[Photodegradation of naproxen in aqueous systems by UV irradiation: mechanism and toxicity of photolysis products].

PubMed

Ma, Du-juan; Liu, Guo-guang; Lü, Wen-ying; Yao, Kun; Zhou, Li-hua; Xie, Cheng-ping

2013-05-01

This paper studies the degradation mechanism, the reaction kinetics and the toxicity of photolysis products of naproxen in waters under UV irradiation (120 W mercury lamp) by quenching experiments of reactive oxygen species (ROS), oxygen concentration experiment and toxicity evaluation using Vibrio fischeri bacteria. The results demonstrated that NPX could be degraded effectively by UV irradiation and the photolysis pathways was the sum of the degradation by direct photolysis and self-sensitization via ROS, and the contribution rates of self-sensitized photodegradation were 0.1%, 80.2%, 35.7% via *OH, (1)O2, O2*-, respectively. The effect of oxygen concentration illustrated that dissolved oxygen had an inhibitory effect on the direct photodegradation of NPX, and the higher the oxygen content, the more obvious the inhibitory effect. The toxicity evaluation illustrated the formation of some intermediate products that were more toxic than NPX during the photodegradation of NPX. The process of NPX degradation in all cases could be fitted by the pseudo first-order kinetics model.

Effect of nitrate, carbonate/bicarbonate, humic acid, and H2O2 on the kinetics and degradation mechanism of Bisphenol-A during UV photolysis.

PubMed

Kang, Young-Min; Kim, Moon-Kyung; Zoh, Kyung-Duk

2018-08-01

In this study, the effects of natural water components (nitrate, carbonate/bicarbonate, and humic acid) on the kinetics and degradation mechanisms of bisphenol A (BPA) during UV-C photolysis and UV/H 2 O 2 reaction were examined. The presence of NO 3 - (0.04-0.4 mM) and CO 3 2- /HCO 3 - (0.4-4 mM) ions increased BPA degradation during UV photolysis. Humic acid less than 3 mg/L promoted BPA degradation, but greater than 3 mg/L of humic acid inhibited BPA degradation. During the UV/H 2 O 2 reaction, all water matrix components acted as radical scavengers in the order of humic acid > CO 3 2- /HCO 3 -  > NO 3 - . All of the degradation reactions agreed with the pseudo-first-order kinetics. While eight byproducts (m/z = 122, 136, 139, 164, 181, 244, 273, 289) were identified in UV-C/NO 3 - photolysis reaction, four (m/z = 122, 136, 164, 244) and three byproducts (m/z = 122, 136, 164) were observed during UV-C/NO 3 - /CO 3 2- /HCO 3 - and UV-C/CO 3 2- /HCO 3 - reactions. Nitrogenated and hydrogenated byproducts were first observed during the UV-C/NO 3 - photolysis, but only hydrogenated byproducts as adducts were detected during the UV-C/NO 3 - /CO 3 2- /HCO 3 - photolysis. Nitrogenated and hydrogenated byproducts were formed in the early stage of degradation by OH or NO 2 radicals, and these byproducts were subsequently degraded into smaller compounds with further reaction during UV-C/NO 3 - and UV-C/NO 3 - /CO 3 2- /HCO 3 - reactions. In contrast, BPA was directly degraded into smaller compounds by β-scission of the isopropyl group by CO 3 - /HCO 3 radicals during UV-C/CO 3 2- /HCO 3 - reaction. Our results imply that the water components can change the degradation mechanism of BPA during UV photolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multi-photon UV photolysis of gaseous polycyclic aromatic hydrocarbons: Extinction spectra and dynamics

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

Walsh, A. J.; Gash, E. W.; Mansfield, M. W. D.

The extinction spectra of static naphthalene and static biphenylene vapor, each buffered with a noble gas at room temperature, were measured as a function of time in the region between 390 and 850 nm after UV multi-photon laser photolysis at 308 nm. Employing incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), the spectra were found to be unstructured with a general lack of isolated features suggesting that the extinction was not solely based on absorption but was in fact dominated by scattering from particles formed in the photolysis of the respective polycyclic aromatic hydrocarbon. Following UV multi-photon photolysis, the extinction dynamicsmore » of the static (unstirred) closed gas-phase system exhibits extraordinary quasi-periodic and complex oscillations with periods ranging from seconds to many minutes, persisting for up to several hours. Depending on buffer gas type and pressure, several types of dynamical responses could be generated (classified as types I, II, and III). They were studied as a function of temperature and chamber volume for different experimental conditions and possible explanations for the oscillations are discussed. A conclusive model for the observed phenomena has not been established. However, a number of key hypotheses have made based on the measurements in this publication: (a) Following the multi-photon UV photolysis of naphthalene (or biphenylene), particles are formed on a timescale not observable using IBBCEAS. (b) The observed temporal behavior cannot be described on basis of a chemical reaction scheme alone. (c) The pressure dependence of the system's responses is due to transport phenomena of particles in the chamber. (d) The size distribution and the refractive indices of particles are time dependent and evolve on a timescale of minutes to hours. The rate of particle coagulation, involving coalescent growth and particle agglomeration, affects the observed oscillations. (e) The walls of the chamber act

Multi-photon UV photolysis of gaseous polycyclic aromatic hydrocarbons: Extinction spectra and dynamics

NASA Astrophysics Data System (ADS)

Walsh, A. J.; Ruth, A. A.; Gash, E. W.; Mansfield, M. W. D.

2013-08-01

The extinction spectra of static naphthalene and static biphenylene vapor, each buffered with a noble gas at room temperature, were measured as a function of time in the region between 390 and 850 nm after UV multi-photon laser photolysis at 308 nm. Employing incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), the spectra were found to be unstructured with a general lack of isolated features suggesting that the extinction was not solely based on absorption but was in fact dominated by scattering from particles formed in the photolysis of the respective polycyclic aromatic hydrocarbon. Following UV multi-photon photolysis, the extinction dynamics of the static (unstirred) closed gas-phase system exhibits extraordinary quasi-periodic and complex oscillations with periods ranging from seconds to many minutes, persisting for up to several hours. Depending on buffer gas type and pressure, several types of dynamical responses could be generated (classified as types I, II, and III). They were studied as a function of temperature and chamber volume for different experimental conditions and possible explanations for the oscillations are discussed. A conclusive model for the observed phenomena has not been established. However, a number of key hypotheses have made based on the measurements in this publication: (a) Following the multi-photon UV photolysis of naphthalene (or biphenylene), particles are formed on a timescale not observable using IBBCEAS. (b) The observed temporal behavior cannot be described on basis of a chemical reaction scheme alone. (c) The pressure dependence of the system's responses is due to transport phenomena of particles in the chamber. (d) The size distribution and the refractive indices of particles are time dependent and evolve on a timescale of minutes to hours. The rate of particle coagulation, involving coalescent growth and particle agglomeration, affects the observed oscillations. (e) The walls of the chamber act as a sink

Comparison of classical fenton, nitrilotriacetic acid (NTA)-Fenton, UV-Fenton, UV photolysis of Fe-NTA, UV-NTA-Fenton, and UV-H2O2 for the degradation of cyclohexanoic acid.

PubMed

Zhang, Ying; Klamerth, Nikolaus; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

2017-05-01

The treatment of a naphthenic acid model compound, cyclohexanoic acid, with classical Fenton, UV-H 2 O 2 , UV-Fenton, nitrilotriacetic acid (NTA)-Fenton, UV-NTA-Fenton, and UV photolysis of Fe-NTA processes at pHs 3 and 8 was investigated. At 1.47 mM H 2 O 2 , 0.089 mM Fe, and 0.18 mM NTA, the UV-NTA-Fenton process at pH 3 exhibited the highest H 2 O 2 decomposition (100% in 25 min), CHA removal (100% in 12 min) with a rate constant of 0.27 ± 0.025 min -1 , and NTA degradation (100% in 6 min). Due to the formation of H 2 O 2 -Fe(III)NTA adduct, the total Fe concentration in the UV-NTA-Fenton system (0.063 mM at the end of the reaction) at pH 8 was much higher than that in the UV photolysis of Fe(III)NTA process (0.024 mM). The co-complexing effect of borate buffer helped to keep iron soluble; however, it imposed a negative influence on the CHA degradation in the UV-NTA-Fenton process (68% CHA removal in 60 min in the borate buffer compared to 92% in MilliQ water). The results demonstrated that the most efficient process for the CHA degradation under the experimental conditions was the UV-NTA-Fenton process at pH 3. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic studies of the reaction between pesticides and hydroxyl radical generated by laser flash photolysis.

PubMed

Gozzi, Fábio; Oliveira, Silvio C; Dantas, Renato F; Silva, Volnir O; Quina, Frank H; Machulek, Amilcar

2016-03-30

Due to contamination of the environment by pesticides and their mishandling, there is the need for treatment of contaminated sites and correct disposal of materials containing them. Thus, studies with advanced oxidation processes are expanding and can determine the rate constant of the hydroxyl radical with organic compounds of great importance in environmental contamination. In this context, the use of laser flash photolysis has been shown to be viable for the determination of these constants. The reaction rate constants of different pesticides with HO(•) in degassed acetonitrile have been determined. They were 1.6 × 10(9)  M(-1)  s(-1), 0.6 × 10(9)  M(-1)  s(-1), 1.2 × 10(9)  M(-1)  s(-1), 2.4 × 10(9)  M(-1)  s(-1) and 2.2 × 10(9)  M(-1)  s(-1) for the pesticides carbaryl, propoxur, fenoxycarb, ethoxysulfuron and chlorimuron-ethyl, respectively. These values are about an order of magnitude smaller than the diffusion controlled rate and correlate with the relative rates of disappearance of the pesticides in the photo-Fenton reaction in water. The correlation of the relative rate constants determined by laser flash photolysis with the relative rates of photo-Fenton degradation of the pesticides is compelling evidence for the participation of the hydroxyl radical in the degradation of these pesticides in the latter system. © 2015 Society of Chemical Industry.

Efficacy of UV-C photolysis of bisphenol A on transcriptome alterations of genes in zebrafish embryos.

PubMed

Saeed, Asma; Hashmi, Imran; Zare, Ava; Mehrabani-Zeinabad, Mitra; Achari, Gopal; Habibi, Hamid R

2016-09-18

The purpose of this study was to investigate the efficacy of UV-C direct photolysis of bisphenol A (BPA) as a remediation method of BPA contamination. We used zebrafish embryos as a model organism to test the toxicity and residual biological activity by measuring cytochrome P4501A1 (CYP1A), aromatase B (Aro B) and heat shock proteins (HSP-70) transcript levels. The mRNA levels of CYP1A gene increased about two fold while exposure of zebrafish embryos at 72 hpf resulted in significant induction (P = 0.048) of Aro B at 100 µg/L of BPA. Exposure of zebrafish embryos at 72 hpf to increasing concentrations of BPA resulted in significant induction (P = 0.0031) of HSP-70 transcript level. UV treatment of BPA resulted in a significant reduction in toxicity by reducing mortality of zebrafish embryos. The results suggest that UV-C direct photolysis may be an effective method for remediation of BPA contamination. Further studies will be necessary for better understanding of the identity and relative activity of the UV degradation by-products.

Photolysis of Mono- and Dichloramines in UV/Hydrogen Peroxide: Effects on 1,4-Dioxane Removal and Relevance in Water Reuse.

PubMed

Patton, Samuel; Romano, Mariano; Naddeo, Vincenzo; Ishida, Kenneth P; Liu, Haizhou

2018-06-05

Growing demands and increasing scarcity of fresh water resources necessitate potable water reuse, which has been implemented with the aid of UV-based advanced oxidation processes (UV/AOPs) that remove potentially hazardous trace organic contaminants from reclaimed water. During the potable reuse treatment process, chloramines are added to prevent membrane fouling that are carried over to the UV/AOP, where hydrogen peroxide (H 2 O 2 ) is commonly added. However, the impact of chloramines on the photolysis of H 2 O 2 and the overall performance of the UV/AOP remains unknown. This study investigated the impacts of the photochemistry of monochloramine (NH 2 Cl) and dichloramine (NHCl 2 ) associated with the photolysis of H 2 O 2 on the degradation of 1,4-dioxane (1,4-D), a trace organic contaminant ubiquitous in recycled water. Results indicated that NH 2 Cl and NHCl 2 alone functioned as oxidants upon UV photolysis, which produced HO • and Cl 2 •- as the two primary oxidative radicals. The speciation of chloramines did not have a significant impact on the degradation kinetics. The inclusion of monochloramine in UV/H 2 O 2 greatly decreased 1,4-D removal efficiency. HO • was the major radical in the mixed H 2 O 2 /chloramine system. Results from this study suggest that recognizing the existence of chloramines in UV/H 2 O 2 systems is important for predicting UV/AOP performance in the treatment train of potable reuse.

Photolysis of low concentration H2S under UV/VUV irradiation emitted from high frequency discharge electrodeless lamps.

PubMed

Xu, Jianhui; Li, Chaolin; Liu, Peng; He, Di; Wang, Jianfeng; Zhang, Qian

2014-08-01

The photolysis of low concentration of H2S malodorous gas was studied under UV irradiation emitted by self-made high frequency discharge electrodeless lamp with atomic mercury lines at 185/253.7nm. Experiments results showed that the removal efficiency (ηH2S) of H2S was decreased with increasing initial H2S concentration and increased slightly with gas residence time. ηH2S was increased dramatically with relative humidity from<5% to 43% while the concentration of oxygen in gas environments affected the removal of H2S. The mechanisms for direct and indirect photolysis (generation of ozone) were illustrated by the experimental results on photolysis of H2S under argon environments and ozonation of H2S under air environments, respectively. The overall ηH2S by photolysis is higher than the combination of ηH2S by direct photolysis and ozonation, suggesting that hydroxyl radical-mediated indirect photolysis played an important role during photolysis processes. The main photolysis product was confirmed to be SO4(2-) with ion chromatograph. Copyright © 2014 Elsevier Ltd. All rights reserved.

Nanosecond laser photolysis studies of vitamin K 3 in aqueous solution

NASA Astrophysics Data System (ADS)

Chen, J. F.; Ge, X. W.; Chu, G. S.; Zhang, Z. C.; Zhang, M. W.; Yao, S. D.; Lin, N. Y.

1999-06-01

Vitamin K 3 in aqueous solution was investigated by 248 nm laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments by Mn 2+ and O 2. In neutral solutions, the intermediates recorded were assigned to excited triplet states and dehydrogenated radicals of vitamin K 3. In comparison with the results of pulse radiolytical experiment, vitamin K 3 not only has strong electron affinity but could also could be photoionized by UV laser light. All this shows that vitamin K 3 acts as an effective electron carrier and electron transfer agent.

Magnetic Field Effect: An Efficient Tool To Investigate The Mechanism Of Reactions Using Laser Flash Photolysis Technique

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

Basu, Samita; Bose, Adity; Dey, Debarati

2008-04-24

Magnetic field effect combined with laser flash photolysis technique have been used to study the mechanism of interactions between two drug-like quinone molecules, Menadione (1,4-naphthoquinone, MQ) and 9, 10 Anthraquinone (AQ) with one of the DNA bases, Adenine in homogeneous acetonitrile/water and heterogeneous micellar media. A switchover in reaction mode from electron transfer to hydrogen abstraction is observed with MQ on changing the solvent from acetonitrile/water to micelle; whereas, AQ retains its mode of interaction towards Adenine as electron transfer in both the media due to its bulky structure compared to MQ.

Magnetic Field Effect: An Efficient Tool To Investigate The Mechanism Of Reactions Using Laser Flash Photolysis Technique

NASA Astrophysics Data System (ADS)

Basu, Samita; Bose, Adity; Dey, Debarati

2008-04-01

Magnetic field effect combined with laser flash photolysis technique have been used to study the mechanism of interactions between two drug-like quinone molecules, Menadione (1,4-naphthoquinone, MQ) and 9, 10 Anthraquinone (AQ) with one of the DNA bases, Adenine in homogeneous acetonitrile/water and heterogeneous micellar media. A switchover in reaction mode from electron transfer to hydrogen abstraction is observed with MQ on changing the solvent from acetonitrile/water to micelle; whereas, AQ retains its mode of interaction towards Adenine as electron transfer in both the media due to its bulky structure compared to MQ.

Sensitized and heavy atom induced production of acenaphthylene triplet: A laser flash photolysis study

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

Samanta, A.; Fessenden, R.W.

1989-07-27

The triplet state of acenaphthylene has been examined by nanosecond laser flash photolysis using sensitization and heavy atom perturbation techniques. Although acenaphthylene does not form any observable triplet upon direct flash excitation, a transient with microsecond lifetime ({lambda}{sub max} = 315 nm) is observable when a solution of the sample is excited by sensitizers (benzophenone, thioxanthone, benzil). This transient is ascribed to the triplet of acenaphthylene on the basis of its quenching behavior toward oxygen, ferrocene, azulene, and {beta}-carotene. Quantitative data concerning the triplet-triplet absorption and quenching constants are presented. The triplet energy is estimated to lie between 46 andmore » 47 kcal/mol. The triplet can also be produced by direct excitation in solvents containing heavy atoms (ethyl bromide, ethyl iodide). The triplet yield is found to increase with an increase of the amount of the heavy atom containing solvent. No saturation limit is obtained. These facts together with the effect of heavy atoms on the T{sub 1} {yields} S{sub 0} process allow the differing behavior of ethyl bromide and ethyl iodide on the photodimerization process of acenaphthylene to be explained. Triplet-state parameters (extinction coefficient and triplet yield) have been estimated in these solvents by the energy-transfer technique and actinometry.« less

Formation of tryptophan radicals in irradiated aqueous solutions of hexachloroplatinate(IV): a flash photolysis study.

PubMed

Zang, L; Rodgers, M A

1999-10-01

The oxidation of tryptophan photosensitized by PtCl6(2-) has been investigated in aqueous solutions at different pH using nanosecond laser flash photolysis. Cationic and neutral radicals of tryptophan were detected at pH 2.8 and 8.5, respectively. The generation of the radical was attributed to oxidation by Cl2- that was formed from the homolytic bond cleavage in the excited state of PtCl6(2-). The bimolecular rate constant derived from the kinetics analysis, 2.8 +/- 0.2 x 10(9) M-1 s-1, is in good agreement with the value obtained in earlier pulse radiolysis studies. Both the cationic and neutral radicals decayed by second-order kinetics, consistent with the dimerization process.

Degradation of 4-chloro 2-aminophenol using a novel combined process based on hydrodynamic cavitation, UV photolysis and ozone.

PubMed

Barik, Arati J; Gogate, Parag R

2016-05-01

The degradation of 4-chloro 2-aminophenol (4C2AP), an acute toxic organic compound, has been studied using different approaches based on the hydrodynamic cavitation (HC) with orifice plate as cavitating device, photolysis (UV) and ozonation (O3). The dependency of extent of degradation on operating parameters like operating pressure (2-5 bar), initial pH (3-8) and temperature (30-38 °C) have been established initially to maximize the efficacy of hydrodynamic cavitation. Subsequently the degradation has been studied using combined treatment strategies as HC+UV, HC+O3, UV+O3 and HC+UV+O3 at the established optimum parameters of operating temperature as 30 °C, initial pH of 6 and inlet pressure of 4 bar. The maximum extent of degradation as 96.85% and 73.6% reduction in TOC has been obtained using hydrodynamic cavitation in combination with UV photolysis and ozonation under the optimized operating conditions. The degradation products of 4C2AP have been identified using GC-MS. The present work has clearly established the efficacy of combined treatment approach (HC+UV+O3) for the removal of organic pollutant for the first time. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of the transient species generated by the photoionization of Berberine: A laser flash photolysis study

NASA Astrophysics Data System (ADS)

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.

Photolysis of the organic UV filter, avobenzone, combined with octyl methoxycinnamate by nano-TiO2 composites.

PubMed

Kim, E J; Kim, M J; Im, N R; Park, S N

2015-08-01

A protection of the skin from harmful UV rays is important in preventing the skin damage and skin aging when exposed to sunlight. Titanium dioxide composites are used as a UV filter in sunscreen products combined with organic compounds such as butyl methoxydibenzoyl methane (avobenzone) and octyl methoxycinnamate (OMC) to improve the function of the sunscreen. In this study, the photolysis of avobenzone and OMC caused by the photocatalytic TiO2 nano composites (NCs) is investigated. Three different types of oil/water (O/W) sunscreen formulations containing avobenzone and OMC were prepared. Each formulation contained one of three different types of surface modified TiO2 NCs, which were WP-S (small sized hydrophilic TiO2NCs, ~10nm), OP-S (small sized hydrophobic TiO2NCs, ~15nm), and OP-L (large sized hydrophobic TiO2NCs, ~200nm). The physicochemical properties of the NCs were analyzed using biophysical tools. Addition of a different size of TiO2NCs into O/W sunscreen formulations significantly increased the photolysis of OMC. Effect of quercetin on degradation of avobenzone and OMC by the NCs was also studied for all three formulations. Although the OP-S NCs showed the lowest photocatalytic ability and the highest UV blocking capability, the NCs promoted the photolysis of OMC to the greatest extent. These results can be utilized to design more effective sunscreens, which could potentially ensure optimal photo-protection. Copyright © 2015 Elsevier B.V. All rights reserved.

Photodegradation of gallic acid under UV irradiation: insights regarding the pH effect on direct photolysis and the ROS oxidation-sensitized process of DOM.

PubMed

Du, Yingxun; Chen, Hui; Zhang, Yuanyuan; Chang, Yuguang

2014-03-01

In this study, the degradation of gallic acid (GA), a model compound for dissolved organic matter (DOM) in controlled UV/N2, UV/air, UV/Fe(3+)/N2, and UV/Fe(3+)/air systems was investigated to elucidate the contribution of direct photolysis and reactive oxygen species (ROS) oxidation to GA degradation at various pH values. In general, the order of the degradation rate of GA in these four systems was as follows: UV/Fe(3+)/air>UV/air>UV/Fe(3+)/N2≈UV/N2. In the UV/N2 system, GA underwent slow direct photolysis, the rate of which decreased with decreasing pH. In the UV/Fe(3+)/air system, the most rapid GA degradation was achieved at pH 5. ROS are mainly derived from two sources. The first source is attributed to the role of DO and the other is attributed to the interaction of Fe(3+) and DO. The contribution of ROS to GA oxidation is much greater (>71%) than that of direct photolysis (<29%) at each pH value and is most obvious at pH 5. H2O2 formation was detected during GA degradation in the UV/air and UV/Fe(3+)/air systems. Using ROS scavengers, it was found that oxidation by OH was the main mechanism of GA degradation in the UV/Fe(3+)/air system. Based on the experimental results, a mechanism for GA degradation and ROS formation involving the effect of pH was proposed. This study furthers our understanding of changes in DOM degradation mechanisms due to global acidification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Aqueous photolysis of the organic ultraviolet filter chemical octyl methoxycinnamate.

PubMed

MacManus-Spencer, Laura A; Tse, Monica L; Klein, Jacob L; Kracunas, Alison E

2011-05-01

Organic UV filter chemicals are the active ingredients in personal care products designed to protect the skin from UV radiation, and hundreds of tons are estimated to be produced annually. Despite their entrance into the aquatic environment by both direct and indirect routes and their detection in surface waters and fish, little is known about their environmental fate. UV filter chemicals are designed to be photostable, but some undergo transformation upon exposure to UV light. Octyl methoxycinnamate (OMC), a commonly used UV filter chemical, degrades rapidly by direct photolysis; previous studies have focused on its photoisomerization, and a few investigators have reported the formation of cyclodimers. Here, we present the kinetics and quantum efficiency of the direct photolysis of OMC and confirm that dimerization occurs as a result of direct photolysis in aqueous solution. Likely identities of the dimers are offered based on comparison to reported results for other cinnamate derivatives. We have identified additional products of direct photolysis that have not been previously reported and investigated their photostability, as well as the mechanism of product formation. There is also some evidence of indirect photolysis in the presence of dissolved natural organic matter.

Laser Flash Photolysis Studies of Radical-Radical Reaction Kinetics: The O((sup 3)P(sub J)) + BrO Reaction

NASA Technical Reports Server (NTRS)

Thorn, R. P.; Cronkhite, J. M.; Nicovich, J. M.; Wine, P. H.

1997-01-01

A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction 0((sup 3)P(sub j)) + Br yields(k1) BrO((sup 2)P(sub J)) + O2 as a function of temperature (231-328 K) and pressure (25-150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T) = 1.91 x 10(exp -11)(230/J) cu cm/ molecule.s; the absolute accuracy of measured values for k1 is estimated to vary from +/- 20 percent at at T approximately 230 K to +/- 30 percent at T approximately 330 K. Our results demonstrate that the O((sup 3)P(sub j)) + BrO rate coefficient is significantly faster than previously 'guesstimated,' and suggest that the catalytic cycle with the O((sup 3)P(sub j)) + BrO reaction as its rate-limiting step is the dominant stratospheric BrO(x), odd-oxygen destruction cycle at altitudes above 24 km.

Infrared measurements on ultraviolet photolysis products at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Dong, Weibing; He, Ping; Wang, Jessie; Zhou, Zhaohui; Wang, Hongxin

2013-01-01

Combination of ultraviolet (UV) photolysis with infrared (IR) spectroscopy (or UV/IR for abbreviation) is a powerful tool to study various chemical photoreactions, while cryostat and sample-cell windows define the working ranges for both UV and IR beams. Although diamond window has a very wide transmission range from UV to IR, the extreme cost, the absorptions at 1800-2600 cm-1 and other problems prevent it from being the solution for all cases. In this paper, a gas-exchange cryostat was modified to realize a UV/mid-IR experiment at cryogenic temperatures. Several windows (including diamond) were discussed as options. A di-nitrogen iron complex trans-[Fe(DMeOPrPE)2(N2)H][BPh4] [DMeOPrPE = 1,2-bis(dimethoxypropylphosphino)ethane] was studied as a real photolysis example. Alternatively, a cold-finger cryostat was modified for UV/far-IR compatible experiments. Non-photolysis samples K5[Mo4O11(R,S-Hhomocit)2]Cl·5H2O (H4homocit = homocitric acid) and [(n-Bu)4N]2[Fe4S4(PPh)4] were studied at cryogenic temperatures. Sample cell windows can also be used as a natural way for choosing photolysis wavelength (in addition to the use of optical filters).

Photophysical and photochemical effects of UV and VUV photo-oxidation and photolysis on PET and PEN

NASA Astrophysics Data System (ADS)

Morgan, Andrew

Polyethylene Terephthalate (PET) is a widely used polymer in the bottling, packaging, and clothing industry. In recent years an increasing global demand for PET has taken place due to the Solar Disinfection (SODIS) process. SODIS is a method of sterilizing fresh water into drinkable water. The PET bottles are used in the process to contain the water during solar irradiation due to its highly transparent optical property. Alongside PET, polyethylene 2,6-napthalate (PEN) is used in bottling and flexible electronic applications. The surface of PEN would need to be modified to control the hydrophilicity and the interaction it exudes as a substrate. The UV light absorption properties of PET and PEN are of great importance for many applications, and thus needs to be studied along with its photochemical resistance. The optical and chemical nature of PET was studied as it was treated by UV photo-oxidation, photo-ozonation, and photolysis under atmospheric pressure. Another investigation was also used to study PEN and PET as they are treated by vacuum UV (VUV) photo-oxidation, VUV photolysis, and remote oxygen reactions. The extent of the photoreactions' effect into the depth of the polymers is examined as treatment conditions are changed. The different experimental methods established the rate of several competing photoreactions on PET and PEN during irradiance, and their effect on the optical quality of the polymers.

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

PubMed

Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

2011-07-01

Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis

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

Muralidharan, S.; Ferraudi, G.; Schmatz, K.

1982-08-01

Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9more » figures, 3 tables.« less

UV absorption cross sections between 290 and 380 nm of a series of furanaldehydes: Estimation of their photolysis lifetimes

NASA Astrophysics Data System (ADS)

Colmenar, Inmaculada; González, Sergio; Jiménez, Elena; Martín, Pilar; Salgado, Sagrario; Cabañas, Beatriz; Albaladejo, José

2015-02-01

Furanaldehydes, such as 2-furanaldehyde (also known as furfural), 3-furanaldehyde and 5-methyl-2-furanaldehyde, are aromatic aldehydes which can be present in the atmosphere as primary and secondary pollutants. The atmospheric removal initiated by sunlight for these species is not well-known in the solar actinic region (at λ > 290 nm), mainly due to the absence of data concerning the UV absorption cross sections (σλ) and photolysis frequencies (Ji(z,θ)). In this work σλ for the mentioned furanaldehydes have been determined between 290 and 380 nm at room temperature for the first time. Experiments were performed in an absorption jacketed Pyrex cell, employing a deuterium lamp as irradiation source and a CCD detector. The obtained absorption spectra exhibit absorption maxima around 320 nm with absolute absorption cross sections of 1.13, 0.75 and 1.14 × 10-19 cm2 molecule-1 for 2-furanaldehyde, 3-furanaldehyde and 5-methyl-2-furanaldehyde, respectively. The reported UV absorption cross sections were used to provide estimates of Ji(z,θ) and, therefore, estimates of the lifetime (τhν) due to this atmospheric removal process, under different solar radiation situations. Estimated τhν have been compared with the lifetimes due to the homogeneous reaction with the main diurnal tropospheric oxidants. The results obtained suggest that photolysis in the actinic region can be the main degradation pathway for these furanaldehydes when assuming a quantum yield (Φλ) of unity and the maximum solar actinic flux, while photolysis can compete with the reaction of OH radicals when assuming Φλ = 0.1. On the contrary, the removal of all three furanaldehydes by the reactions with OH radicals becomes more important than the UV photolysis under low solar actinic flux conditions independently of Φλ. If the emission source of these furanaldehydes also occurs during the nighttime NO3 radicals will dominate the elimination process of these species.

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

NASA Technical Reports Server (NTRS)

Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

2002-01-01

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

Tunable UV Laser Photolysis of NF2: Quantum Yield for NF(a1 delta) Production.

DTIC Science & Technology

1988-05-25

UV Laser Photolysis of NF2: Quantum Yield for NF(a A) Production ’v0 LR. F. HEIDNER, H . HELVAJIAN , 4and J. B. KOFFEND Aerophysics Laboratory...experiments, the chemistry of NF2 with various hydrocarbons has been studied. It has also been shown that the addition-elimination reaction between H and NF2...COMPLI R LEN SP, 3 ,HAND L BE AM~ H O [ I , , i 1 CAIHOC IAM COOLED GaAs CAPACITANCE PHOTOTUIBE MANOMETER _ LENS /’~ ~L + . ANMEE _.... BANDPASS FILTER

UV Photolysis of Chloramine and Persulfate for 1,4-Dioxane Removal in Reverse-Osmosis Permeate for Potable Water Reuse.

