concentrations of [bmim][PF6] in binary solution.

  11. Photolysis of benzophenone with two-step two-laser excitation

    Institute of Scientific and Technical Information of China (English)

    CAI; Xichen

    2001-01-01

    [1]Carmichael, I., Hug, G. L., Triplet-triplet absorption spectra of organic molecules in condensed phases, J. Phys. Chem. Ref. Data, 1986, 15(1): 1-20.[2]Nikogosyan, D. N., Two-quantum UV photochemistry of nucleic acids: comparison with conventional low-intensity UV photochemistry and radiation chemistry, Int. J. Radiat. Biol., 1990, 57(2): 233-299.[3]Yao, S. D., Sheng, S. G., Cai, J. H. et al., Nanosecond pulse radiolysis studies in China, Radiat. Phys. Chem., 1995, 46:105-109.[4]Baumann, H.. Merckel, C., Timpe, H. -J., The laser versus the lamp: reactivity of the diphenyl ketyl radical in the ground and excited states. Chem. Phys. Lett., 1984, 103(6): 497-502.[5]Barral-Tosh, S., Chattopadhyay, S. K., Das, P. K., A laser flash photolysis study of paraquat reduction by photogenerated aromatic ketyl radicals and carbonyl triplets, J. Phys. Chem., 1984, 88: 1404-1408.[6]Elisei. F., Favaro, G., Ion-forming processes on 248 nm laser excitation of benzophenone in aqueous solution: a time-resolved absorption and conductivity study, J. Photochem. Photobiol. A: Chem., 1991, 59:243-253.

  12. UV photolysis, organic molecules in young disks, and the origin of meteoritic amino acids

    CERN Document Server

    Throop, Henry

    2011-01-01

    The origin of complex organic molecules such as amino acids and their precursors found in meteorites and comets is unknown. Previous studies have accounted for the complex organic inventory of the Solar System by aqueous chemistry on warm meteoritic parent bodies, or by accretion of organics formed in the interstellar medium. This paper proposes a third possibility: that complex organics were created in situ by ultraviolet light from nearby O/B stars irradiating ices already in the Sun's protoplanetary disk. If the Sun was born in a dense cluster near UV-bright stars, the flux hitting the disk from external stars could be many orders of magnitude higher than that from the Sun alone. Such photolysis of ices in the laboratory can rapidly produce amino acid precursors and other complex organic molecules. I present a simple model coupling grain growth and UV exposure in a young circumstellar disk. It is shown that the production may be sufficient to create the Solar System's entire complex organic inventory withi...

  13. Impact of nitrous acid photolysis on the total hydroxyl radical budget during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono study in Milan

    Science.gov (United States)

    Alicke, B.; Platt, U.; Stutz, J.

    2002-11-01

    The photolysis of nitrous acid (HONO) in the early morning hours is believed to be a significant source of hydroxyl radicals (OH), the most important daytime oxidizing species. Although the importance of this mechanism has been recognized for many years, no accurate experimental quantification is available. Here we present measurements of HONO, NO2, SO2, O3 and HCHO by Differential Optical Absorption Spectroscopy (DOAS) during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono (LOOP/PIPAPO) study in May-June 1998 in Milan, Italy. The concentration of NO and J(NO2)/J(HONO) were simultaneously monitored by in situ monitors. The photolysis frequencies of HCHO and O3 were determined with a radiative transfer model. High nocturnal HONO mixing ratios of up to 4.4 ppb were regularly observed. Elevated daytime HONO levels during cloudy periods show that the formation of HONO proceeds after sunrise and therefore also represents a source of hydroxyl radicals throughout the day. Averaged over 24 hours, HCHO photolysis is the most important source of OH in Milan, followed by either ozone or HONO photolysis. Our observations indicate that on certain days the OH production from HONO can be even more important than that from ozone photolysis. The diurnal variation of the different OH formation mechanisms shows that HONO photolysis is by far the most important source in the early hours of the morning, and can be as large as and even surpass the total OH production at noon.