PubMed

Li, Wei; Patton, Samuel; Gleason, Jamie M; Mezyk, Stephen P; Ishida, Kenneth P; Liu, Haizhou

2018-06-05

A sequential combination of membrane treatment and UV-based advanced oxidation processes (UV/AOP) has become the industry standard for potable water reuse. Chloramines are used as membrane antifouling agents and therefore carried over into the UV/AOP. In addition, persulfate (S 2 O 8 2- ) is an emerging oxidant that can be added into a UV/AOP, thus creating radicals generated from both chloramines and persulfate for water treatment. This study investigated the simultaneous photolysis of S 2 O 8 2- and monochloramine (NH 2 Cl) on the removal of 1,4-dioxane (1,4-D) for potable-water reuse. The dual oxidant effects of NH 2 Cl and S 2 O 8 2- on 1,4-D degradation were examined at various levels of oxidant dosage, chloride, and solution pH. Results showed that a NH 2 Cl-to-S 2 O 8 2- molar ratio of 0.1 was optimal, beyond which the scavenging by NH 2 Cl of HO • , SO 4 •- , and Cl 2 •- radicals decreased the 1,4-D degradation rate. At the optimal ratio, the degradation rate of 1,4-D increased linearly with the total oxidant dose up to 6 mM. The combined photolysis of NH 2 Cl and S 2 O 8 2- was sensitive to the solution pH due to a disproportionation of NH 2 Cl at pH lower than 6 into less-photoreactive dichloramine (NHCl 2 ) and radical scavenging by NH 4 + . The presence of chloride transformed HO • and SO 4 •- to Cl 2 •- that is less-reactive with 1,4-D, while the presence of dissolved O 2 promoted gaseous nitrogen production. Results from this study suggest that the presence of chloramines can be beneficial to persulfate photolysis in the removal of 1,4-D; however, the treatment efficiency depends on a careful control of an optimal NH 2 Cl dosage and a minimal chloride residue.

The Formation of Racemic Amino Acids by UV Photolysis of Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Small biologically relevant organic molecules including the amino acids glycine, alanine, and marine were formed in the laboratory by the UV (Ultraviolet) photolysis of realistic interstellar ice analogs, composed primarily of H2O, and including CH3OH, NH3, and HCN, under interstellar conditions. N-formyl glycine, cycloserine (4-amino-3-isoxazolidinone), and glycerol were detected before hydrolysis, and glycine, racemic alanine, racemic marine, glycerol, ethanolamine, and glyceric acid were found after hydrolysis. This suggests that some meteoritic amino acids (and other molecules) may be the direct result of interstellar ice photochemistry, expanding the current paradigm that they formed by reactions in liquid water on meteorite parent bodies.

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

EPA Science Inventory

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...

Photolysis of low concentration H2S under UV/VUV irradiation emitted from microwave discharge electrodeless lamps.

PubMed

Xia, Lan-Yan; Gu, Ding-Hong; Tan, Jing; Dong, Wen-Bo; Hou, Hui-Qi

2008-04-01

The photolysis of simulating low concentration of hydrogen sulfide malodorous gas was studied under UV irradiation emitted by self-made microwave discharge electrodeless lamps (i.e. microwave UV electrodeless mercury lamp (185/253.7 nm) and iodine lamp (178.3/180.1/183/184.4/187.6/206.2 nm)). Experiments results showed that the removal efficiency (eta H2S) of hydrogen sulfide was decreased with increasing initial H2S concentration and increased slightly with gas residence time; H2S removal efficiency was decreased dramatically with enlarged pipe diameter. Under the experimental conditions with pipe diameter of 36 mm, gas flow rate of 0.42 standard l s(-1), eta H2S was 52% with initial H2S concentration of 19.5 mg m(-3) by microwave mercury lamp, the absolute removal amount (ARA) was 4.30 microg s(-1), and energy yield (EY) was 77.3 mg kW h(-1); eta H2S was 56% with initial H2S concentration of 18.9 mg m(-3) by microwave iodine lamp, the ARA was 4.48 microg s(-1), and the EY was 80.5mg kW h(-1). The main photolysis product was confirmed to be SO4(2-) with IC.

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

PubMed

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H 2 O 2 ), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H 2 O 2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of UV photolysis, nanofiltration, and their combination to remove hormones from a drinking water source and reduce endocrine disrupting activity.

PubMed

Sanches, Sandra; Rodrigues, Alexandre; Cardoso, Vitor V; Benoliel, Maria J; Crespo, João G; Pereira, Vanessa J

2016-06-01

A sequential water treatment combining low pressure ultraviolet direct photolysis with nanofiltration was evaluated to remove hormones from water, reduce endocrine disrupting activity, and overcome the drawbacks associated with the individual processes (production of a nanofiltration-concentrated retentate and formation of toxic by-products). 17β-Estradiol, 17α-ethinylestradiol, estrone, estriol, and progesterone were spiked into a real water sample collected after the sedimentation process of a drinking water treatment plant. Even though the nanofiltration process alone showed similar results to the combined treatment in terms of the water quality produced, the combined treatment offered advantage in terms of the load of the retentate and decrease in the endocrine-disrupting activity of the samples. Moreover, the photolysis by-products produced, with higher endocrine disrupting activity than the parent compounds, were effectively retained by the membrane. The combination of direct LP/UV photolysis with nanofiltration is promising for a drinking water utility that needs to cope with sudden punctual discharges or deterioration of the water quality and wants to decrease the levels of chemicals in the nanofiltration retentate.

EFFECTS OF SUSPENDED SEDIMENTS ON PHOTOLYSIS RATES OF DISSOLVED POLLUTANTS

EPA Science Inventory

Data are presented concerning the effects of suspended sediments upon photolysis rates of dissolved ultraviolet (u.v.) absorbing pollutants. The malachite green leucocyanide actinometer was found to be a convenient and sensitive device for measurement of solar u.v. radiation (abo...

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

PubMed

Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

2017-01-03

The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

NASA Technical Reports Server (NTRS)

Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

1981-01-01

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

Welding of silver nanowire networks via flash white light and UV-C irradiation for highly conductive and reliable transparent electrodes

PubMed Central

Chung, Wan-Ho; Kim, Sang-Ho; Kim, Hak-Sung

2016-01-01

In this work, silver nanowire inks with hydroxypropyl methylcellulose (HPMC) binders were coated on polyethylene terephthalate (PET) substrates and welded via flash white light and ultraviolet C (UV-C) irradiation to produce highly conductive transparent electrodes. The coated silver nanowire films were firmly welded and embedded into PET substrate successfully at room temperature and under ambient conditions using an in-house flash white light welding system and UV-C irradiation. The effects of light irradiation conditions (light energy, irradiation time, pulse duration, and pulse number) on the silver nanowire networks were studied and optimized. Bending fatigue tests were also conducted to characterize the reliability of the welded transparent conductive silver nanowire films. The surfaces of the welded silver nanowire films were analyzed via scanning electron microscopy (SEM), while the transmittance of the structures was measured using a spectrophotometer. From the results, a highly conductive and transparent silver nanowire film with excellent reliability could be achieved at room temperature under ambient conditions via the combined flash white light and UV-C irradiation welding process. PMID:27553755

Welding of silver nanowire networks via flash white light and UV-C irradiation for highly conductive and reliable transparent electrodes

NASA Astrophysics Data System (ADS)

Chung, Wan-Ho; Kim, Sang-Ho; Kim, Hak-Sung

2016-08-01

In this work, silver nanowire inks with hydroxypropyl methylcellulose (HPMC) binders were coated on polyethylene terephthalate (PET) substrates and welded via flash white light and ultraviolet C (UV-C) irradiation to produce highly conductive transparent electrodes. The coated silver nanowire films were firmly welded and embedded into PET substrate successfully at room temperature and under ambient conditions using an in-house flash white light welding system and UV-C irradiation. The effects of light irradiation conditions (light energy, irradiation time, pulse duration, and pulse number) on the silver nanowire networks were studied and optimized. Bending fatigue tests were also conducted to characterize the reliability of the welded transparent conductive silver nanowire films. The surfaces of the welded silver nanowire films were analyzed via scanning electron microscopy (SEM), while the transmittance of the structures was measured using a spectrophotometer. From the results, a highly conductive and transparent silver nanowire film with excellent reliability could be achieved at room temperature under ambient conditions via the combined flash white light and UV-C irradiation welding process.

Study of the chemistry of ortho- and para-biphenylnitrenes by laser flash photolysis and time-resolved IR experiments and by B3LYP and CASPT2 calculations.

PubMed

Tsao, Meng-Lin; Gritsan, Nina; James, Tammi R; Platz, Matthew S; Hrovat, David A; Borden, Weston Thatcher

2003-08-06

The photochemistry of ortho-biphenyl azide (1a) has been studied by laser flash photolysis (LFP), with UV-vis and IR detection of the transient intermediates formed. LFP (266 nm) of 1a in glassy 3-methylpentane at 77 K releases singlet ortho-biphenylnitrene (1b) (lambda(max) = 410 nm, tau = 59 +/- 6 ns), which under these conditions decays cleanly to the lower energy triplet state. In fluid solution at 298 K, 1b rapidly (tau < 10 ns) partitions between formation of isocarbazole (4) (lambda(max) = 430 nm, tau = 70 ns) and benzazirine (1e) (lambda(max) = 305 nm, tau = 12 ns). Isocarbazole 4 undergoes a 1,5-hydrogen shift, with k(H)/k(D) = 3.4 at 298 K to form carbazole 9 and smaller amounts of two other isocarbazoles (7 and 8). Benzazirine 1e ring-opens reversibly to azacycloheptatetraene (1f), which serves as a reservoir for singlet nitrene 1b. Azacycloheptatetraene 1f ultimately forms carbazole 9 on the millisecond time scale by the pathway 1f --> 1e --> 1b --> 4 --> 9. The energies of the transient intermediates and of the transition structures connecting them were successfully predicted by CASPT2/6-31G calculations. The electronic and vibrational spectra of the intermediates, computed by density functional theory, support the assignment of the transient spectra, observed in the formation of 9 from 1a.

All-photonic drying and sintering process via flash white light combined with deep-UV and near-infrared irradiation for highly conductive copper nano-ink

PubMed Central

Hwang, Hyun-Jun; Oh, Kyung-Hwan; Kim, Hak-Sung

2016-01-01

We developed an ultra-high speed photonic sintering method involving flash white light (FWL) combined with near infrared (NIR) and deep UV light irradiation to produce highly conductive copper nano-ink film. Flash white light irradiation energy and the power of NIR/deep UV were optimized to obtain high conductivity Cu films. Several microscopic and spectroscopic characterization techniques such as scanning electron microscopy (SEM), a x-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy were employed to characterize the Cu nano-films. Optimally sintered Cu nano-ink films produced using a deep UV-assisted flash white light sintering technique had the lowest resistivity (7.62 μΩ·cm), which was only 4.5-fold higher than that of bulk Cu film (1.68 μΩ•cm). PMID:26806215

All-photonic drying and sintering process via flash white light combined with deep-UV and near-infrared irradiation for highly conductive copper nano-ink.

PubMed

Hwang, Hyun-Jun; Oh, Kyung-Hwan; Kim, Hak-Sung

2016-01-25

We developed an ultra-high speed photonic sintering method involving flash white light (FWL) combined with near infrared (NIR) and deep UV light irradiation to produce highly conductive copper nano-ink film. Flash white light irradiation energy and the power of NIR/deep UV were optimized to obtain high conductivity Cu films. Several microscopic and spectroscopic characterization techniques such as scanning electron microscopy (SEM), a x-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy were employed to characterize the Cu nano-films. Optimally sintered Cu nano-ink films produced using a deep UV-assisted flash white light sintering technique had the lowest resistivity (7.62 μΩ·cm), which was only 4.5-fold higher than that of bulk Cu film (1.68 μΩ•cm).

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

PubMed

Chen, Ling; Zhou, Hai-Yun; Deng, Qin-Ying

2007-06-01

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

A high-resolution, confocal laser-scanning microscope and flash photolysis system for physiological studies.

PubMed

Parker, I; Callamaras, N; Wier, W G

1997-06-01

We describe the construction of a high-resolution confocal laser-scanning microscope, and illustrate its use for studying elementary Ca2+ signalling events in cells. An avalanche photodiode module and simple optical path provide a high efficiency system for detection of fluorescence signals, allowing use of a small confocal aperture giving near diffraction-limited spatial resolution (< 300 nm lateral and < 400 nm axial). When operated in line-scan mode, the maximum temporal resolution is 1 ms, and the associated computer software allows complete flexibility to record line-scans continuously for long (minutes) periods or to obtain any desired pixel resolution in x-y scans. An independent UV irradiation system permits simultaneous photolysis of caged compounds over either a uniform, wide field (arc lamp source) or at a tightly focussed spot (frequency-tripled Nd:YAG laser). The microscope thus provides a versatile tool for optical studies of dynamic cellular processes, as well as excellent resolution for morphological studies. The confocal scanner can be added to virtually any inverted microscope for a component cost that is only a small fraction of that of comparable commercial instruments, yet offers better performance and greater versatility.

Direct UV photolysis of selected pharmaceuticals, personal care products and endocrine disruptors in aqueous solution.

PubMed

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.

Photolysis of oxyfluorfen in aqueous methanol.

PubMed

Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

2013-01-01

Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.

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

PubMed

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

2018-04-30

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

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

PubMed

Li, Kun; Wang, Mei; Wang, Jin; Zhu, Rongrong; Sun, Dongmei; Sun, Xiaoyu; Wang, Shi-Long

2013-01-01

Photoexcitation to generate triplet state has been proved to be the main photoreaction in homogeneous system for many benzoquinone derivatives, including oxidized coenzyme Q (CoQ) and its analogs. In the present study, microemulsion of CoQ, a heterogeneous system, is employed to mimic the distribution of CoQ in biomembrane. The photochemistry of CoQ(10) in microemulsion and cyclohexane is investigated and compared using laser flash photolysis and results show that CoQ(10) undergoes photoionization via a monophotonic process to generate radical cation of CoQ(10) in microemulsion and photoexcitation to generate excited triplet state in cyclohexane. Meanwhile, photoreactions of duroquinone (DQ) and CoQ(0) in microemulsion are also investigated to analyze the influence of molecular structure on the photochemistry of benzoquinone derivatives in microemulsion. Results suggest that photoexcitation, which is followed by excited state-involved hydrogen-abstraction reaction, is the main photoreaction for DQ and CoQ(0) in microemulsion. However, photoexcited CoQ(0) also leads to the formation of hydrated electrons. The isoprenoid side chain-involved high resonance stabilization is proposed to explain the difference in photoreactions of CoQ(0) and CoQ(10) in microemulsion. Considering that microemulsion is close to biomembrane system, its photoionization in microemulsion may be helpful to understand the real photochemistry of biological quinones in biomembrane system. © 2012 Tongji University. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Comments on a Method to Measure Sucralose Using UV Photodegradation Followed by UV Spectrophotometry.

PubMed

Fang, Te; Andrews, Susan A; Hofmann, Ron

2017-05-01

A simple and quick method to measure sucralose in aqueous solution at concentrations in the order of 0.1-1.2 g·L-1 proposed by Idris et al. uses UV irradiation prior to UV spectrophotometry. The photolysis of sucralose forms a photoactive compound characterized by maximum absorbance at approximately 270 nm. The conditions required for sucralose photolysis, however, had not been completely reported. In this work, the procedure described by Idris et al. was replicated using a low-pressure UV lamp to irradiate sucralose samples with a wider range of initial concentrations (0.04-10 g·L-1) with known fluences. It was determined that care must be taken to ensure that the same fluence is applied for both calibration and measurement steps because the absorbance of the sucralose photolysis product is a function of the applied fluence. The way the samples are irradiated also has an impact on the results in that the method exhibits a greater linear range if an apparatus is used that maximizes the fluence rate (e.g., by placing samples closer to the UV source or using a higher-intensity lamp).

Laser photolysis studies of ω-bond dissociation in aromatic carbonyls with a C-C triple bond stimulated by triplet sensitization.

PubMed

Yamaji, Minoru; Horimoto, Ami; Marciniak, Bronislaw

2017-07-14

We have prepared three types of carbonyl compounds, benzoylethynylmethyl phenyl sulfide (2@SPh), (p-benzoyl)phenylethynylmethyl phenyl sulfide (3@SPh) and p-(benzoylethynyl)benzyl phenyl sulfide (4@SPh) with benzoyl and phenylthiylmethyl groups, which are interconnected with a C-C triple bond and a phenyl ring. Laser flash photolysis of 3@SPh and 4@SPh in acetonitrile provided the transient absorption spectra of the corresponding triplet states where no chemical reactions were recognized. Upon laser flash photolysis of 2@SPh, the absorption band due to the phenylthiyl radical (PTR) was obtained, indicating that the C-S bond cleaved in the excited state. Triplet sensitization of these carbonyl compounds using acetone and xanthone was conducted using laser photolysis techniques. The formation of triplet 3@SPh was seen in the transient absorption, whereas the PTR formation was observed for 2@SPh and 4@SPh, indicating that the triplet states were reactive for the C-S bond dissociation. The C-S bond dissociation mechanism for 4@SPh upon triplet sensitization is discussed in comparison with those for 2@SPh and 3@SPh.

Hydrogen bonding effects on the reorganization energy for photoinduced charge separation reaction between porphyrin and quinone studied by nanosecond laser flash photolysis.

PubMed

Yago, Tomoaki; Gohdo, Masao; Wakasa, Masanobu

2010-02-25

Alcohol concentration dependences of photoinduced charge separation (CS) reaction of zinc tetraphenyl-porphyrin (ZnTPP) and duroquinone (DQ) were investigated in benzonitrile by a nanosecond laser flash photolysis technique. The photoinduced CS reaction was accelerated by the addition of alcohols, whereas the addition of acetonitrile caused little effect on the CS reactions. The simple theory was developed to calculate an increase in reorganization energies induced by the hydrogen bonding interactions between DQ and alcohols using the chemical equilibrium constants for the hydrogen bonding complexes through the concerted pathway and the stepwise one. The experimental results were analyzed by using the Marcus equation where we took into account the hydrogen bonding effects on the reorganization energy and the reaction free energy for the CS reaction. The observed alcohol concentration dependence of the CS reaction rates was well explained by the formation of the hydrogen bonding complexes through the concerted pathway, demonstrating the increase in the reorganization energy by the hydrogen bonding interactions.

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

NASA Technical Reports Server (NTRS)

Nickolaisen, Scott L.; Sander, Stanley P.; Friedl, Randall R.

1996-01-01

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3. [in troposphere

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Anderson, P. C.; Klais, O.

1979-01-01

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

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

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

Meusinger, Carl; Johnson, Matthew S.; Berhanu, Tesfaye A.

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 amore » 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.« less

Studies on photoinduced H-atom and electron transfer reactions of o-naphthoquinones by laser flash photolysis.

PubMed

Pan, Yang; Fu, Yao; Liu, Shaoxiong; Yu, Haizhu; Gao, Yuhe; Guo, Qingxiang; Yu, Shuqin

2006-06-15

The quenching of the triplets of 1,2-naphthoquinone (NQ) and 1,2-naphthoquinone-4-sulfonic acid sodium salt (NQS) by various electron and H-atom donors was investigated by laser flash photolysis measurement in acetonitrile and benzene. The results showed that the reactivities and configurations of 3NQ* (3NQS*) are governed by solvent polarity. All the quenching rate constants (kq) measured in benzene are larger than those in acetonitrile. The SO3Na substituent at the C-4 position of NQS makes 3NQS* more reactive than 3NQ* in electron/H-atom transfer reactions. Large differences of kq values were discovered in H-atom transfer reactions for alcohols and phenols, which can be explained by different H-abstraction mechanisms. Detection of radical cations of amines/anilines in time-resolved transient absorption spectra confirms an electron transfer mechanism. Triplets are identified as precursors of formed radical anions of NQ and NQS in photoinduced reactions. The dependence of electron transfer rate constants on the free energy changes (DeltaG) was treated by using the Rehm-Weller equation. For the four anilines with different substituents on the para or meta position of amidocyanogen, good correlation between log kq values with Hammett sigma constants testifies the correctness of empirical Hammett equation. Charge density distributions, adiabatic ionization/affinity potentials and redox potentials of NQ (NQS) and some quenchers were studied by quantum chemistry calculation.

Jitter-correction for IR/UV-XUV pump-probe experiments at the FLASH free-electron laser

DOE PAGES

Savelyev, Evgeny; Boll, Rebecca; Bomme, Cedric; ...

2017-04-10

In pump-probe experiments employing a free-electron laser (FEL) in combination with a synchronized optical femtosecond laser, the arrival-time jitter between the FEL pulse and the optical laser pulse often severely limits the temporal resolution that can be achieved. Here, we present a pump-probe experiment on the UV-induced dissociation of 2,6-difluoroiodobenzene C 6H 3F 2I) molecules performed at the FLASH FEL that takes advantage of recent upgrades of the FLASH timing and synchronization system to obtain high-quality data that are not limited by the FEL arrival-time jitter. Here, we discuss in detail the necessary data analysis steps and describe the originmore » of the time-dependent effects in the yields and kinetic energies of the fragment ions that we observe in the experiment.« less

Laser flash photolysis and magnetic-field-effect studies on interaction of thymine and thymidine with menadione: role of sugar in controlling reaction pattern

NASA Astrophysics Data System (ADS)

Bose, Adity; Dey, Debarati; Basu, Samita

2008-04-01

The magnetic field effect (MFE) in conjunction with laser flash photolysis has been used for the study of the interaction of one of the small drug like quinone molecules, 2-methyl, 1,4-naphthoquinone, commonly known as menadione (MQ), with one of the DNA bases, thymine (THN), and its corresponding nucleoside, thymidine (THDN), in acetonitrile (ACN) and sodium dodecylsulfate (SDS) micelles. It has been observed that THN undergoes electron transfer (ET) and hydrogen (H) abstraction with MQ, while THDN undergoes only H abstraction in both the media. However, our earlier studies showed that a purine base, adenine (ADN), and its nucleoside, 2'-deoxyadenosine (ADS), undergo ET in ACN and H abstraction in SDS. Here we have attempted to explain the differences in the reactions of these DNA bases with MQ. We also reveal the crucial role of a sugar unit in altering the behavior of purine and pyrimidine bases with respect to ET and H abstraction.

Synthesis and characterization of TiO₂ and TiO₂/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

PubMed

Ramos, Dayana Doffinger; Bezerra, Paula C S; Quina, Frank H; Dantas, Renato F; Casagrande, Gleison A; Oliveira, Silvio C; Oliveira, Márcio R S; Oliveira, Lincoln C S; Ferreira, Valdir S; Oliveira, Samuel L; Machulek, Amilcar

2015-01-01

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

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

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K.; Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309

2012-10-28

Oxalyl chloride, (ClCO){sub 2}, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO){sub 2} and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11more » discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, {Phi}({lambda}), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO){sub 2} has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl){sub 2}+ hv{yields} ClCO*+ Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO*{yields} Cl + CO (3a), {yields} ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M {yields} Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO){sub 2}. {Phi}(193 nm) was found to be 2.07 {+-} 0.37 independent of bath gas pressure (25.8-105.7 Torr, N{sub 2}), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO){sub 2} is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 {+-} 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 {+-} 0.26 independent of bath gas pressure (15-70 Torr, N{sub 2}). {Phi}(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N{sub 2}). The

Laser flash photolysis and CIDNP studies of steric effects on coupling rate constants of imidazolidine nitroxide with carbon-centered radicals, methyl isobutyrate-2-yl and tert-butyl propionate-2-yl.

PubMed

Zubenko, Dmitry; Tsentalovich, Yuri; Lebedeva, Nataly; Kirilyuk, Igor; Roshchupkina, Galina; Zhurko, Irina; Reznikov, Vladimir; Marque, Sylvain R A; Bagryanskaya, Elena

2006-08-04

Time-resolved chemically induced dynamic nuclear polarization (TR-CIDNP) and laser flash photolysis (LFP) techniques have been used to measure rate constants for coupling between acrylate-type radicals and a series of newly synthesized stable imidazolidine N-oxyl radicals. The carbon-centered radicals under investigation were generated by photolysis of their corresponding ketone precursors RC(O)R (R = C(CH3)2-C(O)OCH3 and CH(CH3)-C(O)-OtBu) in the presence of stable nitroxides. The coupling rate constants kc for modeling studies of nitroxide-mediated polymerization (NMP) experiments were determined, and the influence of steric and electronic factors on kc values was addressed by using a Hammett linear free energy relationship. The systematic changes in kc due to the varied steric (Es,n) and electronic (sigmaL,n) characters of the substituents are well-described by the biparameter equation log(kc/M- 1s(-1)) = 3.52sigmaL,n + 0.47Es,n + 10.62. Hence, kc decreases with the increasing steric demand and increases with the increasing electron-withdrawing character of the substituents on the nitroxide.

Kinetics of activation of a Ca2+-dependent K+ current induced by flash photolysis of caged carbachol in isolated guinea-pig outer hair cells.

PubMed

Chan, E; Evans, M G

1998-09-18

It has been shown that the application of acetylcholine activates a Ca2+-dependent K+ current in outer hair cells, and the resulting hyperpolarization is thought to be an important part of the inhibition mediated by cholinergic efferent nerve fibres to the cochlea. In order to study the kinetics of the current, flash photolysis has been used to apply a cholinergic agonist, carbachol, rapidly to isolated outer hair cells. A delay in the onset of the outward potassium current following photorelease of carbachol was consistently observed, and the activation phase of the response could be described by a sigmoidal-like function with a mean delay of 59 ms and time constant of 71 ms. The sum of these values lies within the time scale reported for the onset of the inhibition following electrical stimulation of the efferent nerves. Although a distinct current attributable to an acetylcholine receptor was not visible in these experiments, indirect evidence for a carbachol-induced influx of Ca2+ was obtained.

The effects of MgADP on cross-bridge kinetics: a laser flash photolysis study of guinea-pig smooth muscle.

PubMed Central

Nishiye, E; Somlyo, A V; Török, K; Somlyo, A P

1993-01-01

1. The effects of MgADP on cross-bridge kinetics were investigated using laser flash photolysis of caged ATP (P3-1(2-nitrophenyl) ethyladenosine 5'-triphosphate), in guinea-pig portal vein smooth muscle permeabilized with Staphylococcus aureus alpha-toxin. Isometric tension and in-phase stiffness transitions from rigor state were monitored upon photolysis of caged ATP. The estimated concentration of ATP released from caged ATP by high-pressure liquid chromatography (HPLC) was 1.3 mM. 2. The time course of relaxation initiated by photolysis of caged ATP in the absence of Ca2+ was well fitted during the initial 200 ms by two exponential functions with time constants of, respectively, tau 1 = 34 ms and tau 2 = 1.2 s and relative amplitudes of 0.14 and 0.86. Multiple exponential functions were needed to fit longer intervals; the half-time of the overall relaxation was 0.8 s. The second order rate constant for cross-bridge detachment by ATP, estimated from the rate of initial relaxation, was 0.4-2.3 x 10(4) M-1 s-1. 3. MgADP dose dependently reduced both the relative amplitude of the first component and the rate constant of the second component of relaxation. Conversely, treatment of muscles with apyrase, to deplete endogenous ADP, increased the relative amplitude of the first component. In the presence of MgADP, in-phase stiffness decreased during force maintenance, suggesting that the force per cross-bridge increased. The apparent dissociation constant (Kd) of MgADP for the cross-bridge binding site, estimated from its concentration-dependent effect on the relative amplitude of the first component, was 1.3 microM. This affinity is much higher than the previously reported values (50-300 microM for smooth muscle; 18-400 microM for skeletal muscle; 7-10 microM for cardiac muscle). It is possible that the high affinity reflects the properties of a state generated during the co-operative reattachment cycle, rather than that of the rigor bridge. 4. The rate constant of Mg

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers.

PubMed

Kanrar, Bappaditya; Bhattacharyya, Anjan

2009-11-01

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (lambda max > or = 250 nm) and sunlight in presence or absence of sensitizers (TiO(2) and KNO(3)). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M(1)-M(5)) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO(2) as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M(1) (Phenol), M(2) [2, 6-Dihydroxy benzoic acid], M(3) [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M(4) [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M(5) as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M(6)-M(11)) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M(6) [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M(7) [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M(8) [4, 6-Dimethoxy-pyrimidin-2-ol], M(9) [6-Methoxy-pyrimidine-2, 4-diol], M(10) [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M(11) [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.

Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources.

PubMed

Sanches, S; Leitão, C; Penetra, A; Cardoso, V V; Ferreira, E; Benoliel, M J; Crespo, M T Barreto; Pereira, V J

2011-09-15

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(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. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrolysis and photolysis of diacylhydrazines-type insect growth regulator JS-118 in aqueous solutions under abiotic conditions.

PubMed

Hu, J-Y; Liu, C; Zhang, Y-C; Zheng, Z-X

2009-05-01

JS-118 is a diacylhydrazines-type insect growth regulator which is now used extensively in China. The hydrolysis and photolysis of the pesticide JS-118 in aqueous solutions have been assessed under natural and controlled conditions in this project. Hydrolysis experimental results show that JS-118 is quite stable in aqueous solutions in dark, with no significant variations be observed in degradation under various conditions. Abiotic hydrolysis is relatively unimportant compared to photolysis. The rate of photodecomposition of JS-118 in aqueous solutions follows first-order kinetics both in UV radiation and natural sunlight. The degradation rates are faster under UV light than sunlight, with the half-lives (t (1/2) = ln2/k) of 6.00-10.85 min and 6.63-10.16 day, respectively. Under UV light, two major photoproducts are detected, and tentatively identified according to HPLC-MS spectral information as N-t-butyl-N-(3,5-dimethylbenzoyl) and 3,7-dimethyl-benzoatedihydrofuran. The corresponding photolysis pathways of JS-118 are also proposed. The results obtained indicate that direct photoreaction is an important dissipation pathway of JS-118 in natural water systems.

Generation mechanism of hydroxyl radical species and its lifetime prediction during the plasma-initiated ultraviolet (UV) photolysis

PubMed Central

Attri, Pankaj; Kim, Yong Hee; Park, Dae Hoon; Park, Ji Hoon; Hong, Young J.; Uhm, Han Sup; Kim, Kyoung-Nam; Fridman, Alexander; Choi, Eun Ha

2015-01-01

Through this work, we have elucidated the mechanism of hydroxyl radicals (OH•) generation and its life time measurements in biosolution. We observed that plasma-initiated ultraviolet (UV) photolysis were responsible for the continues generation of OH• species, that resulted in OH• to be major reactive species (RS) in the solution. The density and lifetime of OH• species acted inversely proportional to each other with increasing depth inside the solution. The cause of increased lifetime of OH• inside the solution is predicted using theoretical and semiempirical calculations. Further, to predict the mechanism of conversion of hydroxide ion (OH−) to OH• or H2O2 (hydrogen peroxide) and electron, we determined the current inside the solution of different pH. Additionally, we have investigated the critical criterion for OH• interaction on cancer cell inducing apoptosis under effective OH• exposure time. These studies are innovative in the field of plasma chemistry and medicine. PMID:25790968

Laser photolysis of caged compounds at 405 nm: photochemical advantages, localisation, phototoxicity and methods for calibration.

PubMed

Trigo, Federico F; Corrie, John E T; Ogden, David

2009-05-30

Rapid, localised photolytic release of neurotransmitters from caged precursors at synaptic regions in the extracellular space is greatly hampered at irradiation wavelengths in the near-UV, close to the wavelength of maximum absorption of the caged precursor, because of inner-filtering by strong absorption of light in the cage solution between the objective and cell. For this reason two-photon excitation is commonly used for photolysis, particularly at multiple points distributed over large fields; or, with near-UV, if combined with local perfusion of the cage. These methods each have problems: the small cross-sections of common cages with two-photon excitation require high cage concentrations and light intensities near the phototoxic limit, while local perfusion gives non-uniform cage concentrations over the field of view. Single-photon photolysis at 405 nm, although less efficient than at 330-350 nm, with present cages is more efficient than two-photon photolysis. The reduced light absorption in the bulk cage solution permits efficient wide-field uncaging at non-toxic intensities with uniform cage concentration. Full photolysis of MNI-glutamate with 100 micros pulses required intensities of 2 mW microm(-2) at the preparation, shown to be non-toxic with repeated exposures. Light scattering at 405 nm was estimated as 50% at 18 microm depth in 21-day rat cerebellum. Methods are described for: (1) varying the laser spot size; (2) photolysis calibration in the microscope with the caged fluorophore NPE-HPTS over the wavelength range 347-405 nm; and (3) determining the point-spread function of excitation. Furthermore, DM-Nitrophen photolysis at 405 nm was efficient for intracellular investigations of Ca2+-dependent processes.

Medium-dependent interactions of quinones with cytosine and cytidine: a laser flash photolysis study with magnetic field effect.

PubMed

Bose, Adity; Basu, Samita

2009-03-01

Laser flash photolysis and an external magnetic field have been used for the study of the interaction of two quinone molecules, namely, 9,10-anthraquinone (AQ) and 2-methyl 1,4-naphthoquinone (or menadione, MQ) with a DNA base, cytosine (C) and its nucleoside cytidine (dC) in two media, a homogeneous one composed of acetonitrile/water (ACN/H(2)O, 9:1, v/v) and a SDS micellar heterogeneous one. We have applied an external magnetic field for the proper identification of the transients formed during the interactions in micellar media. Cytosine exhibits electron transfer (ET) followed by hydrogen abstraction (HA) while dC reveals a reduced ET compared to C, with both quinones in organic homogeneous medium (ACN/H(2)O). Due to a higher electron affinity, AQ supports more faciler ET than MQ with dC in ACN/H(2)O but observations in SDS have been just the reverse. In SDS, ET from dC is completely quenched and a dominant HA is all that could be discerned. This work reveals two main findings: first, a drop in ET on addition of a ribose unit to C, which has been attributed to a role of keto-enol tautomerism in inducing ET from electron-rich nucleus and second, the effect of medium in controlling reaction mechanism by favoring HA with AQ although it is intrinsically more prone towards ET.

UV-photodegradation of desipramine: Impact of concentration, pH and temperature on formation of products including their biodegradability and toxicity.

PubMed

Khaleel, Nareman D H; Mahmoud, Waleed M M; Olsson, Oliver; Kümmerer, Klaus

2016-10-01

Desipramine (DMI) is a widely used tricyclic antidepressant, and it is the major metabolite of imipramine (IMI) and lofepramine (LMI); IMI and LMI are two of the most commonly used tricyclic antidepressants. If DMI enters the aquatic environment, it can be transformed by the environmental bacteria or UV radiation. Therefore, photolysis of DMI in water was performed using a simulated sunlight Xenon-lamp and a UV-lamp. Subsequently, the biodegradability of DMI and its photo-transformation products (PTPs) formed during its UV photolysis was studied. The influence of variable conditions, such as initial DMI concentration, solution pH, and temperature, on DMI UV photolysis behavior was also studied. The degree of mineralization of DMI and its PTPs was monitored. A Shimadzu HPLC-UV apparatus was used to follow the kinetic profile of DMI during UV-irradiation; after that, ion-trap and high-resolution mass spectrometry coupled with chromatography were used to monitor and identify the possible PTPs. The environmentally relevant properties and selected toxicity properties of DMI and the non-biodegradable PTPs were predicted using different QSAR models. DMI underwent UV photolysis with first-order kinetics. Quantum yields were very low. DOC values indicated that DMI formed new PTPs and was not completely mineralized. Analysis by means of high-resolution mass spectrometry revealed that the photolysis of DMI followed three main photolysis pathways: isomerization, hydroxylation, and ring opening. The photolysis rate was inversely proportional to initial DMI concentration. The pH showed a significant impact on the photolysis rate of DMI, and on the PTPs in terms of both formation kinetics and mechanisms. Although temperature was expected to increase the photolysis rate, it showed a non-significant impact in this study. Results from biodegradation tests and QSAR analysis revealed that DMI and its PTPs are not readily biodegradable and that some PTPs may be human and/or eco

Photooxidation of carbofuran by a polychromatic UV irradiation without and with hydrogen peroxide

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

Benitez, F.J.; Beltran-Heredia, J.; Gonzalez, T.

The photodegradation of carbofuran aqueous solutions has been conducted with direct photolysis provided by a polychromatic UV radiation source and by the combination of this UV radiation with hydrogen peroxide. In both processes, the decomposition level obtained as a function of the operating variables is reported, and the presence of tert-butyl alcohol, a scavenger of free radicals, is discussed. While the contribution of hydroxyl radicals is negligible in the direct photolysis, its reactions in the UV/H{sub 2}O{sub 2} system clearly increase the carbofuran decomposition and therefore must be taken into account in the reaction rate equation for the total degradation.more » From the mechanisms proposed, the quantum yields for the direct photolysis and the kinetic constants for the reaction between carbofuran and the hydroxyl radicals generated in the H{sub 2}O{sub 2} photolysis in the combined process are respectively evaluated.« less

Solving Kinetic Equations for the Laser Flash Photolysis Experiment on Nitric Oxide Synthases: Effect of Conformational Dynamics on the Interdomain Electron Transfer.

PubMed

Astashkin, Andrei V; Feng, Changjian

2015-11-12

The production of nitric oxide by the nitric oxide synthase (NOS) enzyme depends on the interdomain electron transfer (IET) between the flavin mononucleotide (FMN) and heme domains. Although the rate of this IET has been measured by laser flash photolysis (LFP) for various NOS proteins, no rigorous analysis of the relevant kinetic equations was performed so far. In this work, we provide an analytical solution of the kinetic equations underlying the LFP approach. The derived expressions reveal that the bulk IET rate is significantly affected by the conformational dynamics that determines the formation and dissociation rates of the docking complex between the FMN and heme domains. We show that in order to informatively study the electron transfer across the NOS enzyme, LFP should be used in combination with other spectroscopic methods that could directly probe the docking equilibrium and the conformational change rate constants. The implications of the obtained analytical expressions for the interpretation of the LFP results from various native and modified NOS proteins are discussed. The mathematical formulas derived in this work should also be applicable for interpreting the IET kinetics in other modular redox enzymes.

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

PubMed Central

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

Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

NASA Technical Reports Server (NTRS)

Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Hand, K. P.; Johnson, R. E.; Loeffler, M. J.; Baragiola, R. A.

2010-01-01

The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carboncontajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

Quantitative assessment on the contribution of direct photolysis and radical oxidation in photochemical degradation of 4-chlorophenol and oxytetracycline.

PubMed

Liu, Yiqing; He, Xuexiang; Fu, Yongsheng; Dionysiou, Dionysios D

2016-07-01

In UV-254 nm/H2O2 advanced oxidation process (AOP), the potential degradation pathways for organic pollutants include (1) hydrolysis, (2) direct H2O2 oxidation, (3) UV direct photolysis, and (4) hydroxyl radical (HO(•)) reaction. In this study, the contribution of these pathways was quantitatively assessed in the photochemical destruction of 4-chlorophenol (4-CP), demonstrating pathways (3) and (4) to be predominantly responsible for the removal of 4-CP by UV/H2O2 in 50 mM phosphate buffer solution. Increasing reaction pH could significantly enhance the contribution of direct photolysis in UV/H2O2 process. The contribution of HO(•) oxidation was improved with increasing initial H2O2 concentration probably due to the increased formation of HO(•). Presence of sodium carbonate (Na2CO3) as in UV/H2O2/Na2CO3 system promoted the degradation of 4-CP, with carbonate radical (CO3 (•-)) reaction and direct photolysis identified to be the main contributing pathways. The trends in the contribution of each factor were further evaluated and validated on the degradation of the antibiotic compound oxytetracycline (OTC). This study provides valuable information on the relative importance of different reaction pathways on the photochemical degradation of organic contaminants such as 4-CP and OTC in the presence and absence of a CO3 (•-) precursor.

Thermal ring closure in Mo(CO){sub 5}L (L = bpy, dmbpy, dpbpy) transients generated by pulsed laser flash photolysis. Mechanistic information from high-pressure effects

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

Reddy, K.B.; Hoffmann, R.; Konya, G.

1992-06-01

The kinetics of the ring-closure reactions of Mo(CO){sub 5}L, produced during the laser flash photolysis of Mo(CO){sub 6} and L where L = 2,2{prime}-bipyridine (bpy), 4,4{prime}-dimethyl-2,2{prime}-bipyridine (dpbpy) and 4,4{prime}-dephenyl-2,2{prime}-bipyridine (dpbpy) were studied as a function of temperature and pressure. The values of the activation parameters and pressure. The values of the activation parameters {Delta}S and {Delta}V are small and negative for L = bpy and dmbpy supporting an associative interchange mechanism (I{sub a}) for CO extrusion. For L = dpbpy, {Delta}V is small and positive in line with a dissociative interchange mechanism (I{sub d}). The results demonstrate a changeover inmore » mechanism from I{sub a} to I{sub d} with increasing steric hindrance on the bidentate ligand L. 36 refs., 1 fig., 2 tabs.« less

Laser flash photolysis experiments on the effects of freezing and salt addition on intramolecular electron transfer within one-electron reduced ascorbate oxidase.

PubMed

Hazzard, J T; Maritano, S; Tollin, G; Marchesini, A

1997-03-01

Laser flash photolysis has been used to investigate the effects of freezing protein solutions and of adding various salts on the kinetics of one-electron photoreduction by 5-deazariboflavin semiquinone (5-DRFH.) of oxidized ascorbate oxidase (AO) from zucchini in 100 mM phosphate buffer (pH 7.0). The initial reaction between oxidized AO and 5-DRFH. is quite rapid (k approximately 10(8) M-1 s-1) and occurs at the blue Type I Cu center. Subsequent to this, a slower, protein concentration-independent intramolecular reoxidation of the Type I Cu is observed, with kET approximately 150 s-1, resulting in 40-50% reoxidation of the blue Cu center and the establishment of an electron transfer (ET) equilibrium between the various Cu centers in AO. When such a sample of AO was frozen overnight at -30 degrees C, flash photolysis of the thawed sample showed no effect on the kinetics of reduction of the Type I Cu by 5-DRFH. However, the rate constant for intramolecular ET decreased to a value of 2.7 s-1, with only 20% reoxidation of the Type I center. Reduction of the enzyme with ascorbic acid, followed by O2 oxidation, resulted in restoration of rapid intramolecular reoxidation (kET = 130 s-1), with 33% of the Type I Cu reduced by 5-DRFH. being reoxidized. These results are consistent with previous work which showed that samples of AO with initially low activity can be reactivated by ascorbic acid turnover in the presence of O2. When AO was frozen in the presence of ascorbic acid, similar inhibition of intramolecular ET was obtained, whereas upon turnover of this sample by further addition of ascorbic acid and exposure to O2, activity was not restored. The effects of addition of (NH4)2SO4, Na2SO4, NH4Cl, NaCl, KCl, and KF on the kinetics of Type I Cu reduction by 5-deazariboflavin semiquinone and on the subsequent intramolecular ET were also examined. A twofold increase in the bimolecular rate constant for reduction of the Type I Cu was observed for the two sodium salts at high

Photolysis of sulfamethoxypyridazine in various aqueous media: aerobic biodegradation and identification of photoproducts by LC-UV-MS/MS.

PubMed

Khaleel, Nareman D H; Mahmoud, Waleed M M; Hadad, Ghada M; Abdel-Salam, Randa A; Kümmerer, Klaus

2013-01-15

Sulfonamides are one of the most frequently used antibiotics worldwide. Therefore, mitigation processes such as abiotic or biotic degradation are of interest. Photodegradation and biodegradation are the potentially significant removal mechanisms for pharmaceuticals in aquatic environments. The photolysis of sulfamethoxypyridazine (SMP) using a medium pressure Hg-lamp was evaluated in three different media: Millipore water pH 6.1 (MW), effluent from sewage treatment plant pH 7.6 (STP), and buffered demineralized water pH 7.4 (BDW). Identification of transformation products (TPs) was performed by LC-UV-MS/MS. The biodegradation of SMP using two tests from the OECD series was studied: Closed Bottle test (OECD 301 D), and Manometric Respirometry test (OECD 301 F). In biodegradation tests, it was found that SMP was not readily biodegradable so it may pose a risk to the environment. The results showed that SMP was removed completely within 128 min of irradiation in the three media, and the degradation rate was different for each investigated type of water. However, dissolved organic carbon (DOC) was not removed in BDW and only little DOC removal was observed in MW and STP, thus indicating the formation of TPs. Analysis by LC-UV-MS/MS revealed new TPs formed. The hydroxylation of SMP represents the main photodegradation pathway. Copyright © 2012 Elsevier B.V. All rights reserved.

Removal of sulfamethoxazole, ibuprofen and nitrobenzene by UV and UV/chlorine processes: A comparative evaluation of 275 nm LED-UV and 254 nm LP-UV.

PubMed

Kwon, Minhwan; Yoon, Yeojoon; Kim, Seonbaek; Jung, Youmi; Hwang, Tae-Mun; Kang, Joon-Wun

2018-10-01

The aim of this study is to evaluate the micropollutant removal capacity of a 275 nm light-emitting diode (LED)-UV/chlorine system. The sulfamethoxazole, ibuprofen, and nitrobenzene removal efficiencies of this system were compared with those of a conventional 254 nm low-pressure (LP)-UV system as a function of the UV dose. In a direct photolysis system, the photon reactivity of sulfamethoxazole is higher than that of nitrobenzene and ibuprofen at both wavelengths. The molar absorption coefficients and quantum yields of each micropollutant were as follows: sulfamethoxazole (ε SMX, 275 nm protonated  = 17,527 M -1  cm -1 , Φ SMX, 275 nm protonated  = 0.239, ε SMX, 275 nm deprotonated  = 8430 M -1  cm -1 , and Φ SMX, 275 nm deprotonated  = 0.026), nitrobenzene (ε NB, 275 nm  = 7176 M -1  cm -1 and Φ NB, 275 nm  = 0.057), and ibuprofen (ε NB, 275 nm  = 200 M -1  cm -1 and Φ IBF, 275 nm  = 0.067). The photon reactivity of chlorine species, i.e., HOCl and OCl-, were determined at 275 nm (ε HOCl, 275 nm  = 28 M -1  cm -1 , Φ HOCl, 275 nm  = 1.97, ε OCl-, 275 nm  = 245 M -1  cm -1 , and Φ OCl-, 275 nm  = 0.8), which indicate that the decomposition rate of OCl - is higher and that of HOCl is lower by 275 nm photolysis than that by 254 nm photolysis (ε HOCl, 254 nm  = 60 M -1  cm -1 , Φ HOCl, 254 nm  = 1.46, ε OCl-, 254 nm  = 58 M -1  cm -1 , and Φ OCl-, 254 nm  = 1.11). In the UV/chlorine system, the removal rates of ibuprofen and nitrobenzene were increased by the formation of OH and reactive chlorine species. The 275-nm LED-UV/chlorine system has higher radical yields at pH 7 and 8 than the 254 nm LP-UV/chlorine system. Copyright © 2018 Elsevier B.V. All rights reserved.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Burkholder, James B

2012-10-28

Oxalyl chloride, (ClCO)(2), has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)(2) and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV∕vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)(2) has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)(2) + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO* → Cl + CO (3a), → ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M → Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO)(2). Φ(193 nm) was found to be 2.07 ± 0.37 independent of bath gas pressure (25.8-105.7 Torr, N(2)), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO)(2) is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 ± 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 ± 0.26 independent of bath gas pressure (15-70 Torr, N(2)). Φ(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N(2)). The low-pressure limit of the total Cl atom quantum yield, Φ(0)(351 nm), was 2

A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

NASA Technical Reports Server (NTRS)

Bosco, S. R.

1982-01-01

The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

Diphosphine is an intermediate in the photolysis of phosphine to phosphorus and hydrogen. [Jupiter atmospheric chemistry

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Benson, R.

1980-01-01

The photolysis of phosphine to red phosphorus (P4) and hydrogen is investigated in light of the potential significance of the reaction in the atmospheric chemistry of Jupiter. It is reported that the photolysis of PH3 at room temperature by a 206.2-nm light source gave rise to a product identified by its UV and IR spectra and gas chromatographic retention time as P2H4, the yield of which is found to increase to a maximum and then decrease to 20% of the maximum value with illumination time. A mechanism for phosphine photolysis including diphosphine formation as an intermediate step is proposed, and it is concluded that P2H4 is a likely constituent of the atmospheres of the Jovian planets.

Sunlight photolysis of benzotriazoles - Identification of transformation products and pathways.

PubMed

Weidauer, Cindy; Davis, Caroline; Raeke, Julia; Seiwert, Bettina; Reemtsma, Thorsten

2016-07-01

Benzotriazoles (BTs) are widely used corrosion inhibitors, incompletely removed in municipal wastewater treatment. The photochemical fate of the three BTs 1H-benzotriazole (1H-BT), 4-methyl-1H-benzotriazole (4Me-BT) and 5-methyl-1H-benzotriazole (5Me-BT) and of three microbial metabolites, was studied under simulated sunlight (290-800 nm) at neutral pH in aqueous solution for 24 h. The half-life, the quantum yield and the reaction rate were determined and a total of 36 photolysis products were detected and identified using liquid chromatography-high resolution-mass spectrometry. The half-lives of all six BTs were in the range of 6-24 h under the experimental conditions. Though the quantum yields were comparatively low (0.0007-0.0021), the environmental half-lives ranged from 2.4 to 8 d, suggesting that sunlight photolysis is still a relevant degradation process of BTs in surface waters. The photolysis pathway of 1H-BT under simulated sunlight differed from that suggested for UV-radiation, in that aminophenol is formed directly rather than via aniline. Similar pathways were found for the other BTs, except for 4-hydroxy-1H-benzotriazole (4OH-BT). Most identified transformation products of the BTs showed a high reactivity and appear not to persist in the environment. Upon co-photolysis of BTs with dissolved organic matter (DOM), however, series of reaction products were determined by Fourier transform - ion cyclotron resonance - mass spectrometry (FTICR-MS) which are formed by reaction of photolysis intermediates of the BTs with DOM. Copyright © 2016 Elsevier Ltd. All rights reserved.

Solar actinic flux spectroradiometry: a technique for measuring photolysis frequencies in the atmosphere.

PubMed

Hofzumahaus, A; Kraus, A; Müller, M

1999-07-20

A spectroradiometer has been developed for direct measurement of the solar actinic UV flux (scalar intensity) and determination of photolysis frequencies in the atmosphere. The instrument is based on a scanning double monochromator with an entrance optic that exhibits an isotropic angular response over a solid angle of 2pi sr. Actinic flux spectra are measured at a resolution of 1 nm across a range of 280-420 nm, which is relevant for most tropospheric photolysis processes. The photolysis frequencies are derived from the measured radiation spectra by use of published absorption cross sections and quantum yields. The advantage of this technique compared with the traditional chemical actinometry is its versatility. It is possible to determine the photolysis frequency for any photochemical reaction of interest provided that the respective molecular photodissociation parameters are known and the absorption cross section falls within a wavelength range that is accessible by the spectroradiometer. The instrument and the calibration procedures are described in detail, and problems specific to measurement of the actinic radiation are discussed. An error analysis is presented together with a discussion of the spectral requirements of the instrument for accurate measurements of important tropospheric photolysis frequencies (J(O(1))(D), J(NO(2)), J(HCHO)). An example of measurements from previous atmospheric chemistry field campaigns are presented and discussed.

Load-dependent mechanical efficiency of individual myosin heads in skeletal muscle fibers activated by laser flash photolysis of caged calcium in the presence of a limited amount of ATP.

PubMed

Sugi, H; Iwamoto, H; Akimoto, T; Ushitani, H

1998-01-01

Although a contracting muscle regulates its energy output depending on the load imposed on it ("Fenn effect"), the mechanism underlying the load-dependent energy output remains obscure. To explore the possibility that the mechanical efficiency, with which chemical energy derived from ATP hydrolysis is converted into mechanical work, of individual myosin heads changes in a load-dependent manner, we examined the auxotonic shortening of glycerinated rabbit psoas muscle fibers, containing ATP molecules almost equal in number to the myosin heads, following laser flash photolysis of caged calcium. Immediately before laser flash activation, almost all of the myosin heads in the fiber are in the state, M.ADP.Pi, and can undergo only one ATP hydrolysis cycle after activation. When the fibers were activated to shorten under various auxotonic loads, the length, force and power output changes were found to be scaled according to the auxotonic load. Both the power and energy outputs were maximal under a moderate auxotonic load. The amount of M.ADP.Pi utilized at a time after activation was estimated from the amount of isometric force developed after interruption of fiber shortening. This amount was minimal in the isometric condition, and increased nearly in proportion to the distance of fiber shortening. These results are taken as evidence that the efficiency of chemo-mechanical energy conversion in individual myosin heads changes in a load-dependent manner.

Aquatic photolysis of β2-agonist salbutamol: kinetics and mechanism studies.

PubMed

Zhou, Lei; Wang, Qi; Zhang, Ya; Ji, Yuefei; Yang, Xi

2017-02-01

Salbutamol (SAL) has been widely used as medicine both in treating asthma and in animal primary production; an increasing number of reports have detected SAL in natural waters. The photolysis kinetic and pathway of SAL in aquatic system were studied, as well as the effect of several natural water constituents, such as nitrate, dissolved oxygen (DO) and ferric ions. According to our research, the direct photolysis of SAL followed pseudo-first-order reaction kinetics. Alkaline condition could promote the degradation of SAL; the increase of solution pH would simultaneously increase the fraction of the deprotonated forms of SAL (including the deprotonated and zwitterionic species), which were easier to be excited, and result in the bathochromic shift of the UV-Vis spectrum and, finally, accelerate the degradation rate of SAL. The presence of nitrate could enhance the removal rate of SAL via generation hydroxyl radical (·OH) under irradiation. In addition, the absence of oxygen in the reaction solution could decrease the photolysis. Moreover, Fe(III) was able to chelate with SAL to form an octahedral complex, which was photochemically reactive. The octahedral complex could generate ·OH to oxidize SAL itself in turn. The pathways of SAL photolysis were also investigated by means of the solid phase extraction (SPE)-LC-MS method. The major pathways of SAL photodegradation included oxidation and side-chain cleavage.

Degradation of herbicide 2,4-dichlorophenoxybutanoic acid in the photolysis of [FeOH]2+ and [Fe(Ox)3]3- complexes: A mechanistic study.

PubMed

Pozdnyakov, Ivan; Sherin, Peter; Grivin, Vjacheslav; Plyusnin, Victor

2016-03-01

In the present work the Fe(III)-assisted photodegradation of the herbicide 2,4-dichlorophenoxybutanoic acid (2,4-DB) has been studied by means of stationary (308 nm) and laser flash (355 nm) photolysis. The initial quantum yield of 2,4-DB photodegradation in [FeOH](2+) and [Fe(Ox)3](3-) systems was evaluated to be 0.11 and 0.17 upon 308 nm exposure, respectively. The prolonged photolysis of [FeOH](2+) and [Fe(Ox)3](3-) systems results in the complete degradation of 2,4-DB with almost complete mineralization of herbicide and its aromatic products in the case of [FeOH](2+) photolysis and the accumulation of some persistent aromatic products in the case of [Fe(Ox)3](3-) photolysis. For both systems the main primary products of 2,4-DB photolysis determined by liquid chromatography - mass spectrometry are products of the hydroxylation, the substitution of chlorine atom to OH group, the loss of aliphatic tail and the opening of benzene ring. The obtained results indicate ROS species (mainly OH radical) to be responsible for the herbicide photodegradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Production of organic compounds in plasmas - A comparison among electric sparks, laser-induced plasmas, and UV light

NASA Technical Reports Server (NTRS)

Scattergood, Thomas W.; Mckay, Christopher P.; Borucki, William J.; Giver, Lawrence P.; Van Ghyseghem, Hilde

1989-01-01

In order to ascertain the features of organic compound-production in planetary atmospheres under the effects of plasmas and shocks, various mixtures of N2, CH4, and H2 modeling the atmosphere of Titan were subjected to discrete sparks, laser-induced plasmas, and UV radiation. The experimental results obtained suggest that UV photolysis from the plasma is an important organic compound synthesis process, as confirmed by the photolysis of gas samples that were exposed to the light but not to the shock waves emitted by the sparks. The thermodynamic equilibrium theory is therefore incomplete in the absence of photolysis.

NF3: UV Absorption Spectrum Temperature Dependence and the Atmospheric and Climate Forcing Implications

NASA Technical Reports Server (NTRS)

Papadimitriou, Vassileios C.; McGillen, Max R.; Fleming, Eric L.; Jackman, Charles H.; Burkholder, James B.

2013-01-01

Nitrogen trifluoride (NF3) is an atmospherically persistent greenhouse gas that is primarily removed by UV photolysis and reaction with O((sup 1)D) atoms. In this work, the NF3 gas-phase UV absorption spectrum, sigma(delta,T), was measured at 16 wavelengths between 184.95 and 250 nm at temperatures between 212 and 296 K. A significant spectrum temperature dependence was observed in the wavelength region most relevant to atmospheric photolysis (200-220 nm) with a decrease in sigma(210 nm,T) of approximately 45 percent between 296 and 212 K. Atmospheric photolysis rates and global annually averaged lifetimes of NF3 were calculated using the Goddard Space Flight Center 2-D model and the sigma(delta,T) parameterization developed in this work. Including the UV absorption spectrum temperature dependence increased the stratospheric photolysis lifetime from 610 to 762 years and the total global lifetime from 484 to 585 years; the NF3 global warming potentials on the 20-, 100-, and 500-year time horizons increased less than 0.3, 1.1, and 6.5 percent to 13,300, 17,700, and 19,700, respectively.

Destruction of microcystins (cyanotoxins) by UV-254 nm-based direct photolysis and advanced oxidation processes (AOPs): influence of variable amino acids on the degradation kinetics and reaction mechanisms.

PubMed

He, Xuexiang; de la Cruz, Armah A; Hiskia, Anastasia; Kaloudis, Triantafyllos; O'Shea, Kevin; Dionysiou, Dionysios D

2015-05-01

Hepatotoxic microcystins (MCs) are the most frequently detected group of cyanobacterial toxins. This study investigated the degradation of common MC variants in water, MC-LR, MC-RR, MC-YR and MC-LA, by UV-254 nm-based processes, UV only, UV/H2O2, UV/S2O8(2-) and UV/HSO5(-). Limited direct photolysis of MCs was observed, while the addition of an oxidant significantly improved the degradation efficiency with an order of UV/S2O8(2-) > UV/HSO5(-) > UV/H2O2 at the same initial molar concentration of the oxidant. The removal of MC-LR by UV/H2O2 appeared to be faster than another cyanotoxin, cylindrospermopsin, at either the same initial molar concentration or the same initial organic carbon concentration of the toxin. It suggested a faster reaction of MC-LR with hydroxyl radical, which was further supported by the determined second-order rate constant of MCs with hydroxyl radical. Both isomerization and photohydration byproducts were observed in UV only process for all four MCs; while in UV/H2O2, hydroxylation and diene-Adda double bond cleavage byproducts were detected. The presence of a tyrosine in the structure of MC-YR significantly promoted the formation of monohydroxylation byproduct m/z 1061; while the presence of a second arginine in MC-RR led to the elimination of a guanidine group and the absence of double bond cleavage byproducts. It was therefore demonstrated in this study that the variable amino acids in the structure of MCs influenced not only the degradation kinetics but also the preferable reaction mechanisms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mechanism of UV-Induced Damage to Mammalian Collagen

DTIC Science & Technology

2014-12-12

enough to use under physiological conditions. We carried out UV photolysis with a UVG – 11 short wavelength hand lamp that emits primarily254 nm. We have...photochemical interaction between UV and mammalian collagen as functions of excitation wavelengths, temperature, fluorescence spectral distribution, and...but has little fluorescence at 325/400 nm (dityrosine). The 325/400 band INCREASES with UV - 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND SUBTITLE 13

A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene.

PubMed

Gritsan, N P; Gudmundsdóttir, A D; Tigelaar, D; Zhu, Z; Karney, W L; Hadad, C M; Platz, M S

2001-03-07

Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet nitrenes were detected by transient absorption spectroscopy, and their spectra are characterized by sharp absorption bands with maxima in the range of 300-365 nm. The kinetics of their decay were analyzed as a function of temperature to yield observed decay rate constants, k(OBS). The observed rate constant in inert solvents is the sum of k(R) + k(ISC) where k(R) is the absolute rate constant of rearrangement of singlet nitrene to an azirine and k(ISC) is the absolute rate constant of nitrene intersystem crossing (ISC). Values of k(R) and k(ISC) were deduced after assuming that k(ISC) is independent of temperature. Barriers to cyclization of 4-fluoro-, 3,5-difluoro-, 2-fluoro-, 2,6-difluoro-, and 2,3,4,5,6-pentafluorophenylnitrene in inert solvents are 5.3 +/- 0.3, 5.5 +/- 0.3, 6.7 +/- 0.3, 8.0 +/- 1.5, and 8.8 +/- 0.4 kcal/mol, respectively. The barrier to cyclization of parent singlet phenylnitrene is 5.6 +/- 0.3 kcal/mol. All of these values are in good quantitative agreement with CASPT2 calculations of the relative barrier heights for the conversion of fluoro-substituted singlet aryl nitrenes to benzazirines (Karney, W. L. and Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347). A single ortho-fluorine substituent exerts a small but significant bystander effect on remote cyclization that is not steric in origin. The influence of two ortho-fluorine substituents on the cyclization is pronounced. In the case of the singlet 2-fluorophenylnitrene system, evidence is presented that the benzazirine is an intermediate and that the corresponding singlet nitrene and benzazirine interconvert. Ab initio calculations at different levels of theory on a series of benzazirines, their isomeric ketenimines, and the transition

Self-initiation of UV photopolymerization reactions using tetrahalogenated bisphenol A (meth)acrylates.