  14. Volatile organic compounds (VOCs) emission characteristics and control strategies for a petrochemical industrial area in middle Taiwan.

    Science.gov (United States)

    Yen, Chia-Hsien; Horng, Jao-Jia

    2009-11-01

    This study investigated VOC emissions from the largest petrochemical industrial district in Taiwan and recommended some control measures to reduce VOC emissions. In addition to the petrochemical industry, the district encompasses a chemical and fiber industry, a plastics industry and a harbor, which together produce more than 95% of the VOC emissions in the area. The sequence of VOC emission was as follows: components (e.g., valves, flanges, and pumps) (47%) > tanks (29%) > stacks (15%) > wastewater treatment facility (6%) > loading (2%) > flares (1%). Other plants producing high-density polyethylene (HDPE), styrene, ethylene glycol (EG), gas oil, and iso-nonyl-alchol (INA) were measured to determine the VOC leaching in the district. The VOC emissions of these 35 plants (90% of all plants) were less than 100 tons/year. About 74% of the tanks were fixed-roof tanks that leached more VOCs than the other types of tanks. To reduce leaching, the components should be checked periodically, and companies should be required to follow the Taiwan EPA regulations. A VOC emission management system was developed in state implementation plans (SIPs) to inspect and reduce emissions in the industrial district.

  15. 40 CFR Table 1 to Subpart B of... - Volatile Organic Compound (VOC) Content Limits for Automobile Refinish Coatings

    Science.gov (United States)

    2010-07-01

    ... Limits for Automobile Refinish Coatings 1 Table 1 to Subpart B of Part 59 Protection of Environment... Automobile Refinish Coatings Pt. 59, Subpt. B, Table 1 Table 1 to Subpart B of Part 59—Volatile Organic Compound (VOC) Content Limits for Automobile Refinish Coatings Coating category Grams VOC per liter...

  16. CAPSTONE REPORT ON THE DEVELOPMENT OF A STANDARD TEST METHOD FOR VOC EMISSIONS FROM INTERIOR LATEX PAINT AND ALKYD PAINTS

    Science.gov (United States)

    The report gives details of a small-chamber test method developed by the EPA for characterizing volatile organic compound (VOC) emissions from interior latex and alkyd paints. Current knowledge about VOC, including hazardous air pollutant, emissions from interior paints generated...

  17. VOC identification and inter-comparison from laboratory biomass burning using PTR-MS and PIT-MS

    Science.gov (United States)

    C. Warneke; J. M. Roberts; P. Veres; J. Gilman; W. C. Kuster; I. Burling; R. Yokelson; J. A. de Gouw

    2011-01-01

    Volatile organic compounds (VOCs) emitted from fires of biomass commonly found in the southeast and southwest U.S. were investigated with PTR-MS and PIT-MS, which are capable of fast measurements of a large number of VOCs. Both instruments were calibrated with gas standards and mass dependent calibration curves are determined. The sensitivity of the PIT-MS linearly...

  18. An Admiralty for Asia: Isaac le Maire and conflicting conceptions about the corporate governance of the VOC

    NARCIS (Netherlands)

    O. Gelderblom (Oscar); A. de Jong (Abe); J. Jonker (Joost)

    2010-01-01

    textabstractThe Dutch East India Company or VOC in 1602 showed many characteristics of modern corporations, including limited liability, freely transferable shares, and well-defined managerial functions. However, we challenge the notion of the VOC as the precursor of modern corporations to argue tha

  19. Measurements of Volatile Organic Compounds (VOCs) on Board of the Zeppelin NT during the PEGASOS Campaign in 2012

    Science.gov (United States)