PubMed

Pelras, Théophile; Knolle, Wolfgang; Naumov, Sergej; Heymann, Katja; Daikos, Olesya; Scherzer, Tom

2017-05-17

The potential of tetrachlorinated and tetrabrominated bisphenol A diacrylates and dimethacrylates for self-initiation of a radical photopolymerization was investigated. The kinetics of the photopolymerization of an acrylic model varnish containing halogenated monomers was studied by real-time FTIR spectroscopy, whereas the formation of reactive species and secondary products was elucidated by laser flash photolysis and product analysis by GC-MS after steady-state photolysis. The interpretation of the experimental data and the analysis of possible reaction pathways were assisted by quantum chemical calculations. It was shown that all halogenated monomers lead to a significant acceleration of the photopolymerization kinetics at a minimum concentration of 5 wt%. Steady-state and laser flash photolysis measurements as well as quantum chemical calculations showed that brominated and chlorinated samples do not follow the same pathway to generate radical species. Whereas chlorinated (meth)acrylates may cleave only at the C-O bonds of the carboxyl groups resulting in acrolein and oxyl radicals for initiation, brominated monomers may cleave either at the C-O bonds or at the C-Br bonds delivering aryl and bromine radicals. The quantum yields for the photolysis of the halogenated monomers were found to be in the order of 0.1 for acrylates and 0.2 for methacrylates (with an estimated error of 25%), independently of the attached Br and Cl halogens. Finally, the trihalogenated bisphenol A di(meth)acrylate radicals and the acrolein radicals were found to show the highest efficiencies for the reaction with another acrylic double bond leading to the formation of a polymer network.

A novel UV-photolysis approach with acetone and isopropyl alcohol for the rapid determination of fluoride in organofluorine-containing drugs by spectrophotometry.

PubMed

Mullapudi, Venkata Balarama Krishna; Dheram, Karunasagar

2018-01-01

A UV photolysis decomposition (UVPD) method for the determination of fluoride in fluorine containing pharmaceuticals by spectrophotometry is reported. It is based on the use of high intensity UV-irradiation in the presence of a digesting solution comprising a mixture of acetone and isopropanol. For the optimization of the UVPD procedure, three bulk drugs (levofloxacin, nebivolol and efavirenz) were chosen as representatives of three diverse compounds containing a single fluorine atom, two fluorine atoms, and trifluoromethyl groups respectively. Operational conditions of the UVPD method, such as concentration and volume of reagents (acetone and isopropyl alcohol), and UV irradiation time (1-6 minutes) were optimized. The efficiency of digestion was evaluated by the determination of fluoride in sample digests. Using the developed method, it was possible for complete conversion of the organofluoride to free fluoride ion for its subsequent determination by spectrophotometry based on bleaching of Zr-xylenol orange-color complex. Quantitative recovery (>98%) of the fluorine in the drug samples could be achieved using a mixture of 2% acetone + 2% isopropyl alcohol + 0.003% Na 2 CO 3 in just 5 minutes of UV irradiation, which can be considered an important aspect considering the difficulties involved in the cleavage of the CF bond. Accuracy was evaluated by comparison of results obtained by the UVPD method with the values estimated using formula weight of the compound and no statistical difference was observed between the results. Therefore, the proposed method is suitable for application in routine analysis of fluoride in organofluorine-containing drugs. Copyright © 2016. Published by Elsevier B.V.

New photolysis system for NO2 measurements in the lower stratosphere

NASA Technical Reports Server (NTRS)

Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Ciciora, S. J.; Proffitt, M. H.; Thompson, T. L.; Mclaughlin, R. J.; Fahey, D. W.

1994-01-01

A new system for NO2 detection has been developed for use on the NASA ER-2 aircraft. The system converts NO2 to NO using UV photolysis with the NO product subsequently detected with an on-board chemiluminescence detector. The new system is compact, light weight, has high time resolution (approximately 1 s), and is significantly more efficient then some previous designs. Details of the system design and airborne performance are discussed.

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO2 photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry.

PubMed

Liang, Jing; Wang, Qiuquan; Huang, Benli

2005-01-01

An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV-UV/TiO2 PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 microL dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV-UV/TiO2 PCRD-KBH4-acid interface. The detection limits obtained for seleno-DL: -cystine (SeCys), selenite (Se(IV)), seleno-DL: -methionine (SeMet), and selenate (Se(VI)) were 2.1, 2.9, 4.3, and 3.5 ng mL(-1), respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV-UV/TiO2 PCRD-ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH4.

Velocity measurement in rocket exhaust and general aerodynamic flows by photolysis of H2O and laser induced fluorescence of OH

NASA Technical Reports Server (NTRS)

Boedeker, Laurence R.

1992-01-01

A 'tagging' approach in which the photolysis of H2O by an excimer laser creates a zone of enhanced OH concentration, while a second, pulsed-UV laser detects tagged-zone convection via time-delayed excitation of OH fluorescence, depends on the photodissociation process and the kinetics of OH decay (relative to velocity). For application to the fuel-rich, high supersonic Mach number exhaust flow of the SSME, the detection of OH is being accomplished with either a pulsed narrowband UV dye laser or a tunable XeCl excimer laser for excitation of an OH 0-0 band transition, while the two-photon photolysis of H2O is conducted by focusing an injection-locked KrF excimer laser into the flow.

Application of UV-irradiated Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton systems to degrade model and natural occurring naphthenic acids.

PubMed

Zhang, Ying; Chelme-Ayala, Pamela; Klamerth, Nikolaus; Gamal El-Din, Mohamed

2017-07-01

Naphthenic acids (NAs) are a highly complex mixture of organic compounds naturally present in bitumen and identified as the primary toxic constituent of oil sands process-affected water (OSPW). This work investigated the degradation of cyclohexanoic acid (CHA), a model NA compound, and natural occurring NAs during the UV photolysis of Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton processes. The results indicated that in the UV-Fe(III)NTA process at pH 8, the CHA removal increased with increasing NTA dose (0.18, 0.36 and 0.72 mM), while it was independent of the Fe(III) dose (0.09, 0.18 and 0.36 mM). Moreover, the three Fe concentrations had no influence on the photolysis of the Fe(III)NTA complex. The main responsible species for the CHA degradation was hydroxyl radical (OH), and the role of dissolved O 2 in the OH generation was found to be negligible. Real OSPW was treated with the UV-Fe(III)NTA and UV-NTA-Fenton advanced oxidation processes (AOPs). The removals of classical NAs (O 2 -NAs), oxidized NAs with one additional oxygen atom (O 3 -NAs) and with two additional oxygen atoms (O 4 -NAs) were 44.5%, 21.3%, and 25.2% in the UV-Fe(III)NTA process, respectively, and 98.4%, 86.0%, and 81.0% in the UV-NTA-Fenton process, respectively. There was no influence of O 2 on the NA removal in these two processes. The results also confirmed the high reactivity of the O 2 -NA species with more carbons and increasing number of rings or double bond equivalents. This work opens a new window for the possible treatment of OSPW at natural pH using these AOPs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evidence for the load-dependent mechanical efficiency of individual myosin heads in skeletal muscle fibers activated by laser flash photolysis of caged calcium in the presence of a limited amount of ATP.

PubMed

Sugi, H; Iwamoto, H; Akimoto, T; Ushitani, H

1998-03-03

Although a contracting muscle regulates its energy output depending on the load imposed on it ("Fenn effect"), the mechanism underlying the load-dependent energy output remains obscure. To explore the possibility that the mechanical efficiency, with which chemical energy derived from ATP hydrolysis is converted into mechanical work, of individual myosin heads changes in a load-dependent manner, we examined the auxotonic shortening of glycerinated rabbit psoas muscle fibers, containing ATP molecules almost equal in number to the myosin heads, after laser-flash photolysis of caged calcium. Immediately before laser-flash activation, almost all of the myosin heads in the fiber are in the state M.ADP.Pi, and can undergo only one ATP hydrolysis cycle after activation. When the fibers were activated to shorten under various auxotonic loads, the length, force, and power output changes were found to be scaled according to the auxotonic load. Both the power and energy outputs were maximal under a moderate auxotonic load. The amount of M.ADP.Pi utilized at a time after activation was estimated from the amount of isometric force developed after interruption of fiber shortening. This amount was minimal in the isometric condition and increased nearly in proportion to the distance of fiber shortening. These results are taken as evidence that the efficiency of chemomechanical energy conversion in individual myosin heads changes in a load-dependent manner.

New Observational Evidence of Flash Mixing on the White Dwarf Cooling Curve

NASA Technical Reports Server (NTRS)

Brown, T. M.; Lanz, T.; Sweigart, A. V.; Cracraft, Misty; Hubeny, Ivan; Landsman, W. B.

2011-01-01

Blue hook stars are a class of subluminous extreme horizontal branch stars that were discovered in UV images of the massive globular clusters w Cen and NGC 2808. These stars occupy a region of the HR diagram that is unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that the blue hook stars are very likely the progeny of stars that undergo extensive internal mixing during a late helium-core flash on the white dwarf cooling curve. This "flash mixing" produces hotter-than-normal EHB stars with atmospheres significantly enhanced in helium and carbon. The larger bolometric correction, combined with the decrease in hydrogen opacity, makes these stars appear sub luminous in the optical and UV. Flash mixing is more likely to occur in stars born with a high helium abundance, due to their lower mass at the main sequence turnoff. For this reason, the phenomenon is more common in those massive globular clusters that show evidence for secondary populations enhanced in helium. However, a high helium abundance does not, by itself, explain the presence of blue hook stars in massive globular clusters. Here, we present new observational evidence for flash mixing, using recent HST observations. These include UV color-magnitude diagrams of six massive globular clusters and far-UV spectroscopy of hot subdwarfs in one of these clusters (NGC 2808).

Unexpected photoproduct generated via the acetone-sensitized photolysis of 5-bromo-2'-deoxyuridine in a water/isopropanol solution: experimental and computational studies.

PubMed

Polska, Katarzyna; Zielonka, Justyna; Chomicz, Lidia; Czerwicka, Małgorzata; Stepnowski, Piotr; Guzow, Katarzyna; Wiczk, Wiesław; Smużyńska, Maria; Kasprzykowski, Franciszek; Żylicz-Stachula, Agnieszka; Skowron, Piotr; Rak, Janusz

2010-12-23

The acetone-sensitized photolysis of 5-bromo-2'-deoxyuridine (5-BrdU) in a water/isopropanol solution with 300 nm photons leads to the formation of 2'-deoxyuridine (dU) and a comparable amount of another photoproduct that has not been reported in the literature so far. The negative and positive mass spectra recorded for this species indicate that they originate from the molecular mass of 286 Da, which corresponds to an adduct of 2'-deoxyuridine and 2-propanol. Quantum chemical calculations carried out at the DFT and TDDFT levels reveal both the structure and the UV spectrum of that adduct. The latter computational characteristic matches well the experimental UV spectrum of the new photoproduct. Our findings indicate that the acetone-sensitized photolysis of 5-BrdU is more complicated than has hitherto been assumed. Nevertheless, since electron transfer is one of the pathways responsible for 5-BrdU decay, acetone-sensitized photolysis of the halogen derivatives of nucleobases could be a convenient tool for studying their radiosensitivity in aqueous solutions.

Removal of trace level amounts of twelve sulfonamides from drinking water by UV-activated peroxymonosulfate.

PubMed

Cui, Changzheng; Jin, Lei; Jiang, Lei; Han, Qi; Lin, Kuangfei; Lu, Shuguang; Zhang, Dong; Cao, Guomin

2016-12-01

Trace levels of residual antibiotics in drinking water may threaten public health and become a serious problem in modern society. In this work, we investigated the degradation of twelve sulfonamides (SAs) at environmentally relevant trace level concentrations by three different methods: ultraviolet (UV) photolysis, peroxymonosulfate (PMS) oxidation, and UV-activated PMS (UV/PMS). Sulfaguanidine, sulfadiazine, sulfamerazine, sulfamethazine, sulfathiazole, sulfamethoxydiazine, and sulfadimethoxine were be effectively removed by direct UV photolysis and PMS oxidation. However, sulfanilamide, sulfamethizole, sulfamethoxazole, sulfisoxazole, and sulfachloropyridazine were not completely degraded, despite prolonging the UV irradiation time to 30min or increasing the PMS concentration to 5.0mg·L -1 . UV/PMS provided more thorough elimination of SAs, as demonstrated by the complete removal of 200ng·L -1 of all SAs within 5min at an initial PMS concentration of 1.0mg·L -1 . UV/PMS promoted SA decomposition more efficiently than UV photolysis or PMS oxidation alone. Bicarbonate concentration and pH had a negligible effect on SA degradation by UV/PMS. However, humic acid retarded the process. Removal of 200ng·L -1 of each SA from a sample of sand-filtered effluent from a drinking water treatment plant (DWTPs) was quickly and completely achieved by UV/PMS. Meanwhile, about 41% of the total organic carbon (TOC) was eliminated. Scavenging experiments showed that sulfate radical (SO 4 - ) was the predominant species involved in the degradation. It is concluded that UV/PMS is a rapid and efficient method for removing trace-level SAs from drinking water. Copyright © 2016 Elsevier B.V. All rights reserved.

Decomposition of Amino Acids in 100 K Ice by UV Photolysis: Implications for Survival on Europa

NASA Astrophysics Data System (ADS)

Goguen, Jay D.; Orzechowska, G.; Johnson, P.; Tsapin, A.; Kanik, I.; Smythe, W.

2006-09-01

We report the rate of decomposition by ultraviolet photolysis of 4 amino acids in a mm-thick crystalline water ice matrix at T=100K to constrain the survivability of these important organic molecules within ice lying near the surfaces of outer solar system bodies. We freeze our ice samples from liquid solution which results in mm-thick samples of crystalline phase hexagonal ice that appears "white” due to multiple scattering from internal microstructure. After irradiating an ice and amino acid mixture with an Argon mini-arc UV continuum light source, we used a derivatization technique based on a fluorescence reaction of amino acids to directly measure the remaining fraction of amino acid. We measured ice samples with 0.14, 0.28 and 1.6 mm thickness, prepared from 10-4 M solutions of glycine, D,L-aspartic, D,L-glutamic, and D,L-phenylalanine irradiated from 10 to 1020 minutes. We find that the half-life for decomposition of the amino acid - ice samples is linearly proportional to their thickness as is expected for a layer with strong multiple scattering. Glycine is the most resistant to destruction and phenylalanine is the most easily destroyed. For the 1.6 mm thick samples under lab conditions, the half-life of glycine was 57 hours, aspartic 21 hours, glutamic 23 hours, and phenylalanine 8 hours. These results can be expressed as a "penetration velocity", the depth to which half of the amino acids are destroyed in a year. We conclude that half of these amino acids in the upper meter of low latitude ice on Europa will be decomposed by solar UV on a 10 year timescale. Photons between 160 and 300 nm wavelength are responsible for this decomposition. Progress on identifying and quantifying the products of this decomposition, potential candidates for in-situ studies, will be discussed. This work was supported in part by JPL IR&TD funds.

Impact of humic acid on the photoreductive degradation of perfluorooctane sulfonate (PFOS) by UV/Iodide process.

PubMed

Sun, Zhuyu; Zhang, Chaojie; Chen, Pei; Zhou, Qi; Hoffmann, Michael R

2017-12-15

Iodide photolysis under UV illumination affords an effective method to produce hydrated electrons (e aq - ) in aqueous solution. Therefore, UV/Iodide photolysis can be utilized for the reductive degradation of many recalcitrant pollutants. However, the effect of naturally occurring organic matter (NOM) such as humic and fulvic acids (HA/FA), which may impact the efficiency of UV/Iodide photoreduction, is poorly understood. In this study, the UV photoreductive degradation of perfluorooctane sulfonate (PFOS) in the presence of I - and HA is studied. PFOS undergoes a relatively slow direct photoreduction in pure water, a moderate level of degradation via UV/Iodide, but a rapid degradation via UV/Iodide/HA photolysis. After 1.5 h of photolysis, 86.0% of the initial [PFOS] was degraded in the presence of both I - and HA with a corresponding defluorination ratio of 55.6%, whereas only 51.7% of PFOS was degraded with a defluorination ratio of 4.4% via UV/Iodide illumination in the absence of HA. The relative enhancement in the presence of HA in the photodegradation of PFOS can be attributed to several factors: a) HA enhances the effective generation of e aq - due to the reduction of I 2 , HOI, IO 3 - and I 3 - back to I - ; b) certain functional groups of HA (i.e., quinones) enhance the electron transfer efficiency as electron shuttles; c) a weakly-bonded association of I - and PFOS with HA increases the reaction probability; and d) absorption of UV photons by HA itself produces e aq - . The degradation and defluorination efficiency of PFOS by UV/Iodide/HA process is dependent on pH and HA concentration. As pH increases from 7.0 to 10.0, the enhancement effect of HA improves significantly. The optimal HA concentration for the degradation of 0.03 mM PFOS is 1.0 mg L -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Dictating photoreactivity through restricted bond rotations: cross-photoaddition of atropisomeric acrylimide derivatives under UV/visible-light irradiation.

PubMed

Iyer, Akila; Jockusch, Steffen; Sivaguru, J

2014-11-13

Nonbiaryl atropisomeric acrylimides underwent facile [2 + 2] photocycloaddition leading to cross-cyclobutane adducts with very high stereospecificity (enantiomeric excess (ee): 99% and diastereomeric excess (de): 99%). The photoreactions proceeded smoothly in isotropic media for both direct and triplet sensitized irradiations. The reactions were also found to be very efficient in the solid state where the same cross-cyclobutane adduct was observed. Photophysical studies enabled us to understand the excited-state photochemistry of acrylimides. The triplet energy was found to be ∼63 kcal/mol. The reactions proceeded predominantly via a singlet excited state upon direct irradiation with very poor intersystem crossing that was ascertained by quantification of the generated singlet oxygen. The reactions progressed smoothly with triplet sensitization with UV or visible-light irradiations. Laser flash photolysis experiments established the triplet transient of atropisomeric acrylimides with a triplet lifetime at room temperature of ∼40 ns.

Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways

PubMed Central

Tang, Yuqing; Shi, Xueting; Liu, Yongze; Zhang, Liqiu

2018-01-01

As a potential endocrine disruptor, clofibric acid (CA) was investigated in this study for its degradation kinetics and pathways in UV/chlorine process. The results showed that CA in both UV photolysis and UV/chlorine processes could be degraded via pseudo-first-order kinetics, while it almost could not be degraded in the dark chlorination process. The observed rate constant (kobs) in UV photolysis was 0.0078 min−1, and increased to 0.0107 min−1 combining with 0.1 mM chlorine. The kobs increased to 0.0447 min−1 with further increasing the chlorine dosage from 0.1 to 1.0 mM, and reached a plateau at higher dosage (greater than 1.0 mM). The higher kobs was obtained at acid solution rather than basic solution. Moreover, the calculated contributions of radical species to kobs indicated that the HO• contributed significantly to CA degradation in acidic conditions, while the reactive chlorine species and UV direct photolysis dominated in neutral and basic solution. The degradation of CA was slightly inhibited in the presence of HCO3− (1 ∼ 50 mM), barely affected by the presence of Cl− (1 ∼ 200 mM) and greatly suppressed by humic acid (0 ∼ 5 mg l−1). Thirteen main degradation intermediates and three degradation pathways of CA were identified during UV/chlorine process. PMID:29515853

Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways.

PubMed

Tang, Yuqing; Shi, Xueting; Liu, Yongze; Feng, Li; Zhang, Liqiu

2018-02-01

As a potential endocrine disruptor, clofibric acid (CA) was investigated in this study for its degradation kinetics and pathways in UV/chlorine process. The results showed that CA in both UV photolysis and UV/chlorine processes could be degraded via pseudo-first-order kinetics, while it almost could not be degraded in the dark chlorination process. The observed rate constant ( k obs ) in UV photolysis was 0.0078 min -1, and increased to 0.0107 min -1 combining with 0.1 mM chlorine. The k obs increased to 0.0447 min -1 with further increasing the chlorine dosage from 0.1 to 1.0 mM, and reached a plateau at higher dosage (greater than 1.0 mM). The higher k obs was obtained at acid solution rather than basic solution. Moreover, the calculated contributions of radical species to k obs indicated that the HO• contributed significantly to CA degradation in acidic conditions, while the reactive chlorine species and UV direct photolysis dominated in neutral and basic solution. The degradation of CA was slightly inhibited in the presence of [Formula: see text] (1 ∼ 50 mM), barely affected by the presence of Cl - (1 ∼ 200 mM) and greatly suppressed by humic acid (0 ∼ 5 mg l -1 ). Thirteen main degradation intermediates and three degradation pathways of CA were identified during UV/chlorine process.

Photodegradation of sulfasalazine and its human metabolites in water by UV and UV/peroxydisulfate processes.

PubMed

Ji, Yuefei; Yang, Yan; Zhou, Lei; Wang, Lu; Lu, Junhe; Ferronato, Corinne; Chovelon, Jean-Marc

2018-04-15

The widespread occurrence of pharmaceuticals and their metabolites in natural waters has raised great concerns about their potential risks on human health and ecological systems. This study systematically investigates the degradation of sulfasalazine (SSZ) and its two human metabolites, sulfapyridine (SPD) and 5-aminosalicylic acid (5-ASA), by UV and UV/peroxydisulfate (UV/PDS) processes. Experimental results show that SPD and 5-ASA were readily degraded upon UV 254 nm direct photolysis, with quantum yields measured to be (8.6 ± 0.8) × 10 -3 and (2.4 ± 0.1) × 10 -2  mol Einstein -1 , respectively. Although SSZ was resistant to direct UV photolysis, it could be effectively removed by both UV/H 2 O 2 and UV/PDS processes, with fluence-based pseudo-first-order rate constants determined to be 0.0030 and 0.0038 cm 2  mJ -1 , respectively. Second-order rate constant between SO 4 •- and SSZ was measured as (1.33 ± 0.01) × 10 9  M -1 s -1 by competition kinetic method. A kinetic model was established for predicting the degradation rate of SSZ in the UV/PDS process. Increasing the dosage of PDS significantly enhanced the degradation of SSZ in the UV/PDS process, which can be well predicted by the developed kinetic model. Natural water constituents, such as natural organic matter (NOM) and bicarbonate (HCO 3 - ), influenced the degradation of SSZ differently. The azo functional group of SSZ molecule was predicted as the reactive site susceptible to electrophilic attack by SO 4 •- by frontier electron densities (FEDs) calculations. Four intermediate products arising from azo bond cleavage and SO 2 extrusion were identified by solid phase extraction-liquid chromatography-triple quadrupole mass spectrometry (SPE-LC-MS/MS). Based on the products identified, detailed transformation pathways for SSZ degradation in the UV/PDS system were proposed. Results reveal that UV/PDS could be an efficient approach for remediation of water

Mechanism of Ferric Oxalate Photolysis

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

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Mechanism of Ferric Oxalate Photolysis

DOE PAGES

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr; ...

2017-06-08

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Degradation mechanism and the toxicity assessment in TiO2 photocatalysis and photolysis of parathion.

PubMed

Kim, Tak-Soo; Kim, Jung-Kon; Choi, Kyungho; Stenstrom, Michael K; Zoh, Kyung-Duk

2006-02-01

The photocatalytic degradation of methyl parathion was carried out using a circulating TiO2/UV reactor. The experimental results showed that parathion was more effectively degraded in the photocatalytic condition than the photolysis and TiO2-only condition. With photocatalysis, 10mg/l parathion was completely degraded within 60 min with a TOC decrease exceeding 90% after 150 min. The main ionic byproducts during photocatalysis were measured. The nitrogen from parathion was recovered mainly as NO3-, NO2- and NH4+, 80% of the sulfur as SO4(2-), and less than 5% of the phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and paraoxon were also identified, and these were further degraded. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by photocatalysis and photolysis. A Microtox test using V. fischeri showed that the toxicity, expressed as the relative toxicity (%), was reduced almost completely after 90 min under photocatalysis, whereas only an 83% reduction was achieved with photolysis alone. Another toxicity test using D. magna also showed that the relative toxicity disappeared after 90 min under photocatalysis, whereas there was a 65% reduction in relative toxicity with photolysis alone. The pattern of toxicity reduction parallels the decrease in parathion and TOC concentrations.

Amino acid residues in Anabaena ferredoxin crucial to interaction with ferredoxin-NADP+ reductase: site-directed mutagenesis and laser flash photolysis.

PubMed

Hurley, J K; Salamon, Z; Meyer, T E; Fitch, J C; Cusanovich, M A; Markley, J L; Cheng, H; Xia, B; Chae, Y K; Medina, M

1993-09-14

Ferredoxin (Fd) functions in photosynthesis to transfer electrons from photosystem I to ferredoxin-NADP+ reductase (FNR). We have made several site-directed mutants of Anabaena 7120 Fd and have used laser flash photolysis to investigate the effects of these mutations on the kinetics of reduction of oxidized Fd by deazariboflavin semiquinone (dRfH.) and the reduction of oxidized Anabaena FNR by reduced Fd. None of the mutations influenced the second-order rate constant for dRfH. reduction by more than a factor of 2, suggesting that the ability of the [2Fe-2S] cluster to participate in electron transfer was not seriously affected. In contrast, a surface charge reversal mutation, E94K, resulted in a 20,000-fold decrease in the second-order rate constant for electron transfer from Fd to FNR, whereas a similar mutation at an adjacent site, E95K, produced little or no change in reaction rate constant compared to wild-type Fd. Such a dramatic difference between contiguous surface mutations suggests a very precise surface complementarity at the protein-protein interface. Mutations introduced at F65 (F65I and F65A) also decreased the rate constant for the Fd/FNR electron transfer reaction by more than 3 orders of magnitude. Spectroscopic and thermodynamic measurements with both the E94 and F65 mutants indicated that the kinetic differences cannot be ascribed to changes in gross conformation, redox potential, or FNR binding constant but rather reflect the protein-protein interactions that control electron transfer. Several mutations at other sites in the vicinity of E94 and F65 (R42, T48, D68, and D69) resulted in little or no perturbation of the Fd/FNR interaction.(ABSTRACT TRUNCATED AT 250 WORDS)

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

PubMed

Shen, Y S; Ku, Y

2002-01-01

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.

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

PubMed

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.

Tailor-made dimensions of diblock copolymer truncated micelles on a solid by UV irradiation.

PubMed

Liou, Jiun-You; Sun, Ya-Sen

2015-09-28

We investigated the structural evolution of truncated micelles in ultrathin films of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, of monolayer thickness on bare silicon substrates (SiOx/Si) upon UV irradiation in air- (UVIA) and nitrogen-rich (UVIN) environments. The structural evolution of micelles upon UV irradiation was monitored using GISAXS measurements in situ, while the surface morphology was probed using atomic force microscopy ex situ and the chemical composition using X-ray photoelectron spectroscopy (XPS). This work provides clear evidence for the interpretation of the relationship between the structural evolution and photochemical reactions in PS-b-P2VP truncated micelles upon UVIA and UVIN. Under UVIA treatment, photolysis and cross-linking reactions coexisted within the micelles; photolysis occurred mainly at the top of the micelles, whereas cross-linking occurred preferentially at the bottom. The shape and size of UVIA-treated truncated micelles were controlled predominantly by oxidative photolysis reactions, which depended on the concentration gradient of free radicals and oxygen along the micelle height. Because of an interplay between photolysis and photo-crosslinking, the scattering length densities (SLD) of PS and P2VP remained constant. In contrast, UVIN treatments enhanced the contrast in SLD between the PS shell and the P2VP core as cross-linking dominated over photolysis in the presence of nitrogen. The enhancement of the SLD contrast was due to the various degrees of cross-linking under UVIN for the PS and P2VP blocks.

Degradation of thiamethoxam and metoprolol by UV, O3 and UV/O3 hybrid processes: Kinetics, degradation intermediates and toxicity

NASA Astrophysics Data System (ADS)

Šojić, D.; Despotović, V.; Orčić, D.; Szabó, E.; Arany, E.; Armaković, S.; Illés, E.; Gajda-Schrantz, K.; Dombi, A.; Alapi, T.; Sajben-Nagy, E.; Palágyi, A.; Vágvölgyi, Cs.; Manczinger, L.; Bjelica, L.; Abramović, B.

2012-11-01

SummaryA comprehensive study of the degradation of thiamethoxam (THIA) and metoprolol (MET) was conducted by using UV-induced photolysis (λ = 254 nm), ozonation, and a combination of these methods. In order to investigate how molecular structure of the substrate influences the rate of its degradation, we compared these three processes for the insecticide THIA and the drug MET (a β1-blocker). Of the three treatments applied, the UV photolysis and the combination of UV/O3 were found to be most effective in the degradation of THIA, while the UV/O3 process appeared to be the most efficient in terms of MET decay. The degradation kinetics was monitored by LC-DAD, and spectrophotometry, while the mineralization of the substrates was studied by TOC analysis. Reaction intermediates were studied in detail and a number of them were identified using LC-MS (ESI+/ESI-). Both parent compounds showed slight toxic effects towards algae Pseudokirchneriella subcapitata and bacteria Vibrio fischeri. However, the toxicity of the solutions containing also the degradation intermediates appeared to be much higher for all the test organisms. The inhibition/mortality rates were reduced most efficiently by the UV/O3 procedure. Ames test and Comet assay were used to follow the genotoxicity during the degradation of the studied compounds. Genotoxic intermediates were frequently detected in the case of MET in the UV treatment alone or in the presence of ozone. Treatments of THIA samples resulted less frequently in genotoxic intermediates. To our best knowledge, this work is the first genotoxicological investigation dealing with the photolytic degradation process of the studied compounds.

Photolytic removal of DBPs by medium pressure UV in swimming pool water.

PubMed

Hansen, Kamilla M S; Zortea, Raissa; Piketty, Aurelia; Vega, Sergio Rodriguez; Andersen, Henrik Rasmus

2013-01-15

Medium pressure UV is used for controlling the concentration of combined chlorine (chloramines) in many public swimming pools. Little is known about the fate of other disinfection by-products (DBPs) in UV treatment. Photolysis by medium pressure UV treatment was investigated for 12 DBPs reported to be found in swimming pool water: chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetronitrile, trichloroacetonitrile, trichloronitromethane, dichloropropanone, trichloropropanone, and chloral hydrate. First order photolysis constants ranged 26-fold from 0.020 min(-1) for chloroform to 0.523 min(-1) for trichloronitromethane. The rate constants generally increased with bromine substitution. Using the UV removal of combined chlorine as an actinometer, the rate constants were recalculated to actual treatment doses of UV applied in a swimming pool. In an investigated public pool the UV dose was equivalent to an applied electrical energy of 1.34 kWh m(-3) d(-1) and the UV dose required to removed 90% of trichloronitromethane was 0.4 kWh m(-3) d(-1), while 2.6 kWh m(-3) d(-1) was required for chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes ranged from 0.6 to 3.1 kWh m(-3) d(-1). It was predicted thus that a beneficial side-effect of applying UV for removing combined chlorine from the pool water could be a significant removal of trichloronitromethane, chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes. Copyright © 2012 Elsevier B.V. All rights reserved.

Acquisition of a Nanosecond Laser Flash Photolysis Spectrometer to Enhance Understanding of Photochemistry and Reaction Kinetics in Undergraduate Research/Curriculum

DTIC Science & Technology

2016-03-31

photolysis # Compound # Compound 1 1,4-Dinitrobenzene 9 Azulene 2 1,2-Dinitrobenzene 10 4-Cyanophenol 3 Ferrocene 11 2-Nitrotoluene 4 4-Phenylphenol 12...Anthracene 4-Hydroxy-3-methoxybenzoic acid Cyclohexane Dithieno[3,2-b:2’,3’-d] thiophene Ferrocene Dimthylaniline Benzene 1,4- Diazabicyclo[2.2.2

Enhanced Heterogeneous Nitrates Photolysis on Ice and Potential Impacts on NOx Emissions

NASA Astrophysics Data System (ADS)

Ayotte, P.; Marcotte, G.; Pronovost, S.; Marchand, P.; Laffon, C.; Parent, P.

2015-12-01

Nitrates photolysis plays a key role in the chemistry of the polar boundary layer and of the lower troposphere over snow-covered areas (1). Using a combination of vibrational (2) and photo-absorption spectroscopies (3), we show that nitric acid is mostly dissociated upon its adsorption onto, and its dissolution within ice at temperatures as low 20K. Using amorphous solid water as a model substrate for the disordered surface layer at the interstitial air-ice interface, UV irradiation in the environmentally relevant n-π* transition uncovers the fact that the photolysis rates are significantly higher for surface-bound nitrates compared to those dissolved within the bulk. The complex coupled interfacial transport and reaction kinetics result in the formation of a thin photochemically active layer at the surface of ice which may magnify the impact of surface-enhanced nitrates photolysis rates on ice thereby providing a significant contribution to the intense photochemical NOxfluxes observed to emanate from the sunlit snowpack upon polar sunrise.(4) (1) F. Dominé, P.B. Shepson, Science, 297, 1506-1510 (2002).(2) P. Marchand, G. Marcotte, and P. Ayotte, Spectroscopic Study of HNO3 Dissociation on Ice, J. Phys. Chem. A 116, 12112-12122 (2012).(3) G. Marcotte, P. Ayotte, A. Bendounan, F. Sirotti, C. Laffon and P. Parent, J. Phys. Chem. Lett. 4, 2643-2648 (2013).(4) G. Marcotte, P. Marchand, S. Pronovost, P. Ayotte, C. Laffon and P. Parent, J. Phys. Chem. A 119, 1996-2005 (2015).

Photodegradation of veterinary ionophore antibiotics under UV and solar irradiation.

PubMed

Sun, Peizhe; Pavlostathis, Spyros G; Huang, Ching-Hua

2014-11-18

The veterinary ionophore antibiotics (IPAs) are extensively used as coccidiostats and growth promoters and are released to the environment via land application of animal waste. Due to their propensity to be transported with runoff, IPAs likely end up in surface waters where they are subject to photodegradation. This study is among the first to investigate the photodegradation of three commonly used IPAs, monensin (MON), salinomycin (SAL) and narasin (NAR), under UV and solar irradiation. Results showed that MON was persistent in a deionized (DI) water matrix when exposed to UV and sunlight, whereas SAL and NAR could undergo direct photolysis with a high quantum yield. Water components including nitrate and dissolved organic matter had a great impact on the photodegradation of IPAs. A pseudosteady state kinetic model was successfully applied to predict IPAs' photodegradation rates in real water matrices. Applying LC/MS/MS, multiple photolytic transformation products of IPAs were observed and their structures were proposed. The direct photolysis of SAL and NAR occurred via cleavage on the ketone moiety and self-sensitized photolysis. With the presence of nitrate, MON was primarily degraded by hydroxyl radicals, whereas SAL showed reactivity toward both hydroxyl and nitrogen-dioxide radicals. Additionally, toxicity tests showed that photodegradation of SAL eliminated its antibiotic properties against Bacillus subtilis.

The role of natural organic matter in nitrite formation by LP-UV/H2O2 treatment of nitrate-rich water.

PubMed

Semitsoglou-Tsiapou, Sofia; Mous, Astrid; Templeton, Michael R; Graham, Nigel J D; Hernández Leal, Lucía; Kruithof, Joop C

2016-12-01

The role of natural organic matter (NOM) on nitrite formation from nitrate photolysis by low pressure ultraviolet lamp (LP-UV) photolysis and LP-UV/H 2 O 2 treatment was investigated. Nitrate levels up to the WHO guideline maximum of 50 mg NO 3 - /L were used in tests. The presence of 4 mg/L Suwannee River natural organic matter (NOM) led to increased nitrite yields compared to NOM-free controls. This was caused partly by NOM scavenging of OH radicals, preserving the produced NO 2 - as well as the ONOO - that leads to NO 2 - formation, but also via the production of radical species ( 1 O 2 , O 2 - and OH) by the photolysis of NOM. In addition, solvated electrons formed by NOM photolysis may reduce nitrate directly to nitrite. For comparison, Nordic Lake NOM, representative of aquatic NOM, as well as Pony Lake NOM, which had a greater nitrogen content (6.51% w/w) than the other two types of NOM, were investigated, yielding similar nitrite levels as Suwannee River NOM. The results suggest that neither the type nor the nitrogen content of the NOM have an effect on the nitrite yields obtained over the range of UV/H 2 O 2 doses applied (UV fluences of 500-2100 mJ/cm 2 and hydrogen peroxide doses of 10, 25, and 50 mg/L). The findings indicate that for UV fluences above 1500 mJ/cm 2 the resulting nitrite concentration can exceed the 0.1 mg/L EU regulatory limit for nitrite, suggesting that nitrite formation by LP-UV advanced oxidation of nitrate-rich waters is important to consider. Copyright © 2016 Elsevier Ltd. All rights reserved.

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.; Chameides, W. L.; Crutzen, P. J.; Fishman, J.

1979-01-01

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Mechanistic study of fulvic acid assisted propranolol photodegradation in aqueous solution.

PubMed

Makunina, Maria P; Pozdnyakov, Ivan P; Chen, Yong; Grivin, Vyacheslav P; Bazhin, Nikolay M; Plyusnin, Victor F

2015-01-01

Laser flash (355 nm) and stationary (365 nm) photolysis were used to study the mechanisms of propranolol photolysis in the presence of fulvic acid in aqueous solutions. The FA-assisted photodegradation of propranolol was observed using UV-A irradiation (where propranolol is stable). Direct evidence indicated that the photodegradation resulted from the static quenching of the FA triplet state by propranolol via the electron transfer mechanism. The triplet state yield (ϕT≈0.6%) and the T-T absorption coefficient (ɛT(620 nm)≈5×10(4) M(-1) cm(-1)) were estimated for the first time by modeling the yields of the FA triplet state in the presence of propranolol. Thus, fulvic acid is a promising agent for accelerating propranolol photodegradation in aqueous solutions under UV-A light irradiation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Study of the spectra of silica colloidal crystals with assembled silver obtained from a photolysis method

NASA Astrophysics Data System (ADS)

Li, Wenjiang; He, Jinglong; He, Sailing

2005-02-01

The colorful artificial 3D silica colloidal crystals (opal) were prepared through self-assembly of silica spheres in the visible frequency range. We directly synthesized nano silver particles in the void of the silica artificial opal film using the photolysis of silver nitrate under UV light, nano silver particles were self-deposited around the surface of silica sphere. The shifts of the stop band of the artificial crystals after exposing different time under UV light were studied. Synthetic silica opal with three-dimensional (3D) structure is potentially useful for the development of diffractive optical devices, micro mechanical systems, and sensory elements because photonic band gaps obtained from self-assembled closely packed periodic structures.

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

PubMed

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. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photodegradation and ecotoxicology of acyclovir in water under UV254 and UV254/H2O2 processes.

PubMed

Russo, Danilo; Siciliano, Antonietta; Guida, Marco; Galdiero, Emilia; Amoresano, Angela; Andreozzi, Roberto; Reis, Nuno M; Li Puma, Gianluca; Marotta, Raffaele

2017-10-01

The photochemical and ecotoxicological fate of acyclovir (ACY) through UV 254 direct photolysis and in the presence of hydroxyl radicals (UV 254 /H 2 O 2 process) were investigated in a microcapillary film (MCF) array photoreactor, which provided ultrarapid and accurate photochemical reaction kinetics. The UVC phototransformation of ACY was found to be unaffected by pH in the range from 4.5 to 8.0 and resembled an apparent autocatalytic reaction. The proposed mechanism included the formation of a photochemical intermediate (ϕ ACY  = (1.62 ± 0.07)·10 -3  mol ein -1 ) that further reacted with ACY to form by-products (k' = (5.64 ± 0.03)·10 -3  M -1  s -1 ). The photolysis of ACY in the presence of hydrogen peroxide accelerated the removal of ACY as a result of formation of hydroxyl radicals. The kinetic constant for the reaction of OH radicals with ACY (k OH/ACY ) determined with the kinetic modeling method was (1.23 ± 0.07)·10 9  M -1  s -1 and with the competition kinetics method was (2.30 ± 0.11)·10 9  M -1  s -1 with competition kinetics. The acute and chronic effects of the treated aqueous mixtures on different living organisms (Vibrio fischeri, Raphidocelis subcapitata, D. magna) revealed significantly lower toxicity for the samples treated with UV 254 /H 2 O 2 in comparison to those collected during UV 254 treatment. This result suggests that the addition of moderate quantity of hydrogen peroxide (30-150 mg L -1 ) might be a useful strategy to reduce the ecotoxicity of UV 254 based sanitary engineered systems for water reclamation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monitoring light-induced structural changes of Channelrhodopsin-2 by UV-visible and Fourier transform infrared spectroscopy.

PubMed

Ritter, Eglof; Stehfest, Katja; Berndt, Andre; Hegemann, Peter; Bartl, Franz J

2008-12-12

Channelrhodopsin-2 (ChR2) is a microbial type rhodopsin and a light-gated cation channel that controls phototaxis in Chlamydomonas. We expressed ChR2 in COS-cells, purified it, and subsequently investigated this unusual photoreceptor by flash photolysis and UV-visible and Fourier transform infrared difference spectroscopy. Several transient photoproducts of the wild type ChR2 were identified, and their kinetics and molecular properties were compared with those of the ChR2 mutant E90Q. Based on the spectroscopic data we developed a model of the photocycle comprising six distinguishable intermediates. This photocycle shows similarities to the photocycle of the ChR2-related Channelrhodopsin of Volvox but also displays significant differences. We show that molecular changes include retinal isomerization, changes in hydrogen bonding of carboxylic acids, and large alterations of the protein backbone structure. These alterations are stronger than those observed in the photocycle of other microbial rhodopsins like bacteriorhodopsin and are related to those occurring in animal rhodopsins. UV-visible and Fourier transform infrared difference spectroscopy revealed two late intermediates with different time constants of tau = 6 and 40 s that exist during the recovery of the dark state. The carboxylic side chain of Glu(90) is involved in the slow transition. The molecular changes during the ChR2 photocycle are discussed with respect to other members of the rhodopsin family.

Monitoring Light-induced Structural Changes of Channelrhodopsin-2 by UV-visible and Fourier Transform Infrared Spectroscopy*

PubMed Central

Ritter, Eglof; Stehfest, Katja; Berndt, Andre; Hegemann, Peter; Bartl, Franz J.

2008-01-01

Channelrhodopsin-2 (ChR2) is a microbial type rhodopsin and a light-gated cation channel that controls phototaxis in Chlamydomonas. We expressed ChR2 in COS-cells, purified it, and subsequently investigated this unusual photoreceptor by flash photolysis and UV-visible and Fourier transform infrared difference spectroscopy. Several transient photoproducts of the wild type ChR2 were identified, and their kinetics and molecular properties were compared with those of the ChR2 mutant E90Q. Based on the spectroscopic data we developed a model of the photocycle comprising six distinguishable intermediates. This photocycle shows similarities to the photocycle of the ChR2-related Channelrhodopsin of Volvox but also displays significant differences. We show that molecular changes include retinal isomerization, changes in hydrogen bonding of carboxylic acids, and large alterations of the protein backbone structure. These alterations are stronger than those observed in the photocycle of other microbial rhodopsins like bacteriorhodopsin and are related to those occurring in animal rhodopsins. UV-visible and Fourier transform infrared difference spectroscopy revealed two late intermediates with different time constants of τ = 6 and 40 s that exist during the recovery of the dark state. The carboxylic side chain of Glu90 is involved in the slow transition. The molecular changes during the ChR2 photocycle are discussed with respect to other members of the rhodopsin family. PMID:18927082

Photochemistry of bromoacetylene - Formation of HBr and quenching of excited Br/4 2P 0 1/2/

NASA Technical Reports Server (NTRS)

Laufer, A. H.

1979-01-01

The photolysis of bromacetylene is examined by means of vacuum ultraviolet flash photolysis-kinetic spectroscopy, with attention given to the production of Br atoms in the 2P 0 3/2 and 2P 0 1/2 states, the production of HBr, and UV absorption attributable to the ethynyl radical. Although Br(2P 0 1/2) and Br(2P 0 3/2) were both directly observed at the shortest delay time after the flash, strongly indicating the presence of the ethynyl radical, transient absorption by C2H was not detected in the range 125 to 180 nm. Quenching rate constants for the decay of the 2P 0 1/2 state of Br, which is observed to form concurrently with the ground state, are derived for quenching by He, CH2Br, CF4, and D2 from the pseudo-first-order decay rates. HBr was observed as a secondary photolysis product, and a model of its formation by the exothermic reaction of ground-state atoms with C2HBR, coupled with the secondary production of Br atoms, is found to agree well with the experiment.

DFT and TD-DFT insights, photolysis and photocatalysis investigation of three dyes with similar structure under UV irradiation with and without TiO2 as a catalyst: Effect of adsorption, pH and light intensity.

PubMed

Bendjabeur, Seyfeddine; Zouaghi, Razika; Zouchoune, Bachir; Sehili, Tahar

2018-02-05

TiO 2 -mediated photocatalytic degradation of three triphenylmethane dyes (basic fuchsin, acid fuchsin and Gentian violet), was investigated in aqueous suspensions in the presence and the absence of titanium dioxide P25 Degussa as photocatalyst. The photodegradation process was investigated using UV-A (365nm) and UV-C (254nm) light alone and UV-A in the presence of TiO 2 ·The effects of various operational parameters were investigated such as: the effect of adsorption in the dark, the influence of pH, the influence of irradiation wavelength and the effect of light intensity. The study of the effect of various parameters reveals that the photolysis of dyes increases with the increase of light intensity, the degradation rate under UV-C (254nm) was found better than under UV-A 365nm. The photocatalytic degradation was found to follow the same order of adsorption. The decolorization and the degradation kinetics were found to follow the pseudo-first-order kinetics. The mineralization of dye was found to follow the same order of disappearance as the photocatalytic degradation and depended directly to its functional groups and its number of carbons. Additionally, density functional theory (DFT) was applied for calculations of both electronic structure and spectroscopic properties of the studied compounds, where the obtained results of the three dyes show that the theoretical electronic spectra and the experimental UV-visible ones are similar in shapes, positions and intensities. Copyright © 2017. Published by Elsevier B.V.

DFT and TD-DFT insights, photolysis and photocatalysis investigation of three dyes with similar structure under UV irradiation with and without TiO2 as a catalyst: Effect of adsorption, pH and light intensity

NASA Astrophysics Data System (ADS)

Bendjabeur, Seyfeddine; Zouaghi, Razika; Zouchoune, Bachir; Sehili, Tahar

2018-02-01

TiO2-mediated photocatalytic degradation of three triphenylmethane dyes (basic fuchsin, acid fuchsin and Gentian violet), was investigated in aqueous suspensions in the presence and the absence of titanium dioxide P25 Degussa as photocatalyst. The photodegradation process was investigated using UV-A (365 nm) and UV-C (254 nm) light alone and UV-A in the presence of TiO2·The effects of various operational parameters were investigated such as: the effect of adsorption in the dark, the influence of pH, the influence of irradiation wavelength and the effect of light intensity. The study of the effect of various parameters reveals that the photolysis of dyes increases with the increase of light intensity, the degradation rate under UV-C (254 nm) was found better than under UV-A 365 nm. The photocatalytic degradation was found to follow the same order of adsorption. The decolorization and the degradation kinetics were found to follow the pseudo-first-order kinetics. The mineralization of dye was found to follow the same order of disappearance as the photocatalytic degradation and depended directly to its functional groups and its number of carbons. Additionally, density functional theory (DFT) was applied for calculations of both electronic structure and spectroscopic properties of the studied compounds, where the obtained results of the three dyes show that the theoretical electronic spectra and the experimental UV-visible ones are similar in shapes, positions and intensities.

Photolysis of Diazo Dye in Aqueous Solutions of Metal Nitrates

NASA Astrophysics Data System (ADS)

Volkova, N. A.; Evstrop'ev, S. K.; Istomina, O. V.; Kolobkova, E. V.

2018-04-01

The photolysis of Chicago Blue Sky diazo dye is studied. It is experimentally shown that the presence of metal nitrates in aqueous solutions changes the photolysis mechanism and sharply increases the photolysis rate.

Comparison of photocatalysis and photolysis of malathion, isomalathion, malaoxon, and commercial malathion--products and toxicity studies.

PubMed

Bavcon Kralj, M; Cernigoj, U; Franko, M; Trebse, P

2007-11-01

Malathion, one of the most widely applied insecticides, is still used in agriculture. There are many studies regarding its degradation under different experimental conditions, but few deal with its transformation products, i.e. malaoxon and isomalathion. Thus, malathion, malaoxon, isomalathion, and Radotion (one of its over 6000 commercial forms) were studied in terms of their degradation kinetics, identification of their transformation products, their toxicity, and their degree of mineralization, during UV photolysis (lambda = 254 nm) and TiO(2) photocatalysis (lambda = 355 nm). The degradation kinetics was similar for all four starting materials. More than 75% of theoretically expected sulfur in PS and P-S groups was oxidized after 240 min of photolysis and photocatalysis. On the other hand, less than 30% of stoichiometrically predicted amounts of phosphate was detected in the photolytic experiments, but more than 80% of expected phosphate was detected after photocatalytic treatment of all four organophosphorous materials. Several transformation products were identified by mass spectra of representative gas chromatographic peaks. Oxidation and isomerization were found as the main reactions of butenedioc acid diethyl esters and their analogs. The formation of malaoxon, isomalathion or trimethyl phosphate esters correlated well with the induced toxicity (inhibition of acetylcholinesterase), which was observed in photocatalysis of malathion and Radotion, and in photolysis of malaoxon and Radotion.

Laser photolysis study of the exciplex between triplet benzil and triethylamine

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

Encinas, M.V.; Scaiano, J.C.

1979-12-19

Nanosecond laser flash photolysis techniques have been used to examine the triplet decay and radical-ion formation in the triethylamine (TEA) - benzil system in wet acetonitrile. Under conditions of high TEA concentrations yielding short triplet lifetime, the formation of the benzil radical anion was found to be considerably slower than the decay of the triplet state. This effect is attributed to the intermediacy of a relatively stable exciplex whose properties are reported here. Results of a study of optical density of the system with time following laser excitation led to the assignment of a lifetime of 55ns to the exciplexmore » formed between the triplet benzil and TEA. A structure is suggested for the exciplex. Results of experiments with the non-polar medium n-heptane indicated a shorter lifetime exciplex or one with very different properties from the species identified in the polar medium, wet acetonitrile. (BLM)« less

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

2002-01-01

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1978-01-01

A cyclic process is described for the solar photolysis of water, including a first stage in which water is reduced in the presence of a Eu(+2) photooxidizable reagent producing hydrogen and spent oxidized Eu(+3) reagent. The spent reagent Eu(+3) is reduced by means of a transition metal ligand complex reductant, RuL(+3) in a photoexcited state, such as a ruthenium pyridyl complex. Due to competing reactions between the photolysis and regeneration products, the photooxidation reaction must be separated from the regeneration in space and time by supporting the reagent and/or the reductant on solid supports and utilizing pH, wavelength and flow control to maximize hydrogen and oxygen production.

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Force, Michael; Briggs, Robert G.; Ferris, James P.; Persans, Peter; Chera, John J.

2008-01-01

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the C tbnd N frequency at 2210 cm -1 in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV

Bromate formation from the oxidation of bromide in the UV/chlorine process with low pressure and medium pressure UV lamps.

PubMed

Fang, Jingyun; Zhao, Quan; Fan, Chihhao; Shang, Chii; Fu, Yun; Zhang, Xiangru

2017-09-01

When a bromide-containing water is treated by the ultraviolet (UV)/chlorine process, hydroxyl radicals (HO) and halogen radicals such as Cl or Br are formed due to the UV photolysis of free halogens. These reactive species may induce the formation of bromate, which is a probable human carcinogen. Bromate formation in the UV/chlorine process using low pressure (LP) and medium pressure (MP) lamps in the presence of bromide was investigated in the present study. The UV/chlorine process significantly enhanced bromate formation as compared to dark chlorination. The bromate formation was elevated with increasing UV fluence, bromide concentration, and pH values under both LP and MP UV irradiations. It was significantly enhanced at pH 9 compared to those at pH 6 and 7 with MP UV irradiation, while it was slightly enhanced at pH 9 with LP UV. The formation by UV/chlorine process started with the formation of free bromine (HOBr/OBr - ) through the reaction of chlorine and bromide, followed by a subsequent oxidation of free bromine and formation of BrO and bromate by reacting with radicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Laser photolysis studies of the phenolic H-atom transfer mechanism for a triplet π,π ∗ ketone in solution revisited

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Aoyama, Yutaka; Furukawa, Takashi; Itoh, Takao; Tobita, Seiji

2006-03-01

The mechanism of the H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-naphthacenequinone (5,12-NQ) has been examined by means of laser flash photolysis at 295 K. Based on the Hammett plots and the Rehm-Weller equation for the quenching rate constants, the phenolic H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-NQ is shown to proceed via the electron transfer followed by proton transfer. The previously proposed mechanism for H-atom transfer of π,π ∗ triplets, that proton transfer is followed by electron transfer, was not verified in the present systems.

UV-C radiation based methods for aqueous metoprolol elimination.

PubMed

Rivas, F J; Gimeno, O; Borralho, T; Carbajo, M

2010-07-15

The endocrine disruptor metoprolol has been oxidised in aqueous solution by means of the systems UV-C, UV-C/H(2)O(2), UV-C/percarbonate, UV-C/monopersulfate, UV-C/TiO(2), UV-C/H(2)O(2)/TiO(2) and photo-Fenton. From simple photolysis experiments the quantum yield of metoprolol has been calculated (roughly 5x10(-3) mol Einstein(-1) at circumneutral pH). Addition of free radicals promoters significantly enhanced the metoprolol depletion rate. Mineralization degree was negligible when no promoter was added, while low values were achieved in the presence of either inorganic peroxides or titanium dioxide. The combination of radiation, hydrogen peroxide and TiO(2) increased the mineralization level up to values in the proximity of 45-50% under the best conditions investigated. The photo-Fenton process was the best system in terms of total oxidation (mineralization degree 70%) when optimum conditions were applied. 2010 Elsevier B.V. All rights reserved.

Comparison of Nitrilotriacetic Acid and [S,S]-Ethylenediamine-N,N'-disuccinic Acid in UV-Fenton for the Treatment of Oil Sands Process-Affected Water at Natural pH.

PubMed

Zhang, Ying; Klamerth, Nikolaus; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

2016-10-04

The application of UV-Fenton processes with two chelating agents, nitrilotriacetic acid (NTA) and [S,S]-ethylenediamine-N,N'-disuccinic acid ([S,S]-EDDS), for the treatment of oil sands process-affected water (OSPW) at natural pH was investigated. The half-wave potentials of Fe(III/II)NTA and Fe(III/II)EDDS and the UV photolysis of the complexes in Milli-Q water and OSPW were compared. Under optimum conditions, UV-NTA-Fenton exhibited higher efficiency than UV-EDDS-Fenton in the removal of acid extractable organic fraction (66.8% for the former and 50.0% for the latter) and aromatics (93.5% for the former and 74.2% for the latter). Naphthenic acids (NAs) removals in the UV-NTA-Fenton process (98.4%, 86.0%, and 81.0% for classical NAs, NAs + O (oxidized NAs with one additional oxygen atom), and NAs + 2O (oxidized NAs with two additional oxygen atoms), respectively) under the experimental conditions were much higher than those in the UV-H 2 O 2 (88.9%, 48.7%, and 54.6%, correspondingly) and NTA-Fenton (69.6%, 35.3%, and 44.2%, correspondingly) processes. Both UV-NTA-Fenton and UV-EDDS-Fenton processes presented promoting effect on the acute toxicity of OSPW toward Vibrio fischeri. No significant change of the NTA toxicity occurred during the photolysis of Fe(III)NTA; however, the acute toxicity of EDDS increased as the photolysis of Fe(III)EDDS proceeded. NTA is a much better agent than EDDS for the application of UV-Fenton process in the treatment of OSPW.

Updates to In-Line Calculation of Photolysis Rates

EPA Science Inventory

How photolysis rates are calculated affects ozone and aerosol concentrations predicted by the CMAQ model and the model?s run-time. The standard configuration of CMAQ uses the inline option that calculates photolysis rates by solving the radiative transfer equation for the needed ...

Photolysis of aromatic pollutants in clean and dirty ice

NASA Astrophysics Data System (ADS)

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.

Fulvic Acid Mediated Photolysis of Ibuprofen in Water.

EPA Science Inventory

Photolysis of the nonsteroidal anti-inflammatory drug ibuprofen was studied in solutions of fulvic acid (FA) isolated from Pony Lake, Antarctica; Suwannee River, GA, USA; and Old Woman Creek, OH, USA. At an initial concentration of 10 µM ibuprofen degrades by direct photolysis...

The near-UV absorber OSSO and its isomers.

PubMed

Wu, Zhuang; Wan, Huabin; Xu, Jian; Lu, Bo; Lu, Yan; Eckhardt, André K; Schreiner, Peter R; Xie, Changjian; Guo, Hua; Zeng, Xiaoqing

2018-05-01

Disulfur dioxide, OSSO, has been proposed as the enigmatic "near-UV absorber" in the yellowish atmosphere of Venus. However, the fundamentally important spectroscopic properties and photochemistry of OSSO are scarcely documented. By either condensing gaseous SO or 266 laser photolysis of an S2O2 complex in Ar or N2 at 15 K, syn-OSSO, anti-OSSO, and cyclic OS([double bond, length as m-dash]O)S were identified by IR and UV/Vis spectroscopy for the first time. The observed absorptions (λmax) for OSSO at 517 and 390 nm coincide with the near-UV absorption (320-400 nm) found in the Venus clouds by photometric measurements with the Pioneer Venus orbiter. Subsequent UV light irradiation (365 nm) depletes syn-OSSO and anti-OSSO and yields a fourth isomer, syn-OSOS, with concomitant dissociation into SO2 and elemental sulfur.

Precision of NO2 photolysis rate measurements

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.

1980-01-01

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species

Arsenic oxidation by UV radiation combined with hydrogen peroxide.

PubMed

Sorlini, S; Gialdini, F; Stefan, M

2010-01-01

Arsenic is a widespread contaminant in the environment around the world. The most abundant species of arsenic in groundwater are arsenite [As(III)] and arsenate [As(V)]. Several arsenic removal processes can reach good removal yields only if arsenic is present as As(V). For this reason it is often necessary to proceed with a preliminary oxidation of As(III) to As(V) prior to the removal technology. Several studies have focused on arsenic oxidation with conventional reagents and advanced oxidation processes. In the present study the arsenic oxidation was evaluated using hydrogen peroxide, UV radiation and their combination in distilled and in real groundwater samples. Hydrogen peroxide and UV radiation alone are not effective at the arsenic oxidation. Good arsenic oxidation yields can be reached in presence of hydrogen peroxide combined with a high UV radiation dose (2,000 mJ/cm(2)). The quantum efficiencies for As(III) oxidation were calculated for both the UV photolysis and the UV/H(2)O(2) processes.

Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

PubMed

Ulliman, Sydney L; McKay, Garrett; Rosario-Ortiz, Fernando L; Linden, Karl G

2018-03-01

While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H 2 O 2 (UV 254  + H 2 O 2  + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H 2 O 2 systems. The effects of iron species (Fe 2+ and Fe 3+ ), iron concentration (0-0.3 mg/L), H 2 O 2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H 2 O 2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H 2 O 2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H 2 O 2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lifetimes and reactivities of some 1,2-didehydroazepines commonly used in photoaffinity labeling experiments in aqueous solutions.

PubMed

Rizk, Mary S; Shi, Xiaofeng; Platz, Matthew S

2006-01-17

The reactive 1,2-didehydroazepine (cyclic ketenimine) intermediates produced upon photolysis of phenyl azide, 3-hydroxyphenyl azide, 3-methoxyphenyl azide, and 3-nitrophenyl azide in water and in HEPES buffer were studied by laser flash photolysis techniques with UV-vis detection of the transient intermediates. The lifetimes of the 1,2-didehydroazepines were obtained along with the absolute rate constants of their reactions with typical amino acids, nucleosides, and other simple reagents present in a biochemical milieu. The nitro substituent greatly accelerates the bimolecular reactions of the cyclic ketenimines, and the 3-methoxy group greatly decelerates the absolute reactivity of 1,2-didehydroazepines. The intermediate produced by photolysis of 3-hydroxyphenyl azide is much more reactive than the intermediate produced by photolysis of 3-methoxyphenyl azide. We propose that the hydroxyl-substituted 1,2-didehydoazepines rapidly (<10 micros) tautomerize in water to form azepinones and much more rapidly than the corresponding 3-methoxy-substituted cyclic ketenimines undergo hydrolysis. Azepinones react more rapidly with nucleophiles than do methoxy-substituted 1,2-didehydroazepines and are the active species present upon the photolysis of 3-hydroxyphenyl azide in aqueous solution.

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm

NASA Technical Reports Server (NTRS)

Brock, J. C.; Watson, R. T.

1980-01-01

The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.