    Jäger, Julia; Hofzumahaus, Andreas; Beck, Harry; Rohrer, Franz; Broch, Sebastian; Fuchs, Hendrik; Gomm, Sebastian; Holland, Frank; Lu, Keding; Kiendler-Scharr, Astrid; Mentel, Thomas; Rose, Bernhard; Wegener, Robert; Wahner, Andreas

    2013-04-01

    Volatile Organic Compounds (VOCs) are mostly emitted at the ground and are degraded by the reactions with OH, NO3 or O3 as they rise upwards in the atmosphere. VOCs play an important role as sources and sinks for radicals in the troposphere. Up to date, most of the VOC measurements were performed from ground based platforms; the profile measurements across the whole planetary boundary layer (PBL) are still quite limited which restrained the exploring of the VOCs chemistry of the entire PBL. This although these measurements are particularly interesting, as most of the chemistry of the VOC degradation in the troposphere takes place in the PBL. Moreover, fast VOCs measurements utilizing Gas Chromatography coupled with Mass Spectrometry (GC-MS) are a challenge due to the great chemical variability of VOC species. Therefore accurate in-situ measurements of VOCs together with other species as CO, NOx, O3 and the OH reactivity, encompassing different levels of altitude and fast time resolution, would essentially improve the understanding of the VOC distribution in the lower troposphere. Here we present the setup and the modifications of the fast GC-MS system and the results of the PEGASOS Zeppelin campaigns in summer 2012. First, we present our developments and modifications of an in-flight GC-MS system to detect volatile non methane hydrocarbons (NMHC) with a time resolution of 3 minutes and a detection limit in the order of 2 pptv. The modified setup enabled us to analyze 70 different VOC species, ranging from alkanes (C4 to C11), aromatics and terpenes to oxygenated hydrocarbons (OVOC) such as alcohols and aldehydes. Second, in contrast to previous airplane studies also utilizing a GC-MS system, the Zeppelin NT as a measuring platform during the PEGASOS campaign enabled us to measure vertical profiles up to 1500m at low travelling speeds which means a high spatial resolution. We will present results for selected VOC that offer new insights on height profiles

  20. TECHNICAL JUSTIFICATION FOR CHOOSING PROPANE AS A CALIBRATION AGENT FOR TOTAL FLAMMABLE VOLATILE ORGANIC COMPOUND (VOC) DETERMINATIONS

    Energy Technology Data Exchange (ETDEWEB)

    DOUGLAS, J.G.

    2006-07-06

    This document presents the technical justification for choosing and using propane as a calibration standard for estimating total flammable volatile organic compounds (VOCs) in an air matrix. A propane-in-nitrogen standard was selected based on a number of criteria: (1) has an analytical response similar to the VOCs of interest, (2) can be made with known accuracy and traceability, (3) is available with good purity, (4) has a matrix similar to the sample matrix, (5) is stable during storage and use, (6) is relatively non-hazardous, and (7) is a recognized standard for similar analytical applications. The Waste Retrieval Project (WRP) desires a fast, reliable, and inexpensive method for screening the flammable VOC content in the vapor-phase headspace of waste containers. Table 1 lists the flammable VOCs of interest to the WRP. The current method used to determine the VOC content of a container is to sample the container's headspace and submit the sample for gas chromatography--mass spectrometry (GC-MS) analysis. The driver for the VOC measurement requirement is safety: potentially flammable atmospheres in the waste containers must be allowed to diffuse prior to processing the container. The proposed flammable VOC screening method is to inject an aliquot of the headspace sample into an argon-doped pulsed-discharge helium ionization detector (Ar-PDHID) contained within a gas chromatograph. No actual chromatography is performed; the sample is transferred directly from a sample loop to the detector through a short, inert transfer line. The peak area resulting from the injected sample is proportional to the flammable VOC content of the sample. However, because the Ar-PDHID has different response factors for different flammable VOCs, a fundamental assumption must be made that the agent used to calibrate the detector is representative of the flammable VOCs of interest that may be in the headspace samples. At worst, we desire that calibration with the selected