Hot Flashes

MedlinePlus

... report menopausal hot flashes than do women of European descent. Hot flashes are less common in women of Japanese and Chinese descent than in white European women. Complications Nighttime hot flashes (night sweats) can ...

UV-Light Exposure of Insulin: Pharmaceutical Implications upon Covalent Insulin Dityrosine Dimerization and Disulphide Bond Photolysis

PubMed Central

Correia, Manuel; Neves-Petersen, Maria Teresa; Jeppesen, Per Bendix; Gregersen, Søren; Petersen, Steffen B.

2012-01-01

In this work we report the effects of continuous UV-light (276 nm, ∼2.20 W.m−2) excitation of human insulin on its absorption and fluorescence properties, structure and functionality. Continuous UV-excitation of the peptide hormone in solution leads to the progressive formation of tyrosine photo-product dityrosine, formed upon tyrosine radical cross-linkage. Absorbance, fluorescence emission and excitation data confirm dityrosine formation, leading to covalent insulin dimerization. Furthermore, UV-excitation of insulin induces disulphide bridge breakage. Near- and far-UV-CD spectroscopy shows that UV-excitation of insulin induces secondary and tertiary structure losses. In native insulin, the A and B chains are held together by two disulphide bridges. Disruption of either of these bonds is likely to affect insulin’s structure. The UV-light induced structural changes impair its antibody binding capability and in vitro hormonal function. After 1.5 and 3.5 h of 276 nm excitation there is a 33.7% and 62.1% decrease in concentration of insulin recognized by guinea pig anti-insulin antibodies, respectively. Glucose uptake by human skeletal muscle cells decreases 61.7% when the cells are incubated with pre UV-illuminated insulin during 1.5 h. The observations presented in this work highlight the importance of protecting insulin and other drugs from UV-light exposure, which is of outmost relevance to the pharmaceutical industry. Several drug formulations containing insulin in hexameric, dimeric and monomeric forms can be exposed to natural and artificial UV-light during their production, packaging, storage or administration phases. We can estimate that direct long-term exposure of insulin to sunlight and common light sources for indoors lighting and UV-sterilization in industries can be sufficient to induce irreversible changes to human insulin structure. Routine fluorescence and absorption measurements in laboratory experiments may also induce changes in protein

UV-light exposure of insulin: pharmaceutical implications upon covalent insulin dityrosine dimerization and disulphide bond photolysis.

PubMed

Correia, Manuel; Neves-Petersen, Maria Teresa; Jeppesen, Per Bendix; Gregersen, Søren; Petersen, Steffen B

2012-01-01

In this work we report the effects of continuous UV-light (276 nm, ~2.20 W.m(-2)) excitation of human insulin on its absorption and fluorescence properties, structure and functionality. Continuous UV-excitation of the peptide hormone in solution leads to the progressive formation of tyrosine photo-product dityrosine, formed upon tyrosine radical cross-linkage. Absorbance, fluorescence emission and excitation data confirm dityrosine formation, leading to covalent insulin dimerization. Furthermore, UV-excitation of insulin induces disulphide bridge breakage. Near- and far-UV-CD spectroscopy shows that UV-excitation of insulin induces secondary and tertiary structure losses. In native insulin, the A and B chains are held together by two disulphide bridges. Disruption of either of these bonds is likely to affect insulin's structure. The UV-light induced structural changes impair its antibody binding capability and in vitro hormonal function. After 1.5 and 3.5 h of 276 nm excitation there is a 33.7% and 62.1% decrease in concentration of insulin recognized by guinea pig anti-insulin antibodies, respectively. Glucose uptake by human skeletal muscle cells decreases 61.7% when the cells are incubated with pre UV-illuminated insulin during 1.5 h. The observations presented in this work highlight the importance of protecting insulin and other drugs from UV-light exposure, which is of outmost relevance to the pharmaceutical industry. Several drug formulations containing insulin in hexameric, dimeric and monomeric forms can be exposed to natural and artificial UV-light during their production, packaging, storage or administration phases. We can estimate that direct long-term exposure of insulin to sunlight and common light sources for indoors lighting and UV-sterilization in industries can be sufficient to induce irreversible changes to human insulin structure. Routine fluorescence and absorption measurements in laboratory experiments may also induce changes in protein

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

PubMed

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

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

NASA Astrophysics Data System (ADS)

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

Photolysis study of octyl p-methoxycinnamate loaded microemulsion by molecular fluorescence and chemometric approach

NASA Astrophysics Data System (ADS)

Nascimento, Danielle Silva; Insausti, Matías; Band, Beatriz Susana Fernández; Grünhut, Marcos

2018-02-01

Octyl p-methoxycinnamate (OMC) is one of the most widely used sunscreen agents. However, the efficiency of OMC as UV filter over time is affected due to the formation of the cis-isomer which presents a markedly lower extinction coefficient (εcis = 12,600 L mol- 1 cm- 1 at 291 nm) than the original trans-isomer (εtrans = 24,000 L mol- 1 cm- 1 at 310 nm). In this work, a novel carrier for OMC based on an oil-in-water microemulsion is proposed in order to improve the photostability of this sunscreen. The formulation was composed of 29.2% (w/w) of a 3:1 mixture of ethanol (co-surfactant) and decaethylene glycol mono-dodecyl ether (surfactant), 1.5% (w/w) of oleic acid (oil phase) and 69.2% (w/w) of water. This microemulsion was prepared in a simple way, under moderate stirring at 25 °C and using acceptable, biocompatible and accessible materials for topical use. OMC was incorporated in the vehicle at a final concentration of 5.0% (w/w), taking into account the maximum permitted levels established by international norms. Then, a photolysis study of the loaded formulation was performed using a continuous flow system. The direct photolysis was monitored over time by molecular fluorescence. The recorded spectra data between 370 y 490 nm were analyzed by multivariate curve resolution-alternating least squares algorithm. The kinetic rate constants corresponding to the photolysis of the trans-OMC were calculated from the concentration profiles, resulting in 0.0049 s- 1 for the trans-OMC loaded microemulsion and 0.0131 s- 1 for the trans-OMC in aqueous media. These results demonstrate a higher photostability of the trans-OMC when loaded in the proposed vehicle with respect to the free trans-OMC in aqueous media.

Photolysis study of octyl p-methoxycinnamate loaded microemulsion by molecular fluorescence and chemometric approach.

PubMed

Nascimento, Danielle Silva; Insausti, Matías; Band, Beatriz Susana Fernández; Grünhut, Marcos

2018-02-15

Octyl p-methoxycinnamate (OMC) is one of the most widely used sunscreen agents. However, the efficiency of OMC as UV filter over time is affected due to the formation of the cis-isomer which presents a markedly lower extinction coefficient (ε cis =12,600L mol -1 cm -1 at 291nm) than the original trans-isomer (ε trans =24,000L mol -1 cm -1 at 310nm). In this work, a novel carrier for OMC based on an oil-in-water microemulsion is proposed in order to improve the photostability of this sunscreen. The formulation was composed of 29.2% (w/w) of a 3:1 mixture of ethanol (co-surfactant) and decaethylene glycol mono-dodecyl ether (surfactant), 1.5% (w/w) of oleic acid (oil phase) and 69.2% (w/w) of water. This microemulsion was prepared in a simple way, under moderate stirring at 25°C and using acceptable, biocompatible and accessible materials for topical use. OMC was incorporated in the vehicle at a final concentration of 5.0% (w/w), taking into account the maximum permitted levels established by international norms. Then, a photolysis study of the loaded formulation was performed using a continuous flow system. The direct photolysis was monitored over time by molecular fluorescence. The recorded spectra data between 370 y 490nm were analyzed by multivariate curve resolution-alternating least squares algorithm. The kinetic rate constants corresponding to the photolysis of the trans-OMC were calculated from the concentration profiles, resulting in 0.0049s -1 for the trans-OMC loaded microemulsion and 0.0131s -1 for the trans-OMC in aqueous media. These results demonstrate a higher photostability of the trans-OMC when loaded in the proposed vehicle with respect to the free trans-OMC in aqueous media. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface studies of low molecular weight photolysis products from UV-ozone oxidised polystyrene

NASA Astrophysics Data System (ADS)

Davidson, M. R.; Mitchell, S. A.; Bradley, R. H.

2005-05-01

The production of low molecular weight oxidised material during UV-ozone treatment of polystyrene has been studied by XPS, GC-MS, FTIR and UV/visible spectroscopy. XPS analysis of the oxidised polystyrene surfaces before and after washing with water or methanol indicates that the removal of oxidation products and the surface that remains after washing is strongly dependent on the choice of solvent. Methanol washing removes a greater proportion of the more highly oxidised carbonyl and carboxyl groups resulting in a surface with a lower oxygen content than that remaining after water washing. Extended exposure to UV-ozone treatment reveals a two-stage oxidation process with mono-substituted benzene rings such as benzaldehyde, acetophenone and benzoic acid being produced at exposure times less than 15 min. Compounds, more typical of those formed via dehydration reactions of existing oxidised species, are produced at longer exposure times. UV-visible spectroscopy and Fourier transform infrared spectroscopy also confirm the presence of carboxylic acid, aromatic ketones and esters. Measurements of water contact angle on a 10 min treated surface reveals that methanol washing produces a more hydrophilic surface than water washing, the resulting water contact angles being 47° and 62° respectively. Ageing of methanol washed surfaces for 24 h leads to a recovery of the water contact angle back to 62° which suggests some form of post-washing surface relaxation process. Since XPS analyses show no increase in the oxygen concentration of the methanol washed surfaces after a 24 h ageing period, the increase in contact angle found with ageing is attributed to the reorientation of very near-surface functional groups i.e. within the XPS sampling depth.

Controlled On-chip Stimulation of Quantal Catecholamine Release from Chromaffin Cells Using Photolysis of Caged Ca2+ on Transparent Indium-Tin-Oxide Microchip Electrodes

PubMed Central

Chen, Xiaohui; Gao, Yuanfang; Hossain, Maruf; Gangopadhyay, Shubhra; Gillis, Kevin D.

2008-01-01

Photorelease of caged Ca2+ is a uniquely powerful tool to study the dynamics of Ca2+-triggered exocytosis from individual cells. Using photolithography and other microfabrication techniques, we have developed transparent microchip devices to enable photorelease of caged Ca2+ together with electrochemical detection of quantal catecholamine secretion from individual cells or cell arrays as a step towards developing high-throughput experimental devices. A 100 nm - thick transparent Indium-Tin-Oxide (ITO) film was sputter-deposited onto glass coverslips, which were then patterned into 24 cell-sized working electrodes (∼20 μm by 20 μm). We loaded bovine chromaffin cells with acetoxymethyl (AM) ester derivatives of the Ca2+ cage NP-EGTA and Ca2+ indicator dye Fura-4F, then transferred these cells onto the working ITO electrodes for amperometric recordings. Upon flash photorelease of caged Ca2+, a uniform rise of [Ca2+]i within the target cell leads to quantal release of oxidizable catecholamines measured amperometrically by the underlying ITO electrode. We observed a burst of amperometric spikes upon rapid elevation of [Ca2+]i and a “priming” effect of sub-stimulatory [Ca2+]i on the response of cells to subsequent [Ca2+]i elevation, similar to previous reports using different techniques. We conclude that UV photolysis of caged Ca2+ is a suitable stimulation technique for higher-throughput studies of Ca2+-dependent exocytosis on transparent electrochemical microelectrode arrays. PMID:18094774

UV and solar photo-degradation of naproxen: TiO₂ catalyst effect, reaction kinetics, products identification and toxicity assessment.

PubMed

Jallouli, Nabil; Elghniji, Kais; Hentati, Olfa; Ribeiro, Ana R; Silva, Adrián M T; Ksibi, Mohamed

2016-03-05

Direct photolysis and TiO2-photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pHinitial 6.5) was 83% after 3h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO2-UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant (kapp) for NPX degradation by photolysis ranged from 0.0050 min(-1) at pH 3.5 to 0.0095 min(-1) at pH 6.5, while it was estimated to be 0.0063 min(-1) under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of UV dose on the UV/H2O2 process for the degradation of carbamazepine in wastewater.

PubMed

Somathilake, Purnima; Dominic, John Albino; Achari, Gopal; Langford, Cooper H; Tay, Joo-Hwa

2018-05-02

This study evaluates the influence of UV dose on degradation of carbamazepine (CBZ) in wastewater under UV-C (λ = 254 nm) photolysis with and without H 2 O 2 . The rate of degradation of CBZ exhibited a direct dependence on the intensity of incident UV irradiation as the rate of degradation was observed to increase linearly (R 2  = 0.98) with UV intensity between 1.67 and 8.95 × 10 17 photons/s. More than 95% of the CBZ that spiked in wastewater rapidly degraded within 4 min with a first-order rate constant of 1.2 min -1 for an optimum H 2 O 2 dose of 100 mg/L. Bench-scale continuous flow reactor experiments also showed that CBZ degraded with first-order kinetics at a rate constant of 1.02 min -1 . The kinetic parameters obtained for a continuous bench-scale reactor were in good agreement with the relationships developed through batch experiments with only a marginal deviation of ± 6.5%. The relationship between UV intensity and CBZ degradation rate obtained in this study was extrapolated to the UV disinfection unit of a wastewater treatment plant to predict possible degradation of CBZ during UV disinfection. The addition of 100 mg/L of H 2 O 2 to the secondary-treated effluent entering the UV disinfection unit is predicted to achieve over 60% degradation of CBZ.

Increased formation of halomethanes during chlorination of chloramphenicol in drinking water by UV irradiation, persulfate oxidation, and combined UV/persulfate pre-treatments.

PubMed

Wenhai, Chu; Tengfei, Chu; Erdeng, Du; Deng, Yang; Yingqing, Guo; Naiyun, Gao

2016-02-01

Ultraviolet/persulfate (UV/PS) has been widely used to generate sulfate radicals for degradation of water organic pollutants in previous studies. However, its impacts on disinfection byproduct formation during post-chlorination of degraded compounds is unclear. The objective of this study was to evaluate the impacts of UV irradiation, PS oxidation, and the combined UV/PS advanced oxidation process (AOP) pre-treatments on halomethane formation during the following chlorination of chloramphenicol (CAP), a model antibiotic commonly found in wastewater-impacted water. Results showed that CAP could be transformed to more trichloromethane (TCM) than monochloromethane (MCM) and dichloromethane (DCM) in the presence of excess chlorine. UV photolysis, PS oxidation and UV/PS AOP all directly decomposed CAP to produce halomethanes (HMs) before post-chlorination. Moreover, UV and UV/PS pre-treatments both enhanced the formation of all the HMs in the subsequent chlorination. PS pre-oxidation decreased the TCM formation during post-chlorination, but increased the yields of MCM, DCM and total HMs. UV pre-irradiation significantly increased the bromide utilization of HMs, whereas UV/PS pre-oxidation decreased the bromine incorporation and utilization of HMs from the chlorination of CAP in a low-bromide water. UV irradiation, PS oxidation, and UV/PS AOP can inactivate pathogens and degrade organic pollutants, but this benefit should be weighed against a potential risk of the increased halomethane formation from degraded organic pollutants with and without post-chlorination. Copyright © 2015 Elsevier Inc. All rights reserved.

Flash Mixing of the White Dwarf Cooling Curve Spectroscopic Confirmation in NGC 2808

NASA Technical Reports Server (NTRS)

Brown, Thomas M.; Lanz, Thierry; Sweigart, Allen V.; Cracraft, Misty; Hubeny, Ivan; Landsman, Wayne B.

2009-01-01

We present new HST far-UV spectroscopy of two dozen hot evolved stars in NGC 2808, a massive globular cluster with a large population of "blue-hook" stars. The blue-hook stars are found in ultraviolet color-magnitude diagrams of the most massive globular clusters, where they fall at luminosities immediately below the hot end of the horizontal branch (HB), in a region of the HR diagram unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that these subluminous HB stars are very likely the progeny of stars that undergo extensive internal mixing during a late He-core flash on the white dwarf cooling curve. This flash mixing leads to hotter temperatures and an enormous enhancement of the surface He and C abundances; the hotter temperatures and associated decrease in the hydrogen opacity shortward of the Lyman limit makes the stars brighter in the extreme UV but appear sub luminous in the UV and optical. Our far-UV spectroscopy demonstrates that, relative to normal HB stars at the same color, the blue-hook stars of NGC 2808 are hotter and greatly enhanced in He and C, thus providing unambiguous evidence of flash mixing in the subluminous population. Although the C abundance in the blue-hook stars is orders of magnitude larger than that in the normal HB stars, the atmospheric C abundance in both the blue-hook and normal HB stars appears to be affected by gravitational settling. The abundance variations seen in C, Si, and the Fe-peak elements indicate that atmospheric diffusion is at play in our sample, with all of our hot subdwarfs at 25,000 K to 50,000 K exhibiting large enhancements of the iron-peak elements. The hottest subdwarfs in our blue-hook sample may be pulsators, given that they fall in the temperature range of newly-discovered pulsating subdwarfs in omega Cen.

Effect of Wildfire Aerosols on NO2 Photolysis and Ozone Production at the Mt. Bachelor Observatory

NASA Astrophysics Data System (ADS)

Baylon, P.; Jaffe, D. A.; Hall, S. R.; Ullmann, K.; Lefer, B. L.

2015-12-01

In this study, we have two goals: to quantify the effect of biomass burning aerosols on jNO2 photolysis and to look at O3 formation in biomass burning plumes as it relates to jNO2 photolysis. Wildfire plumes were observed during the summer of 2015 at the Mt. Bachelor Observatory, a high-elevation (2.8 km a.s.l.) mountaintop site located in central Oregon. These plumes were identified using the following criteria: (1) 5-minute ambient aerosol scattering σsp ≥ 20 Mm-1 for at least two hours, (2) 5-minute CO ≥ 150 ppbv for at least two hours, (3) strong correlation (r2 ≥ 0.70) between σsp and CO, and (4) consistent air mass back trajectories indicating transport over known fire locations. We measure nitrogen oxides using a chemiluminescence detector and jNO2 photolysis using a diode array actinic flux spectroradiometer. We also measure O3 using two techniques: (a) UV method with a cavity ring-down spectrometer and (b) chemiluminescence method with a custom-made instrument. We compare fire event observations between these two procedures to prove consistency. Based on these measurements, we quantify a lower bound for the HO2 and RO2 radical concentrations in wildfire plumes. We then look at plume and non-plume data and examine deviations from the photostationary state. Finally, we use the TUV model v5.2 to simulate clear-sky conditions and therefore quantify the reduction/enhancement in jNO2 values and O3 production due to wildfire aerosols. This gives us insight into the photochemical environment in biomass burning plumes, which until now, remains poorly understood.

Laser photolysis of DPNI-GABA, a tool for investigating the properties and distribution of GABA receptors and for silencing neurons in situ.

PubMed

Trigo, Federico F; Papageorgiou, George; Corrie, John E T; Ogden, David

2009-07-30

Laser photolysis to release GABA at precisely defined times and locations permits investigation of the distribution of functional GABA(A) receptors in neuronal compartments, the activation kinetics and pharmacology of GABA(A) receptors in situ, and the role of individual neurons in neural circuits by selective silencing with low GABA concentrations. We describe the experimental evaluation and applications of a new nitroindoline-caged GABA, DPNI-GABA, modified to minimize the pharmacological interference commonly found with caged GABA reagents, but retaining the advantages of nitroindoline cages. Unlike the 5-methoxycarbonylmethyl-7-nitroindolinyl-GABA tested previously, DPNI-GABA inhibited GABA(A) receptors with much lower affinity, reducing peak GABA-evoked responses with an IC(50) of approximately 0.5 mM. Most importantly, the kinetics of receptor activation, determined as 10-90% rise-times, were comparable to synaptic events and were little affected by DPNI-GABA present at 1mM concentration, permitting photolysis of DPNI-GABA to mimic synaptic activation of GABA(A) receptors. With a laser spot of 1 microm applied to cerebellar molecular layer interneurons, the spatial resolution of uncaging DPNI-GABA in dendrites was estimated as 2 microm laterally and 7.5 microm focally. Finally, at low DPNI-GABA concentration, photorelease restricted to the area of the soma suppressed spiking in single Purkinje neurons or molecular layer interneurons for periods controlled by the flash intensity and duration. DPNI-GABA has properties better adapted for fast kinetic studies with laser photolysis at GABA(A) receptors than previously reported caged GABA reagents, and can be used in experiments where spatial resolution is determined by the dimensions of the laser light spot.

Optimal flash rate and duty cycle for flashing visual indicators.

NASA Technical Reports Server (NTRS)

Markowitz, J.

1971-01-01

This experiment examined the ability of observers to determine, as quickly as possible, whether a visual indicator was steadily on or flashing. Six flash rates (periods) were combined factorially with three duty cycles (on-off ratios) to define 18 ?types' of intermittent signals. Experimental sessions were divided into six runs of 100 trials, each run utilizing one of the six flash rates. On any given trial in a run, the probability of a steady signal occurring was 0.5 and the probability of a flashing signal occurring was 0.5. A different duty cycle was employed daily for each experimental session. In all, 400 trials were devoted to each of the flash rates at each duty cycle. Accuracy and latency of response were the dependent variables of interest. The results show that the observers view the light for an interval of time appropriate to the expected flash rate and duty cycle; whether they judge the light to be steady or intermittent depends upon whether the light is extinguished during the predetermined waiting period. Adoption of this temporal criterion delays responding in comparison to those tasks involving responses to light onset. The decision or response criteria held by the observers are also sensitive to the parameters of the flashing light: observers become increasingly willing to call a flashing light ?steady' as flash duration increases.

Photophysical properties of C60 colloids suspended in water with Triton X-100 surfactant: excited-state properties with femtosecond resolution.

PubMed

Clements, Andrew F; Haley, Joy E; Urbas, Augustine M; Kost, Alan; Rauh, R David; Bertone, Jane F; Wang, Fei; Wiers, Brian M; Gao, De; Stefanik, Todd S; Mott, Andrew G; Mackie, David M

2009-06-11

We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.

NAND FLASH Radiation Tolerant Intelligent Memory Stack (RTIMS FLASH)

NASA Astrophysics Data System (ADS)

Sellier, Charles; Wang, Pierre

2014-08-01

The NAND Flash Radiation Tolerant and Intelligent Memory Stack (RTIMS FLASH) is a User's Friendly, Plug-and- Play and Radiation Protected high density NAND Flash Memory. It provides a very high density, radiation hardened by design and non-volatile memory module suitable for all space applications such as commercial or scientific geo-stationary missions, earth observation, navigation, manned space vehicles and deep space scientific exploration. The Intelligent Memory Module embeds a very high density of non-volatile NAND Flash memory and one Intelligent Flash Memory Controller (FMC). The FMC provides the module with a full protection against the radiation effects such as SEL, SEFI and SEU. It's also granting the module with bad block immunity as well as high level service functions that will benefit to the user's applications.

Sulfur mass-independent fractionation during photolysis and photoexcitation of SO2 and CS2 and implications to the source reactions for Archean sulfur isotope anomaly

NASA Astrophysics Data System (ADS)

Ono, S.; Whitehill, A. R.; Oduro, H. D.

2012-12-01

Signatures of sulfur mass-independent fractionations (S-MIF) in Archean sedimentary rocks provide critical constraints on the atmospheric oxygen level of an early atmosphere and documents fundamental difference in early sulfur biogeochemical cycle from that of today. Archcean sulfide and sulfate minerals often yield correlated relationships among δ34S, Δ33S and Δ36S values. Our goal is to use this S-MIF pattern to pinpoint the S-MIF source reaction(s), and to constrain early atmospheric conditions beyond the oxygen level. Such an effort may lead to a new hypothesis about the cause of the Great Oxidation Event at 2.4 Billion years ago. We will present new results of laboratory photochemical experiments that are designed to calibrate the pattern of S-MIF during the photochemistry of SO2 and CS2 as a function of UV spectrum regions, partial pressure of SO2 and CS2 (0.1 mbar and above) and total N2 pressure (0.25 to 1.0 bar). Both SO2 and CS2 exhibit high energy absorption band (190 to 220 nm) that leads to direct photolysis (SO2 → SO + O or CS2 → CS + S), and low energy band (>240 nm for SO2 and 280 nm for CS2) that excites molecules to low lying electronic states under dissociation thresholds. Broadband UV light sources (Xenon or Deuterium arc lamps) are used in combination with a series of bandpass (200±35 nm), longpass (250 or 280 nm) filters to isolate specific electronic transitions. Excited state SO2 is trapped by acetylene and excited state CS2 polymerizes in the reactor, and are collected for sulfur isotope ratio analysis. Although SO2 photolysis under 190 to 220 nm is thought to be the main Archean S-MIF source reaction, its S-MIF is characterized by high δ34S values (up to 140 ‰) and relatively low Δ36S/Δ33S values (-3.3 to -5.9) compared to Archean data (-0.9 to -1.5). Strong pSO2 dependence suggests S-MIF is primarily due to isotopologue self-shielding at least under our experimental conditions. In contrast, SO2 photoexciation under >250 nm

Degradation of sulfamethoxazole by UV, UV/H2O2 and UV/persulfate (PDS): Formation of oxidation products and effect of bicarbonate.

PubMed

Yang, Yi; Lu, Xinglin; Jiang, Jin; Ma, Jun; Liu, Guanqi; Cao, Ying; Liu, Weili; Li, Juan; Pang, Suyan; Kong, Xiujuan; Luo, Congwei

2017-07-01

The frequent detection of sulfamethoxazole (SMX) in wastewater and surface waters gives rise of concerns about their ecotoxicological effects and potential risks to induce antibacterial resistant genes. UV/hydrogen peroxide (UV/H 2 O 2 ) and UV/persulfate (UV/PDS) advanced oxidation processes have been demonstrated to be effective for the elimination of SMX, but there is still a need for a deeper understanding of product formations. In this study, we identified and compared the transformation products of SMX in UV, UV/H 2 O 2 and UV/PDS processes. Because of the electrophilic nature of SO 4 - , the second-order rate constant for the reaction of sulfate radical (SO 4 - ) with the anionic form of SMX was higher than that with the neutral form, while hydroxyl radical (OH) exhibited comparable reactivity to both forms. The direct photolysis of SMX predominately occurred through cleavage of the NS bond, rearrangement of the isoxazole ring, and hydroxylation mechanisms. Hydroxylation was the dominant pathway for the reaction of OH with SMX. SO 4 - favored attack on NH 2 group of SMX to generate a nitro derivative and dimeric products. The presence of bicarbonate in UV/H 2 O 2 inhibited the formation of hydroxylated products, but promoted the formation of the nitro derivative and the dimeric products. In UV/PDS, bicarbonate increased the formation of the nitro derivative and the dimeric products, but decreased the formation of the hydroxylated dimeric products. The different effect of bicarbonate on transformation products in UV/H 2 O 2 vs. UV/PDS suggested that carbonate radical (CO 3 - ) oxidized SMX through the electron transfer mechanism similar to SO 4 - but with less oxidation capacity. Additionally, SO 4 - and CO 3 - exhibited higher reactivity to the oxazole ring than the isoxazole ring of SMX. Ecotoxicity of transformation products was estimated by ECOSAR program based on the quantitative structure-activity relationship analysis as well as by experiments using

pH induced polychromatic UV treatment for the removal of a mixture of SMX, OTC and CIP from water.

PubMed

Avisar, D; Lester, Y; Mamane, H

2010-03-15

Water and wastewater effluents contain a vast range of chemicals in mixtures that have different chemical structures and characteristics. This study presents a treatment technology for the removal of mixtures of antibiotic residues (sulfamethoxazole (SMX), oxytetracycline (OTC) and ciprofloxacin (CIP)) from contaminated water. The treatment combines pH modification of the water to an optimal value, followed by a photolytic treatment using direct polychromatic ultraviolet (UV) irradiation by medium pressure UV lamp. The pH adjustment of the treated water leads to structural modifications of the pollutant's molecule thus may enhance direct photolysis by UV light. Results showed that an increase of water pH from 5 to 7 leads to a decrease in degradation rate of SMX and an increase in degradation rate of OTC and CIP, when studied separately and not in a mixture. Thus, the optimal pH values for UV photodegradation in a mixture, involve initial photolysis at pH 5 and then gradually changing the pH from 5 to 7 during the UV exposure. For example, this resulted in 99% degradation of SMX at pH 5 and enhanced degradation of OTC and CIP from 54% and 26% to 91% and 96% respectively when pH was increased from 5 to 7. Thus the pH induced photolytic treatment has a potential in improving treatment of antibiotics in mixtures. (c) 2009 Elsevier B.V. All rights reserved.

UV Absorption Cross Sections of Nitrous Oxide (N2O) and Carbon Tetrachloride (CCl4) Between 210 and 350 K and the Atmospheric Implications

NASA Technical Reports Server (NTRS)

Carlon, Nabilah Rontu; Papanastasiou, Dimitrios K.; Fleming, Eric L.; Jackman, Charles H.; Newman, Paul A.; Burkholder, James B.

2010-01-01

Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at 27 temperatures in the range 210-350 K. In addition, UV absorption spectra of CCl4 are reported between 200-235 nm as a function of temperature (225-350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5-7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in 37 atmospheric model calculations is presented.

Soft Ultraviolet (UV) Photopatterning and Metallization of Self-Assembled Monolayers (SAMs) Formed from the Lipoic Acid Ester of α-Hydroxy-1-acetylpyrene: The Generality of Acid-Catalyzed Removal of Thiol-on-Gold SAMs using Soft UV Light.

PubMed

Pukenas, Laurynas; Prompinit, Panida; Nishitha, Boda; Tate, Daniel J; Singh, N D Pradeep; Wälti, Christoph; Evans, Stephen D; Bushby, Richard J

2017-05-31

Under a layer of 0.1 M HCl in isopropanol, soft ultraviolet (UV) (365 nm) photolysis of the thiol-on-gold self-assembled monolayer (SAM) derived from the lipoic acid ester of α-hydroxy-1-acetylpyrene results in the expected removal of the acetylpyrene protecting group. When photolyzing through a mask, this can be used to produce a patterned surface and, at a controlled electrochemical potential, it is then possible to selectively and reversibly electrodeposit copper on the photolyzed regions. Rather surprisingly, under these photolysis conditions, there is not only the expected photodeprotection of the ester but also partial removal of the lipoic acid layer which has been formed. In further studies, it is shown that this type of acid-catalyzed photoremoval of SAM layers by soft UV is a rather general phenomenon and results in the partial removal of the thiol-on-gold SAM layers derived from other ω-thiolated carboxylic acids. However, this phenomenon is chain-length dependent. Under conditions in which there is a ∼60% reduction in the thickness of the SAM derived from dithiobutyric acid, the SAM derived from mercaptoundecanoic acid is almost unaffected. The process by which the shorter-chain SAM layers are partially removed is not fully understood because these compounds do not absorb significantly in the 365 nm region of the spectrum! Significantly, this study shows that acid catalysis photolysis of thiol-on-gold SAMs needs to be used with caution.

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

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

Berhanu, Tesfaye A.; Erbland, Joseph; 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 ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results frommore » 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

340nm UV LED excitation in time-resolved fluorescence system for europium-based immunoassays detection

NASA Astrophysics Data System (ADS)

Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Pedersen, Christian

2017-02-01

In immunoassay analyzers for in-vitro diagnostics, Xenon flash lamps have been widely used as excitation light sources. Recent advancements in UV LED technology and its advantages over the flash lamps such as smaller footprint, better wall-plug efficiency, narrow emission spectrum, and no significant afterglow, have made them attractive light sources for gated detection systems. In this paper, we report on the implementation of a 340 nm UV LED based time-resolved fluorescence system based on europium chelate as a fluorescent marker. The system performance was tested with the immunoassay based on the cardiac marker, TnI. The same signal-to-noise ratio as for the flash lamp based system was obtained, operating the LED below specified maximum current. The background counts of the system and its main contributors were measured and analyzed. The background of the system of the LED based unit was improved by 39% compared to that of the Xenon flash lamp based unit, due to the LEDs narrower emission spectrum and longer pulse width. Key parameters of the LED system are discussed to further optimize the signal-to-noise ratio and signal-to-background, and hence the sensitivity of the instrument.

[Photodegradation of UV filter PABA in nitrate solution].

PubMed

Meng, Cui; Ji, Yue-Fei; Zeng, Chao; Yang, Xi

2011-09-01

The aqueous photolysis of a UV filter p-aminobenzoic acid (PABA) using Xe lamp as simulated solar irradiation source was investigated in the presence of nitrate ions. The effects of pH, concentration of nitrate ions and concentration of humic substance in natural water on the photodegradation of PABA were studied. The results showed that photodegradation of PABA in nitrate solution followed the first order kinetics. The increasing concentration of nitrate ion increased favored the photodegradaton of PABA, of which the first order constant increased from 0.002 2 min(-10 to 0.017 9 min(-1). The photodegradation of PABA promoted with the increase of pH while the increasing concentration of humic substance showed inhibiting effect. Hydroxyl radicals determined by the molecular probe method played a very importnant role in the photolysis process of PABA. Photoproducts upon irradiation of PABA in nitrate solution were isolated by means of solid-phase extraction (SPE) and identified by LC-MS techniques. The probable photoinduced degradation pathways in nitrate solution were proposed.

FLASH Interface; a GUI for managing runtime parameters in FLASH simulations

NASA Astrophysics Data System (ADS)

Walker, Christopher; Tzeferacos, Petros; Weide, Klaus; Lamb, Donald; Flocke, Norbert; Feister, Scott

2017-10-01

We present FLASH Interface, a novel graphical user interface (GUI) for managing runtime parameters in simulations performed with the FLASH code. FLASH Interface supports full text search of available parameters; provides descriptions of each parameter's role and function; allows for the filtering of parameters based on categories; performs input validation; and maintains all comments and non-parameter information already present in existing parameter files. The GUI can be used to edit existing parameter files or generate new ones. FLASH Interface is open source and was implemented with the Electron framework, making it available on Mac OSX, Windows, and Linux operating systems. The new interface lowers the entry barrier for new FLASH users and provides an easy-to-use tool for experienced FLASH simulators. U.S. Department of Energy (DOE), NNSA ASC/Alliances Center for Astrophysical Thermonuclear Flashes, U.S. DOE NNSA ASC through the Argonne Institute for Computing in Science, U.S. National Science Foundation.

Flash Platform Examination

DTIC Science & Technology

2011-03-01

than would be performed in software”[108]. Uro Tinic, one of the Flash player’s engineers, further clarifies exactly what Flash player 10 hardware...www.adobe.com/products/flashplayer/features/ (Access date: 28 Sep 2009). [109] Uro , T. What Does GPU Acceleration Mean? (online), http...133] Shorten, A. (2009), Design to Development: Flash Catalyst to Flash Builder, In Proceedings of Adobe Max 2009, Los Angeles, CA. 142 DRDC

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

PubMed

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

NASA Astrophysics Data System (ADS)

Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

2015-07-01

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA 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 5 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, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, 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 cloud water and aerosol chemistry.

Tracing nitrogenous disinfection byproducts after medium pressure UV water treatment by stable isotope labeling and high resolution mass spectrometry.

PubMed

Kolkman, Annemieke; Martijn, Bram J; Vughs, Dennis; Baken, Kirsten A; van Wezel, Annemarie P

2015-04-07

Advanced oxidation processes are important barriers for organic micropollutants (e.g., pharmaceuticals, pesticides) in (drinking) water treatment. Studies indicate that medium pressure (MP) UV/H2O2 treatment leads to a positive response in Ames mutagenicity tests, which is then removed after granulated activated carbon (GAC) filtration. The formed potentially mutagenic substances were hitherto not identified and may result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM). In this study we present an innovative approach to trace the formation of disinfection byproducts (DBPs) of MP UV water treatment, based on stable isotope labeled nitrate combined with high resolution mass spectrometry. It was shown that after MP UV treatment of artificial water containing NOM and nitrate, multiple nitrogen containing substances were formed. In total 84 N-DBPs were detected at individual concentrations between 1 to 135 ng/L bentazon-d6 equivalents, with a summed concentration of 1.2 μg/L bentazon-d6 equivalents. The chemical structures of three byproducts were confirmed. Screening for the 84 N-DBPs in water samples from a full-scale drinking water treatment plant based on MP UV/H2O2 treatment showed that 22 of the N-DBPs found in artificial water were also detected in real water samples.

Flashes and Floaters.

PubMed

Sharma, Priya; Sridhar, Jayanth; Mehta, Sonia

2015-09-01

Flashes and floaters are common ocular complaints. Flashes refer to aberrations of light that are seen in a patient's field of gaze. The flashes can be of varying sizes, colors, frequency, and durations, depending on the cause. Floaters are another common visual phenomenon caused by particles or debris in the vitreous gel of the eye that cause shadows and thus visual changes, especially against bright backgrounds and in brightly lit environments. Flashes and floaters can occur individually or together. This article discusses common causes of flashes and floaters to help with the triaging and management of these patients. Copyright © 2015 Elsevier Inc. All rights reserved.

Photolysis of retinol in liposomes and its protection with tocopherol and oxybenzone.

PubMed

Young, A M; Gregoriadis, G

1996-03-01

In this work the stabilities of retinol in methanolic solutions and liposomal suspensions exposed to UV light were compared using absorbance spectroscopy and the ability of alpha-tocopherol and the sunscreen additive, oxybenzone, to reduce the rate of retinol decomposition assessed. Retinol in methanol decolorized almost completely within a few minutes of exposure to a 6 W 350 nm wavelength lamp. From the concentration dependence of the reaction rates it appears that retinol activated by light can decomposed either directly or after collision with a second retinol molecule. Several reaction products are formed. alpha-Tocopherol solutions were unaffected by 350 nm light but they did darken when irradiated with 250 nm wavelength light. Addition of alpha-tocopherol or removal of oxygen from the retinol in methanol solutions reduced only slightly the rates of retinol photolysis. When dispersed in water within liposomes made of equimolar egg phosphatidylcholine (PC) and cholesterol, up to six-fold increases in the decomposition rate of the retinol were observed. The reaction rate could be reduced but only slightly by increasing the ratio of PC to retinol. A mechanism that explains the concentration dependence of the retinol photolysis is that the reduction in reaction rate on diluting the retinol concentration within a given liposome was due to the prevention of the reaction between one light-activated retinol molecule with another within the same liposome. Incorporation of oxybenzone into the liposomes reduced the reaction rates. The results suggested that most of the protection in this case arises through the oxybenzone closet to the light source absorbing the light, thereby preventing it reaching retinol much further into the sample. Incorporation of alpha-tocopherol into the liposomes could also reduce substantially the photolysis rate of co-entrapped retinol. The mechanism of protection in this case appears to be via the tocopherol quenching activated retinol

Hydrogen chemistry - Perspective on experiment and theory. [atmospheric chemistry

NASA Technical Reports Server (NTRS)

Kaufman, F.

1975-01-01

A review is presented of the advantages and limitations of various experimental methods for the investigation of the kinetics of hydrogen chemistry, including classic thermal and photochemical methods and the crossed molecular beam method. Special attention is given to the flash photolysis-resonance fluorescence apparatus developed by Braun et al, in which repetitive vacuum UV flashes result in the photolytic generation of the desired species, and to the discharge-flow technique. The use of various theoretical methods for the selection or elimination of kinetic data is considered in a brief discussion of the rate theory of two-body encounters and recombination-dissociation processes in neutral reactions. Recent kinetic studies of a series of OH reactions and of a major loss process for odd H in the stratosphere are summarized.

The removal of COD and NH3-N from atrazine production wastewater treatment using UV/O3: experimental investigation and kinetic modeling.

PubMed

Jing, Liang; Chen, Bing; Wen, Diya; Zheng, Jisi; Zhang, Baiyu

2018-01-01

In this study, a UV/O 3 hybrid advanced oxidation system was used to remove chemical oxygen demand (COD), ammonia nitrogen (NH 3 -N), and atrazine (ATZ) from ATZ production wastewater. The removal of COD and NH 3 -N, under different UV and O 3 conditions, was found to follow pseudo-first-order kinetics with rate constants ranging from 0.0001-0.0048 and 0.0015-0.0056 min -1 , respectively. The removal efficiency of ATZ was over 95% after 180 min treatment, regardless the level of UV power. A kinetic model was further proposed to simulate the removal processes and to quantify the individual roles and contributions of photolysis, direct O 3 oxidation, and hydroxyl radical (OH·) induced oxidation. The experimental and kinetic modeling results agreed reasonably well with deviations of 12.2 and 13.1% for the removal of COD and NH 3 -N, respectively. Photolysis contributed appreciably to the degradation of ATZ, while OH· played a dominant role for the removal of both COD and NH 3 -N, especially in alkaline environments. This study provides insights into the treatment of ATZ containing wastewater using UV/O 3 and broadens the knowledge of kinetics of ozone-based advanced oxidation processes.

Mass spectrometry of the photolysis of sulfonylurea herbicides in Prairie waters.

PubMed

Headley, John V; Du, Jing-Long; Peru, Kerry M; McMartin, Dena W

2010-01-01

This review of mass spectrometry of sulfonylurea herbicides includes a focus on studies relevant to Canadian Prairie waters. Emphasis is given to data gaps in the literature for the rates of photolysis of selected sulfonylurea herbicides in different water matrices. Specifically, results are evaluated for positive ion electrospray tandem mass spectrometry with liquid chromatography separation for the study of the photolysis of chlorsulfuron, tribenuron-methyl, thifensulfuron-methyl, metsulfuron-methyl, and ethametsulfuron-methyl. LC-MS/MS is shown to be the method of choice for the quantification of sulfonylurea herbicides with instrumental detection limits ranging from 1.3 to 7.2 pg (on-column). Tandem mass spectrometry coupled with the use of authentic standards likewise has proven to be well suited for the identification of transformation products. To date, however, the power of time-of-flight MS and ultrahigh resolution MS has not been exploited fully for the identification of unknown photolysis products. Dissipation of the herbicides under natural sunlight fit pseudo-first-order kinetics with half-life values ranging from 4.4 to 99 days. For simulated sunlight, radiation wavelengths shorter than 400 nm are required to induce significant photolytic reactions. The correlation between field dissipation studies and laboratory photolysis experiments suggests that photolysis is a major pathway for the dissipation of some sulfonylurea herbicides in natural Prairie waters. 2009 Wiley Periodicals, Inc.

Significant role of UV and carbonate radical on the degradation of oxytetracycline in UV-AOPs: Kinetics and mechanism.

PubMed

Liu, Yiqing; He, Xuexiang; Duan, Xiaodi; Fu, Yongsheng; Fatta-Kassinos, Despo; Dionysiou, Dionysios D

2016-05-15

Carbonate radical (CO3(•-)), a selective oxidant, reacts readily with electron-rich compounds through electron transfer and/or hydrogen abstraction. In this study, the role of CO3(•-) in degrading oxytetracycline (OTC) by UV only, UV/H2O2 and UV/persulfate (UV/PS) advanced oxidation processes (AOPs) in the presence of HCO3(-) or CO3(2-) was investigated. For UV only process, the presence of photosensitizers, i.e., nitrate (NO3(-)) and natural organic matter (NOM), had different impacts on OTC degradation, i.e., an enhancing effect by NO3(-) due to the generation of HO(•) and a slight inhibiting effect by NOM possibly due to a light scattering effect. Differently for UV/H2O2 and UV/PS processes, the presence of NO3(-) hardly influenced the destruction of OTC. Generation of CO3(•-) presented a positive role on OTC degradation by UV/NO3(-)/HCO3(-). Such influence was also observed in the two studied AOPs in the presence of both bicarbonate and other natural water constituents. When various natural water samples from different sources were used as reaction matrices, UV only and UV/H2O2 showed an inhibiting effect while UV/PS demonstrated a comparable or even promoting effect in OTC decomposition. After elucidating the potential contribution of UV direct photolysis via excited state OTC* at an elevated reaction pH condition, putative OTC transformation byproducts via CO3(•-) reaction were identified by ultra-high definition accurate-mass quadrupole time-of-flight tandem mass spectrometry (QTOF/MS). Five different reaction pathways were subsequently proposed, including hydroxylation (+16 Da), quinonization (+14 Da), demethylation (-14 Da), decarbonylation (-28 Da) and dehydration (-18 Da). The significant role of UV at high pH and CO3(•-) on OTC removal from contaminated water was therefore demonstrated both kinetically and mechanistically. Copyright © 2016 Elsevier Ltd. All rights reserved.

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

NASA Technical Reports Server (NTRS)

Mazely, Troy L.; Friedl, Randall R.; Sander, Stanley P.

1965-01-01

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

NASA Technical Reports Server (NTRS)

Trainer, Melissa G.; Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

2012-01-01

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda < 120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120 - 200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

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

PubMed

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.

Flash protection controller

DOEpatents

Galbraith, L.K.

1979-12-07

A controller provides a high voltage to maintain an electro-optic shutter in a transparent condition until a flash of light which would be harmful to personnel is sensed by a phototransistor. The controller then shorts the shutter to ground to minimize light transmission to the user and maintains light transmission at the pre-flash level for a predetermined time to allow the flash to subside. A log converter and differential trigger circuit keep the controller from being triggered by other light flashes which are not dangerous.

Flash protection controller

DOEpatents

Galbraith, Lee K.

1981-01-01

A controller provides a high voltage to maintain an electro-optic shutter in a transparent condition until a flash of light which would be harmful to personnel is sensed by a phototransistor. The controller then shorts the shutter to ground to minimize light transmission to the user and maintains light transmission at the pre-flash level for a predetermined time to allow the flash to subside. A log converter and differential trigger circuit keep the controller from being triggered by other light flashes which are not dangerous.

Lunar Impact Flash Locations

NASA Technical Reports Server (NTRS)

Moser, D. E.; Suggs, R. M.; Kupferschmidt, L.; Feldman, J.

2015-01-01

A bright impact flash detected by the NASA Lunar Impact Monitoring Program in March 2013 brought into focus the importance of determining the impact flash location. A process for locating the impact flash, and presumably its associated crater, was developed using commercially available software tools. The process was successfully applied to the March 2013 impact flash and put into production on an additional 300 impact flashes. The goal today: provide a description of the geolocation technique developed.

The synergetic effect of UV rays on the decomposition of xylene in dielectric barrier discharge plasma and photocatalyst process

NASA Astrophysics Data System (ADS)

Li, Wenjuan; Gu, Zhenyu; Teng, Fuhua; Lu, Jianhai; Dong, Shibi; Miao, Xiaoping; Wu, Zhongbiao

2018-06-01

The degradation of xylene in the dielectric barrier discharge plasma and photocatalyst process was studied, focusing on the synergetic effect of UV rays from plasma process and external UV lamps on the decomposition of xylene. The results showed that xylene could be decomposed by the discharge process in plasma system, whereas the UV rays from plasma process was very weak. After adding TiO2, the removal efficiency of xylene and energy yield in plasma process were enhanced since energetic particles activated the catalysis of TiO2. The removal efficiency of xylene and energy field in plasma and photocatalyst process combined with external UV lamps were further enhanced attributed to the degradation effect of plasma, the catalysis of TiO2 activated by plasma, the photolysis of UV rays and the photocatalysis of photocatalyst. The synergetic effect of UV rays from external UV lamps was obvious.

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

PubMed

Shushakov, Anton A; Pozdnyakov, Ivan P; Grivin, Vjacheslav P; Plyusnin, Victor F; Vasilchenko, Danila B; Zadesenets, Andrei V; Melnikov, Alexei A; Chekalin, Sergey V; Glebov, Evgeni M

2017-07-25

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] and trans,trans,trans-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.

Degradation and Byproduct Formation of Parathion in Aqueous Solutions by UV and UV/H2O2 Treatment

PubMed Central

Wu, Changlong; Linden, Karl G.

2013-01-01

The photodegradation of parathion, a US EPA Contaminant Candidate List pesticide, in aqueous solutions by UV and UV/H2O2 processes in batch reactors was evaluated. Direct photolysis of parathion both by LP (low pressure) and MP (medium pressure) lamps at pH 7 were very slow with quantum yields of 6.67 ± 0.33 ×10−4 and 6.00 ± 1.06 ×10−4 mol E−1, respectively. Hydrogen peroxide enhanced the photodegradation of parathion through the reaction between UV generated hydroxyl radical and parathion with a second-order reaction rate constant of 9.70 ± 0.45×109 M−1 s−1. However, addition of hydrogen peroxide did not result in a linear increase in the degradation rate. An optimum molar ratio between hydrogen peroxide and parathion was determined to be between 300 – 400. Photodegradation of parathion yielded several organic byproducts, of which the paraoxon, 4-nitrophenol, O,O,O-triethyl thiophosphate and O,O diethyl-methyl thiophosphate were quantified and their occurrence during UV/H2O2 processes were discussed. NO2−, PO43−, NO3− and SO42− were the major anionic byproducts of parathion photodegradation and their recover ratio were also discussed. A photodegradation mechanism scheme suggesting three simultaneous pathways was proposed in the study. PMID:18834610

Predicting transformation products from the direct photolysis of organic compounds in aquatic systems

EPA Science Inventory

Direct photolysis is an important degradation pathway for organic compounds bearing sunlight-absorbing chromophores in aquatic systems. An ever-growing body of process science underlying direct photolysis transformation pathways provides the basis for the development of predictiv...

Characterization and Discrimination of Large Caliber Gun Blast and Flash Signatures

DTIC Science & Technology

2011-10-01

from one end of a barrel (the muzzle) by the application of force at the other end. In conventional guns , force is provided by the combustion of a...projectile begins to accelerate down the barrel ; this is known as shot start. As the projectile traverses the gun barrel and additional volume becomes...flash that is used today resulted from this program’s report. Visible and ultraviolet (UV) spectra of 20 mm and .50 caliber machine gun firings were

[Efficiency of photodecomposition of trace NDMA in water by UV irradiation].

PubMed

Xu, Bing-Bing; Chen, Zhong-Lin; Qi, Fei; Ma, Jun

2008-07-01

Efficiency of photodecomposition of trace NDMA by UV irradiation was investigated with analyzing the initial concentration of NDMA, solution pH, irradiation area, irradiation intensity and water quality effect on NDMA photolysis. NDMA could be effectively photodegraded by UV irradiation. The removal efficiency of NDMA was 97.5% after 5 min of UV irradiation. Effect of initial NDMA concentration on photodecomposition of NDMA was not remarkable. With pH value ascending, the removal rate of NDMA photodecomposition decreased. The yields of photoquantum were more under lower solution pH than that under higher pH. NDMA had fastest reaction rate at solution pH = 2.2. Removal efficiency of NDMA increased with the available irradiation area ascending. Increscent ultraviolet irradiation intensity was good for NDMA degradation. Water quality affected the removal of NDMA slightly. The removal efficiency of NDMA in tap water and Songhua River raw water were 96.7% and 94.8%, respectively.

Flash!

NASA Astrophysics Data System (ADS)

Schilling, Govert

2002-04-01

About three times a day our sky flashes with a powerful pulse of gamma ray bursts (GRB), invisible to human eyes but not to astronomers' instruments. The sources of this intense radiation are likely to be emitting, within the span of seconds or minutes, more energy than the sun will in its entire 10 billion years of life. Where these bursts originate, and how they come to have such incredible energies, is a mystery scientists have been trying to solve for three decades. The phenomenon has resisted study -- the flashes come from random directions in space and vanish without trace -- until very recently. In what could be called a cinematic conflation of Flash Gordon and The Hunt for Red October, Govert Schilling's Flash!: The Hunt for the Biggest Explosions in the Universe describes the exciting and ever-changing field of GRB research. Based on interviews with leading scientists, Flash! provides an insider's account of the scientific challenges involved in unravelling the enigmatic nature of GRBs. A science writer who has followed the drama from the very start, Schilling describes the ambition and jealousy, collegiality and competition, triumph and tragedy, that exists among those who have embarked on this recherche. Govert Schilling is a Dutch science writer and astronomy publicist. He is a contributing editor of Sky and Telescope magazine, and regularly writes for the news sections of Science and New Scientist. Schilling is the astronomy writer for de Volkskrant, one of the largest national daily newspapers in The Netherlands, and frequently talks about the Universe on Dutch radio broadcasts. He is the author of more than twenty popular astronomy books, and hundreds of newspaper and magazine articles on astronomy.

Photolysis of rhodamine-WT dye

USGS Publications Warehouse

Tai, D.Y.; Rathbun, R.E.

1988-01-01

Photolysis of rhodamine-WT dye under natural sunlight conditions was determined by measuring the loss of fluorescence as a function of time. Rate coefficients at 30?? north latitude ranged from 4.77 x 10-2 day-1 for summer to 3.16 x 10-2 day-1 for winter. Experimental coefficients were in good agreement with values calculated using a laboratory-determined value of the quantum yield.

Effective absorption cross sections and photolysis rates of anthropogenic and biogenic secondary organic aerosols

NASA Astrophysics Data System (ADS)

Romonosky, Dian E.; Ali, Nujhat N.; Saiduddin, Mariyah N.; Wu, Michael; Lee, Hyun Ji (Julie); Aiona, Paige K.; Nizkorodov, Sergey A.

2016-04-01

Mass absorption coefficient (MAC) values were measured for secondary organic aerosol (SOA) samples produced by flow tube ozonolysis and smog chamber photooxidation of a wide range of volatile organic compounds (VOC), specifically: α-pinene, β-pinene, β-myrcene, d-limonene, farnesene, guaiacol, imidazole, isoprene, linalool, ocimene, p-xylene, 1-methylpyrrole, and 2-methylpyrrole. Both low-NOx and high-NOx conditions were employed during the chamber photooxidation experiments. MAC values were converted into effective molecular absorption cross sections assuming an average molecular weight of 300 g/mol for SOA compounds. The upper limits for the effective photolysis rates of SOA compounds were calculated by assuming unity photolysis quantum yields and convoluting the absorption cross sections with a time-dependent solar spectral flux. A more realistic estimate for the photolysis rates relying on the quantum yield of acetone was also obtained. The results show that condensed-phase photolysis of SOA compounds can potentially occur with effective lifetimes ranging from minutes to days, suggesting that photolysis is an efficient and largely overlooked mechanism of SOA aging.

Rate constant for the reaction NH2 + NO from 216 to 480 K

NASA Technical Reports Server (NTRS)

Stief, L. J.; Brobst, W. D.; Nava, D. F.; Borkowski, R. P.; Michael, J. V.

1982-01-01

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

Flash fire propensity of materials

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Cumming, H. J.

1977-01-01

Flash fire test results on 86 materials, evaluated using the USF flash fire screening test, are presented. The materials which appear least prone to flash fires are PVC, polyphenylene oxide and sulfide, and polyether and polyaryl sulfone; these did not produce flash fires under these particular test conditions. The principal value of these screening tests at the present time is in identifying materials which appear prone to flash fires, and in identifying which formulations of a generic material are more or less prone to flash fires.

A multispectral, high-speed, low-cost device in the UV-MWIR spectral range

NASA Astrophysics Data System (ADS)

Svensson, Thomas; Lindell, Roland; Carlsson, Leif

2011-10-01

This paper presents the design and performance of a multispectral, high-speed, low-cost device. It is composed of six separate single element detectors covering the spectral range from UV to MWIR. Due to the wide spectral ranges of the detectors, these are used in conjunction with spectral filters. The device is a tool to spectrally and temporally resolve large field of view angularly integrated signatures from very fast events and get a total amplitude measure. One application has been to determine the maximal amplitude signal in muzzle flashes. Since the pulse width of a muzzle flash is on the order of 1 ms, a sensor with a bandwidth significantly higher than 1000 Hz is needed to resolve the flash. Examples from experimental trials are given.

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

PubMed

Galí, Martí; Kieber, David J; Romera-Castillo, Cristina; Kinsey, Joanna D; Devred, Emmanuel; Pérez, Gonzalo L; Westby, George R; Marrasé, Cèlia; Babin, Marcel; Levasseur, Maurice; Duarte, Carlos M; Agustí, Susana; Simó, Rafel

2016-12-20

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 m 3 (mol quanta) -1 ). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m 3 (mol quanta) -1 . The largest AQY(330), up to 34 m 3 (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.

Laboratory simulations of PH3 photolysis in the atmospheres of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Khwaja, H.

1985-01-01

The effects of pressure, temperature, light wavelength and intensity, and components of the atmosphere of the Jovian planets on the photolysis of PH3 were experimentally studied. The products of the photolysis, P2H4 and red phosphorus, exhibited little variation when the irradiation experiments were performed under conditions prevalent in Jupiter's atmosphere. No quenching of PH2 radicals by the levels of hydrocarbons present in the Jovian atmosphere was noted. The high partial pressure of hydrogen present on Jupiter should have no effect on the course of the photolysis. The low temperatures on Jupiter and Saturn may result in some condensation of P2H4, but P2H4 had sufficient vapor pressure in the experimental studies at 157 K to be slowly converted to red phosphorus. The products of PH3 photolysis were the same whether a 147, 184.9, or 206.2 nm monochromatic light source or a xenon lamp with a broad spectral output was used.

Implementation of UV-based advanced oxidation processes in algal medium recycling.

PubMed

Wang, Wenxuan; Sha, Jun; Lu, Zhiying; Shao, Senlin; Sun, Peizhe; Hu, Qiang; Zhang, Xuezhi

2018-09-01

Algae show great potential as sustainable feedstock for numerous bioproducts. However, large volume of water consumption during algal biomass production makes that the culture media recycling is a necessity due to economic and environmental concern. To avoid the negative effect of enriched organic matters in the harvested culture media, pre-treatment prior to medium replenishment and reuse is required. In this study, degradation of algenitic organic matters (AOM) in the culture media by UV-based photolysis processes (i.e., direct UV, UV/peroxydisulfate (PDS), UV/H 2 O 2 , and UV/NH 2 Cl) was explored. The results showed that UV, UV/PDS, UV/H 2 O 2 and UV/NH 2 Cl caused a decrease of SUVA for 29.9%, 35.4%, 40.45%, and 22.6%, respectively, though the organic matter was almost not mineralized. Fluorescence excitation-emission matrix combined with parallel factor analysis indicated that UV/PDS and UV/H 2 O 2 degraded 47.26%-56.31% of the fulvic-like and humic-like fractions in AOM. Powder activated carbon absorption and growth evaluation for the AOPs-treated media indicated that UV/PDS and UV/H 2 O 2 processes not only could remove the growth inhibitors in the media, but were also beneficial to the algae growth. These results suggested that UV/PDS and UV/H 2 O 2 could effectively degrade the hydrophobic components in AOM and converted the growth inhibition fraction of AOM in the recycled media into nutrient source for algal growth. Different from the general application of UV-based AOP in the wastewater treatment, this study provided an innovative idea about how to pre-treat AOM in the media recycling: utilization rather than removal, which was a more sustainable and environment-friendly technology. Copyright © 2018 Elsevier B.V. All rights reserved.

Parathion degradation and toxicity reduction in solar photocatalysis and photolysis.

PubMed

Zoh, K D; Kim, T S; Kim, J G; Choi, K; Yi, S M

2006-01-01

The solar photocatalytic degradation of methyl parathion was investigated using a circulating TiO2/solar light reactor. Under solar photocatalysis condition, parathion was more effectively degraded than solar photolysis and TiO2-only conditions. With solar photocatalysis, 20 mg/L of parathion was completely degraded within 60 min with a TOC decrease of 63% after 150 min. The main ionic byproducts during photocatalysis recovered from parathion degradation were mainly as NO3-, NO2- and NH4+, 80% of the sulphur as SO4(2-), and 5% of phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and methyl paraoxon were also identified, and these were further degraded in solar photocatalytic condition. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by solar photocatalysis and photolysis. The Microtox test using V. fischeri showed that the toxicity expressed as EC50 (%) value increased from 5.5% to >82% in solar photocatalysis, indicating that the treated solution is non-toxic, but only increased from 4.9 to 20.5% after 150 min in solar photolysis. The acute toxicity test using D. magna showed that EC50 (%) increased from 0.05 to 1.08% under solar photocatalysis, but only increased to 0.12% after 150 min with solar photolysis, indicating the solution is still toxic. The pattern of toxicity reduction parallels the decrease in TOC and the parathion concentrations.

Transformation of acesulfame in water under natural sunlight: joint effect of photolysis and biodegradation.

PubMed

Gan, Zhiwei; Sun, Hongwen; Wang, Ruonan; Hu, Hongwei; Zhang, Pengfei; Ren, Xinhao

2014-11-01

The transformation of acesulfame in water under environmentally relevant conditions, including direct and indirect photolysis, biodegradation, and hydrolysis, was systematically evaluated. Under natural sunlight, both direct and indirect photolysis of acesulfame were negligible in sterilized systems at neutral or alkaline pH, whereas direct photolysis occurred at pH of 4 with a rate constant of 0.0355 d(-1) in deionized water. No significant reduction in acesulfame contents was found in the dark controls or in the incubation experiments, indicating acesulfame was resistant to hydrolysis and biodegradation. In unsterilized systems, photolysis was substantially enhanced, implying that there was a joint effect of photolysis and biodegradation or that the sterilization process had the secondary effect of inactivating some photosensitizers. The near-surface summer half-life of acesulfame in the water from the Haihe River was 9 d. Specific experiments revealed the involvement of (1)O2/(3)DOM* in acesulfame photolysis, whereas OH exhibited only a slight contribution in the presence of DOM or bicarbonate. As indicated by the total organic carbon data, no significant mineralization occurred in both sterilized and unsterilized systems after acesulfame was irradiated under simulated sunlight for 7 d, suggesting the generation of persistent intermediates. Finally, major degradation intermediates were analyzed, and the degradation pathways of acesulfame under environmentally relevant conditions were proposed for the first time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Daily Physical Activity and Hot Flashes in the Study of Women's Health Across the Nation FLASHES Study

PubMed Central

Gibson, Carolyn; Matthews, Karen; Thurston, Rebecca

2014-01-01

Objective To examine the role of physical activity in menopausal hot flashes. Competing models conceptualize physical activity as a risk or protective factor for hot flashes. Few studies have examined this relationship prospectively using physiologic measures of hot flashes and physical activity. Design Over two 48 hour-periods, 51 participants wore a physiologic hot flash monitor and activity monitor, and reported their hot flashes in an electronic diary. Physiologic hot flashes, reported hot flashes and reported hot flashes without physiological corroboration were related to activity changes using hierarchical generalized linear modeling, adjusting for potential confounders. Setting Community. Patients Midlife women. Interventions None. Main Outcome Measures Physiologically-detected hot flashes and reported hot flashes with and without physiologic corroboration. Results Hot flash reports without physiologic corroboration were more likely after activity increases (OR 1.04, 95% CI: 1.00-1.10, p=.01), particularly among women with higher levels of depressive symptoms (interaction p=.02). No other types of hot flashes were related to physical activity. Conclusion Acute increases in physical activity were associated with increased reporting of hot flashes lacking physiologic corroboration, particularly among women with depressive symptoms. Clinicians should consider the role of symptom perception and reporting in relations between physical activity and hot flashes. PMID:24491454

Active Flash: Out-of-core Data Analytics on Flash Storage

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

Boboila, Simona; Kim, Youngjae; Vazhkudai, Sudharshan S

2012-01-01

Next generation science will increasingly come to rely on the ability to perform efficient, on-the-fly analytics of data generated by high-performance computing (HPC) simulations, modeling complex physical phenomena. Scientific computing workflows are stymied by the traditional chaining of simulation and data analysis, creating multiple rounds of redundant reads and writes to the storage system, which grows in cost with the ever-increasing gap between compute and storage speeds in HPC clusters. Recent HPC acquisitions have introduced compute node-local flash storage as a means to alleviate this I/O bottleneck. We propose a novel approach, Active Flash, to expedite data analysis pipelines bymore » migrating to the location of the data, the flash device itself. We argue that Active Flash has the potential to enable true out-of-core data analytics by freeing up both the compute core and the associated main memory. By performing analysis locally, dependence on limited bandwidth to a central storage system is reduced, while allowing this analysis to proceed in parallel with the main application. In addition, offloading work from the host to the more power-efficient controller reduces peak system power usage, which is already in the megawatt range and poses a major barrier to HPC system scalability. We propose an architecture for Active Flash, explore energy and performance trade-offs in moving computation from host to storage, demonstrate the ability of appropriate embedded controllers to perform data analysis and reduction tasks at speeds sufficient for this application, and present a simulation study of Active Flash scheduling policies. These results show the viability of the Active Flash model, and its capability to potentially have a transformative impact on scientific data analysis.« less

Effects of ultraviolet (UV) irradiation in air and under vacuum on low-k dielectrics

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

Choudhury, F. A.; Nguyen, H. M.; Shohet, J. L., E-mail: shohet@engr.wisc.edu

This work addresses the effect of ultraviolet radiation of wavelengths longer than 250 nm on Si-CH{sub 3} bonds in porous low-k dielectrics. Porous low-k films (k = 2.3) were exposed to 4.9 eV (254 nm) ultraviolet (UV) radiation in both air and vacuum for one hour. Using Fourier Transform Infrared (FTIR) spectroscopy, the chemical structures of the dielectric films were analyzed before and after the UV exposure. UV irradiation in air led to Si-CH{sub 3} bond depletion in the low-k material and made the films hydrophilic. However, no change in Si-CH{sub 3} bond concentration was observed when the same samplesmore » were exposed to UV under vacuum with a similar fluence. These results indicate that UV exposures in vacuum with wavelengths longer than ∼250 nm do not result in Si-CH{sub 3} depletion in low-k films. However, if the irradiation takes place in air, the UV irradiation removes Si-CH{sub 3} although direct photolysis of air species does not occur above ∼242 nm. We propose that photons along with molecular oxygen and, water, synergistically demethylate the low-k films.« less

The photolysis of CO2 at 1849 and 2139A

NASA Technical Reports Server (NTRS)

Krezenski, D.; Simonaitis, R.; Heicklen, J.

1971-01-01

The quantum yield for CO2 photodissociation at 25 C was found to be 1.08 + or - 0.12 for direct photolysis at 1849 A and between 200 and 800 torr; 0.48 + or - 0.02 for the Hg 6(1 P 1) sensitized decomposition between 130 and 730 torr; and 0.16 + or - 0.05 for the direct photolysis at 2139 A and between 300 and 600 torr. At these wavelengths, there was insufficient energy found to produce O(1 D). The primary process used is CO2 + hv yields CO + O(3 P).

Menopausal hot flashes: Randomness or rhythmicity

NASA Astrophysics Data System (ADS)

Kronenberg, Fredi

1991-10-01

Menopausal hot flashes are episodes of flushing, increased heart rate, skin blood flow and skin temperature, and a sensation of heat. The thermoregulatory and cardiovascular concomitants of hot flashes are associated with peaks in the levels of various hormones and neurotransmitters in the peripheral circulation. Although hot flashes affect about 75% of women, and are the primary reason that women at menopause seek medical attention, the mechanism of hot flashes is still not understood. Hot flashes vary in frequency and intensity both within and between individuals, and have been thought of as occurring randomly. Yet, some women report that their hot flashes are worse at a particular time of day or year. Initial examination of subjects' recordings of their hot flashes showed diurnal patterns of hot flash occurrence. There also seems to be a diurnal rhythm of hot flash intensity. Continuous physiological monitoring of hot flashes is facilitating the analysis of these patterns, which is revealing circadian and ultradian periodicities. The occurrence of hot flashes can be modulated by external and internal factors, including ambient temperature and fever. Rhythms of thermoregulatory and endocrine functions also may influence hot flash patterns. Examination of the interrelationships between the various systems of the body involved in hot flashes, and a multidisciplinary approach to the analysis of hot flash patterns, will aid our understanding of this complex phenomenon.

Mask replication using jet and flash imprint lithography

NASA Astrophysics Data System (ADS)

Selinidis, Kosta S.; Jones, Chris; Doyle, Gary F.; Brown, Laura; Imhof, Joseph; LaBrake, Dwayne L.; Resnick, Douglas J.; Sreenivasan, S. V.

2011-11-01

The Jet and Flash Imprint Lithography (J-FILTM) process uses drop dispensing of UV curable resists to assist high resolution patterning for subsequent dry etch pattern transfer. The technology is actively being used to develop solutions for memory markets including Flash memory and patterned media for hard disk drives. It is anticipated that the lifetime of a single template (for patterned media) or mask (for semiconductor) will be on the order of 104 - 105imprints. This suggests that tens of thousands of templates/masks will be required to satisfy the needs of a manufacturing environment. Electron-beam patterning is too slow to feasibly deliver these volumes, but instead can provide a high quality "master" mask which can be replicated many times with an imprint lithography tool. This strategy has the capability to produce the required supply of "working" templates/masks. In this paper, we review the development of the mask form factor, imprint replication tools and the semiconductor mask replication process. A PerfectaTM MR5000 mask replication tool has been developed specifically to pattern replica masks from an ebeam written master. Performance results, including image placement, critical dimension uniformity, and pattern transfer are covered in detail.

Why Flash Type Matters: A Statistical Analysis

NASA Astrophysics Data System (ADS)

Mecikalski, Retha M.; Bitzer, Phillip M.; Carey, Lawrence D.

2017-09-01

While the majority of research only differentiates between intracloud (IC) and cloud-to-ground (CG) flashes, there exists a third flash type, known as hybrid flashes. These flashes have extensive IC components as well as return strokes to ground but are misclassified as CG flashes in current flash type analyses due to the presence of a return stroke. In an effort to show that IC, CG, and hybrid flashes should be separately classified, the two-sample Kolmogorov-Smirnov (KS) test was applied to the flash sizes, flash initiation, and flash propagation altitudes for each of the three flash types. The KS test statistically showed that IC, CG, and hybrid flashes do not have the same parent distributions and thus should be separately classified. Separate classification of hybrid flashes will lead to improved lightning-related research, because unambiguously classified hybrid flashes occur on the same order of magnitude as CG flashes for multicellular storms.

Continuous Monitoring of Photolysis Products by Thz Spectroscopy

NASA Astrophysics Data System (ADS)

Omar, Abdelaziz; Cuisset, Arnaud; Mouret, Gaël; Hindle, Francis; Eliet, Sophie; Bocquet, Robin

2015-06-01

We demonstrate the potential of THz spectroscopy to monitor the real time evolution of the gas phase concentration of photolysis products and determine the kinetic reaction rate constant. In the primary work, we have chosen to examine the photolysis of formaldehyde (H_2CO). Exposure of H_2CO to a UVB light (250 to 360 nm) in a single pass of 135 cm length cell leads to decomposition via two mechanisms: the radical channel with production of HCO and the molecular channel with production of CO. A commercial THz source (frequency multiplication chain) operating in the range 600-900 GHz was used to detect and quantify the various chemical species as a function of time. Monitoring the concentrations of CO and H_2CO via rotational transitions, allowed the kinetic rate of H_2CO consummation to be obtained, and an estimation of the rate constants for both the molecular and radical photolysis mechanisms. We have modified our experimental setup to increase the sensitivity of the spectrometer and changed sample preparation protocol specifically to quantify the HCO concentration. Acetaldehyde was used as the precursor for photolysis by UVC resulting in the decompositon mechanism can be described by: CH_3CHO+hν→ CH_3 + HCO → CH_4 + CO Frequency modulation of the source and Zeeman modulation is used to achieve the high sensitivity required. Particular attention has been paid to the mercury photosensitization effect that allowed us to increase the HCO production enabling quantification of the monitored radical. We quantify the HCO radical and start a spectroscopic study of the line positions. H. M. Pickett and T. L. Boyd, Chem. Phys. Lett, Vol 58, 446-449, (1978) S. Eliet, A. Cuisset, M Guinet, F. Hindle, G. Mouret, R. Bocquet, and J. Demaison, Journal of Molecular Spectroscopy, Vol 279, 12-15 (2012). G. Mouret, M. Guinet, A. Cuisset, L. Croizé, S. Eliet, R. Bocquet and F. Hindle, Sensors Journal. IEEE, Vol 13, 133 - 138, (2013)

Degradation of 40 selected pharmaceuticals by UV/H2O2.

PubMed

Wols, B A; Hofman-Caris, C H M; Harmsen, D J H; Beerendonk, E F

2013-10-01

The occurrence of pharmaceuticals in source waters is increasing. Although UV advanced oxidation is known to be an effective barrier against micropollutants, degradation rates are only available for limited amounts of pharmaceuticals. Therefore, the degradation of a large group of pharmaceuticals has been studied in this research for the UV/H2O2 process under different conditions, including pharmaceuticals of which the degradation by UV/H2O2 was never reported before (e.g., metformin, paroxetine, pindolol, sotalol, venlafaxine, etc.). Monochromatic low pressure (LP) and polychromatic medium pressure (MP) lamps were used for three different water matrices. In order to have well defined hydraulic conditions, all experiments were conducted in a collimated beam apparatus. Degradation rates for the pharmaceuticals were determined. For those compounds used in this research that are also reported in literature, measured degradation results are in good agreement with literature data. Pharmaceutical degradation for only photolysis with LP lamps is small, which is increased by using a MP lamp. Most of the pharmaceuticals are well removed when applying both UV (either LP or MP) and H2O2. However, differences in degradation rates between pharmaceuticals can be large. For example, ketoprofen, prednisolone, pindolol are very well removed by UV/H2O2, whereas metformin, cyclophosphamide, ifosfamide are very little removed by UV/H2O2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of Nicotinamide on the Photolysis of Riboflavin in Aqueous Solution

PubMed Central

Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Anwar, Zubair; Qadeer, Kiran; Noor, Adnan; Evstigneev, Maxim P.

2016-01-01

The photolysis of riboflavin (RF) in aqueous solution in the presence of nicotinamide (NA) by visible light has been studied in the pH range 1.0–12.0 and the various photoproducts have been identified as known compounds. RF has been determined in degraded solutions by a specific multicomponent spectrometric method in the presence of its photoproducts and NA. The second-order rate constants (k2) for the bimolecular interaction of RF and NA range from 0.54 (pH 1.0) to 9.66 M–1 min–1 (pH 12.0). The log k2–pH profile for the photolysis reaction follows a sigmoid curve showing a gradual increase in the rate of pH due to a change in the ionization behavior of the molecule. The lower rate in the acid region is probably due to protonation of the molecule since the cationic form of RF is less susceptible to photolysis than the neutral form. Similarly, a slowing of the rate in the alkaline region is due to anion formation of the molecule. NA is involved as an electron acceptor during the sequence of reactions and thus enhances the rate of photolysis of RF. Absorption and fluorescence measurements did not provide evidence for the complex formation between the two compounds under the present conditions. PMID:27222605

A flash-lamp based device for fluorescence detection and identification of individual pollen grains.

PubMed

Kiselev, Denis; Bonacina, Luigi; Wolf, Jean-Pierre

2013-03-01

We present a novel optical aerosol particle detector based on Xe flash lamp excitation and spectrally resolved fluorescence acquisition. We demonstrate its performances on three natural pollens acquiring in real-time scattering intensity at two wavelengths, sub-microsecond time-resolved scattering traces of the particles' passage in the focus, and UV-excited fluorescence spectra. We show that the device gives access to a rather specific detection of the bioaerosol particles.

In Situ Investigation the Photolysis of the PAHs Adsorbed on Mangrove Leaf Surfaces by Synchronous Solid Surface Fluorimetry

PubMed Central

Wang, Ping; Wu, Tun-Hua; Zhang, Yong

2014-01-01

An established synchronous solid surface fluorimetry (S-SSF) was utilized for in situ study the photolysis processes of anthracene (An) and pyrene (Py) adsorbed on the leaf surfaces of Kandelia obovata seedlings (Ko) and Aegiceras corniculata (L.) Blanco seedlings (Ac). Experimental results demonstrated that the photolysis of An and Py adsorbed on the leaf surfaces of two mangrove species under the laboratory conditions, followed first-order kinetics with their photolysis rates in the order of Ac>Ko. In addition, with the same amount of substances, the photolysis rate of An adsorbed on the same mangrove leaf surfaces was much faster than the adsorbed Py. In order to investigate further, the photolysis processes of An and Py in water were also studied for comparison. And the photolysis of An and Py in water also followed first-order kinetics. Moreover, for the same initial amount, the photolysis rate of the PAH in water was faster than that adsorbed on the leaf surfaces of two mangrove species. Therefore, photochemical behaviors of PAHs were dependent not only on their molecular structures but also the physical-chemical properties of the substrates on which they are adsorbed. PMID:24404158

CCD imaging sensor with flashed backside metal film

NASA Technical Reports Server (NTRS)

Janesick, James R. (Inventor)

1991-01-01

A backside illuminated CCD imaging sensor for reading out image charges from wells of the array of pixels is significantly improved for blue, UV, far UV and low energy x-ray wavelengths (1-5000.ANG.) by so overthinning the backside as to place the depletion edge at the surface and depositing a thin transparent metal film of about 10.ANG. on a native-quality oxide film of less than about 30.ANG. grown on the thinned backside. The metal is selected to have a higher work function than that of the semiconductor to so bend the energy bands (at the interface of the semiconductor material and the oxide film) as to eliminate wells that would otherwise trap minority carriers. A bias voltage may be applied to extend the frontside depletion edge to the interface of the semiconductor material with the oxide film in the event there is not sufficient thinning. This metal film (flash gate), which improves and stabilizes the quantum efficiency of a CCD imaging sensor, will also improve the QE of any p-n junction photodetector.

Multiple transformation pathways of p-arsanilic acid to inorganic arsenic species in water during UV disinfection.

PubMed

Li, Suqi; Xu, Jing; Chen, Wei; Yu, Yingtan; Liu, Zizheng; Li, Jinjun; Wu, Feng

2016-09-01

p-Arsanilic acid (p-ASA) is widely used in China as livestock and poultry feed additive for promoting animal growth. The use of organoarsenics poses a potential threat to the environment because it is mostly excreted by animals in its original form and can be transformed by UV-Vis light excitation. This work examined the initial rate and efficiency of p-ASA phototransformation under UV-C disinfection lamp. Several factors influencing p-ASA phototransformation, namely, pH, initial concentration, temperature, as well as the presence of NaCl, NH4(+), and humic acid, were investigated. Quenching experiments and LC-MS were performed to investigate the mechanism of p-ASA phototransformation. Results show that p-ASA was decomposed to inorganic arsenic (including As(III) and As(V)) and aromatic products by UV-C light through direct photolysis and indirect oxidation. The oxidation efficency of p-ASA by direct photosis was about 32%, and those by HO and (1)O2 were 19% and 49%, respectively. Cleavage of the arsenic-benzene bond through direct photolysis, HO oxidation or (1)O2 oxidation results in simultaneous formation of inorganic As(III), As(IV), and As(V). Inorganic As(III) is oxidized to As(IV) and then to As(V) by (1)O2 or HO. As(IV) can undergo dismutation or simply react with oxygen to produce As(V) as well. Reactions of the organic moieties of p-ASA produce aniline, aminophenol and azobenzene derivatives as main products. The photoconvertible property of p-ASA implies that UV disinfection of wastewaters from poultry and swine farms containing p-ASA poses a potential threat to the ecosystem, especially agricultural environments. Copyright © 2016. Published by Elsevier B.V.

Multi- and unisensory visual flash illusions.

PubMed

Courtney, Jon R; Motes, Michael A; Hubbard, Timothy L

2007-01-01

The role of stimulus structure in multisensory and unisensory interactions was examined. When a flash (17 ms) was accompanied by multiple tones (each 7 ms, SOA < or =100 ms) multiple flashes were reported, and this effect has been suggested to reflect the role of stimulus continuity in multisensory interactions. In experiments 1 and 2 we examined if stimulus continuity would affect concurrently presented stimuli. When a relatively longer flash (317 ms) was accompanied by multiple tones (each 7 ms), observers reported perceiving multiple flashes. In experiment 3 we tested whether a flash presented near fixation would induce an illusory flash further in the periphery. One flash (17 ms) presented 5 degrees below fixation was reported as multiple flashes if presented with two flashes (each 17 ms, SOA =100 ms) 2 degrees above fixation. The extent to which these data support a phenomenological continuity principle and whether this principle applies to unisensory perception is discussed.

Two-flash thresholds as a function of flash luminance and area.

DOT National Transportation Integrated Search

1968-09-01

The recent use of strobe lights in aviation suggests the possibility of using temporal patterns of short duration flashes as information-carrying signals. Under night flight conditions, two-flash thresholds were obtained using a two-interval, tempora...

Why is gas phase 2-nitrophenol photolysis a potentially important source of OH radicals in the polluted atmosphere?

NASA Astrophysics Data System (ADS)

Zhu, L.

2017-12-01

2-Nitrophenol is an important component of "brown carbon" in the atmosphere. The concentration of 2-nitrophenol is higher in polluted urban areas where there are increased emissions of aromatic hydrocarbons. To assess the air quality impacts of pollutant emissions, it is important to understand the oxidant formation potential of the emitted species. Photolysis is the dominant atmospheric removal process for 2-nitrophenol. Although photodissociation dynamics studies of 2-nitrophenol have reported OH formation at photolysis wavelengths of 266 nm, 355 nm, and over the 361-390 nm range, and HONO has been observed as a product from 2-nitrophenol photolysis in an environmental chamber, the lack of quantitative absorption cross section and product quantum yield information has prevented quantitative assessment of the extent of oxidant formation from the photolysis of 2-nitrophenol in the atmosphere. My group determined the gas phase absorption cross sections of 2-nitrophenol in the 295-400 nm region by using cavity ring-down spectroscopy. The OH, HONO, and NO2 formation channels following the gas phase photolysis of 2-nitrophenol at 308 and 351 nm were investigated. Direct NO2 formation was not observed. OH and HONO were direct products from the 2-nitrophenol photolysis, and their quantum yields were obtained. The sum of the OH and the HONO quantum yields was about unity at both photolysis wavelengths. The estimated photolysis rate constant of 2-nitrophenol was about twice that of NO2. I will discuss the importance of 2-nitrophenol gas phase photolysis as a potential source of OH and HONO in regions of high anthropogenic emissions.

Photochemical reactions in interstellar grains photolysis of CO, NH3, and H2O

NASA Technical Reports Server (NTRS)

Agarwal, V. K.; Ferris, J. P.; Schutte, W.; Greenberg, J. M.; Briggs, R.

1985-01-01

The interstellar grains are currently considered to be the basic building blocks of comets and, possibly, meteorites. To test this theory, a simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH3:H2O gas mixture on an Al block at 10 K, with concomitant irradiation with vacuum UV. The results of the HPLC and IR analyses of the nonvolatile residue formed by photolysis at 10 K are compared with those observed at 77 K and 298 K. Some of the compounds that may be present on the surfaces of interstellar dust particles have been identified, and some specific predictions concerning the types of molecular species present in comets could be drawn. The results also suggest that photochemical reactions may have been important for the formation of meteorite components. The implication of the findings to the questions of the source of organic matter on earth and the origin of life are discussed.

Laboratory studies of stratospheric bromine chemistry: Kinetics of the reactions of bromine monoxide with nitrogen dioxide and atomic oxygen

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton

A laser flash photolysis - long path absorption - technique has been employed to study the kinetics of the reaction BrO+NO2+M(k(sub 16)) yields products as a function of temperature (248-346 K), pressure (16-800 Torr), and buffer gas identity (N2, CF4). 351 nm photolysis of NO2/Br2/N2 mixtures generated BrO. The BrO decay in the presence of excess NO2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k(sub 16)(P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k(sub 16)(P,T) for use in modeling stratospheric BrO(x) chemistry. The kinetics of the important stratospheric reaction BrO+O(P-3)(k(sub 14)) yields Br+O2 in N2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25-150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of Br2/O3/N2 mixtures produces O atoms in excess over Br2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolysis a small fraction of the O3 to generate O(P-3). The decay of O(P-3) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resoved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k(sub 14)(T) is k(sub 14)(T) = 1.64 x 10(exp -11) exp(263/T) cm(exp 3) molecule(exp-1)s(exp -1). The absolute accuracy of k(sub 14)(T) at any temperature within the range studied is estimated to be +/- 25%. Possible kinetic interferences from production

Evaluation of peracetic acid permeation during flash sterilization through pharmaceutical plastic polymers used in cytotoxic reconstitution units.

PubMed

Havard, Laurent; Fellous-Jerome, Joelle; Bonan, Brigitte; Pradeau, Dominique; Prognon, Patrice

2005-01-01

Peracetic acid (PAA) permeation in flash sterilization was studied using three different plastic infusion bags made of polypropylene and polyethylene, filled with glucose 5% or NaCl 0.9%. The pH was measured and acetic acid (AA) and PAA concentrations were made by reverse phase high-performance liquid chromatography (RP-HPLC). PAA was derivatized by oxidation of methyl tolyl sulfide (MTS) into methyl tolyl sulfoxide (MTSO) detected by ultraviolet (UV) absorbance at 230 nm. The technique has a sensitivity of 0.3 microg x L(-1) and was highly specific. Results showed that pH measurements remain constant and demonstrated the absence of PAA permeation, which was confirmed by the absence of AA permeation regardless of the brand tested, with both unwrapped and overwrapped infusion bags, when flash sterilization is applied. These results allow flash sterilization to be performed with unwrapped infusion bags without any risk of drug degradation by PAA. This makes compounding safer and easier, which improves productivity.

Accounting for dissociation and photolysis: a review of the algal toxicity of triclosan.

PubMed

Roberts, Jayne; Price, Oliver R; Bettles, Nicola; Rendal, Cecilie; van Egmond, Roger

2014-11-01

Triclosan, an antimicrobial agent commonly used in down-the-drain consumer products, is toxic to freshwater microalgae. However, the rapid photolysis and pH-dependent dissociation of this compound may give rise to uncertainty in growth inhibition tests with freshwater microalgae, if these are not well characterized. Methods are presented to minimize these uncertainties by stabilizing pH with an organic buffering agent (Bis-Tris) and by the application of ultraviolet (UV) covers to remove UV wavelengths. Toxicity tests with these methods were in compliance with the validity criteria of the Organisation for Economic Co-operation and Development test 201, and no negative effects were seen in controls relative to the unmodified method. The methods were used for toxicity tests with triclosan at pH levels of 7.0, 8.0, and 8.5, yielding effective concentration, 10% values of 0.5 µg/L, 0.6 µg/L, and 12.1 µg/L, respectively. The observed change in toxicity with pH was proportional to the change in bioconcentration factor (BCF) as calculated using the cell model (a dynamic flux model based on the Fick-Nernst-Planck equations, in this case parameterized for an algal cell). Effect concentrations produced with the methods presented in the present study offer robust data on which to base risk assessment, and it is suggested that similar approaches be used to minimize uncertainty when other compounds that dissociate and photolyse are tested. © 2014 SETAC.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-08-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

DOE PAGES

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; ...

2015-08-20

This paper presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C 12 and C 16 n-alkane reactions with OH at low and high NO x. Simulations are conducted formore » typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NO x) to ~45 % (high NO x) for α-pinene, ~15 % for toluene, ~25 % for C 12 n-alkane, and ~10 % for C 16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C 16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA

Determination of hydrocarbon abundances and the strength of eddy mixing in the stratosphere of Neptune: Analysis of UVS solar occultation lightcurves

NASA Technical Reports Server (NTRS)

Bishop, James

1995-01-01

Work on completing our analysis of the Voyager UVS solar occultation data acquired during Neptune encounter is essentially complete, as testified by the attached poster materials. The photochemical modeling addresses the recent revision in branching ratios for radical production in the photolysis of methane at H Lyman alpha implied by the lab measurements of Mordaunt et al. (1993). The software generated in this effort has been useful for checking the degree to which photochemical models addressing other datasets (mainly infrared) are consistent with the UVS data. This work complements the UVS modeling results in that the IR data refer to deeper pressure levels; as regards the modeling of UVS data, the most significant result is the convincing support for the presence of a stagnant lower stratosphere. Evidence for strong dynamical (mixing) transport of minor constituents at shallower pressures is provided by the UVS data analysis.

All-Solid-State UV Transmitter Development for Ozone Sensing Applications

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.; Singh, Upendra N.; Armstrong, Darrell Jr.

2009-01-01

In this paper, recent progress made in the development of an all-solid-state UV transmitter suitable for ozone sensing applications from space based platforms is discussed. A nonlinear optics based UV setup based on Rotated Image Singly Resonant Twisted Rectangle (RISTRA) optical parametric oscillator (OPO) module was effectively coupled to a diode pumped, single longitudinal mode, conductively cooled, short-pulsed, high-energy Nd:YAG laser operating at 1064 nm with 50 Hz PRF. An estimated 10 mJ/pulse with 10% conversion efficiency at 320 nm has been demonstrated limited only by the pump pulse spatial profile. The current arrangement has the potential for obtaining greater than 200 mJ/pulse. Previously, using a flash-lamp pumped Nd:YAG laser with round, top-hat profile, up to 24% IR-UV conversion efficiency was achieved with the same UV module. Efforts are underway to increase the IR-UV conversion efficiency of the all solid-state setup by modifying the pump laser spatial profile along with incorporating improved OPO crystals.

Flash-Type Discrimination

NASA Technical Reports Server (NTRS)

Koshak, William J.

2010-01-01

This viewgraph presentation describes the significant progress made in the flash-type discrimination algorithm development. The contents include: 1) Highlights of Progress for GLM-R3 Flash-Type discrimination Algorithm Development; 2) Maximum Group Area (MGA) Data; 3) Retrieval Errors from Simulations; and 4) Preliminary Global-scale Retrieval.

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

PubMed

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. Published by Elsevier Ltd.

The October 2014 United States Treasury bond flash crash and the contributory effect of mini flash crashes

PubMed Central

Levine, Zachary S.; Floridi, Luciano

2017-01-01

We investigate the causal uncertainty surrounding the flash crash in the U.S. Treasury bond market on October 15, 2014, and the unresolved concern that no clear link has been identified between the start of the flash crash at 9:33 and the opening of the U.S. equity market at 9:30. We consider the contributory effect of mini flash crashes in equity markets, and find that the number of equity mini flash crashes in the three-minute window between market open and the Treasury Flash Crash was 2.6 times larger than the number experienced in any other three-minute window in the prior ten weekdays. We argue that (a) this statistically significant finding suggests that mini flash crashes in equity markets both predicted and contributed to the October 2014 U.S. Treasury Bond Flash Crash, and (b) mini-flash crashes are important phenomena with negative externalities that deserve much greater scholarly attention. PMID:29091931

Sulfur and Sulfuric Acid Microphysics in the Venus Atmosphere: Implications for the Unknown UV Absorber

NASA Astrophysics Data System (ADS)

Gao, P.; Carlson, R. W.; Robinson, T. D.; Crisp, D.; Lyons, J. R.; Yung, Y. L.

2016-12-01

A mystery that has continued to plague our sister planet, Venus, for nearly a century is the nature of the brightness contrasts observed crisscrossing its disk in near-ultraviolet wavelength images. These contrasts - specifically the dark regions - have been attributed to the actions of an unknown UV absorber, knowing the identity of which is integral to understanding the Venus atmosphere due to the high rates of mesospheric heating attributed to the absorption of solar UV. One possible candidate for the UV absorber is polysulfur, which form from polymerization of elemental sulfur arising from SO2 photolysis at the Venus cloud tops under low O2 conditions. In this work we investigate the microphysics of condensed polysulfur and its interaction with the sulfuric acid clouds. We consider the "gumdrop model", where sulfur is allowed to condense onto sulfuric acid cloud particles. We explore the possibility that S2 vapor may condense faster than its loss to gas phase reactions that produce higher allotropes, leading to solid state polymerization to S8. This process may explain the ephemeral and variable nature of the UV absorption.

Photolysis of O3 at 3130A

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Braslavsky, S.; Heicklen, J.; Nicolet, M.

1972-01-01

The photolysis of O3 at 3130 A and 25 C has been studied in the presence of a large excess of N2O to react with any O(1D) atoms produced. From the N2 produced, the quantum efficiency for O(1D) production was found to be 0.50 + or - 0.03.

High Energy, Single-Mode, All-Solid-State and Tunable UV Laser Transmitter

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.; Singh, Upendra N.; Hovis, FLoyd

2007-01-01

A high energy, single mode, all solid-state Nd:YAG laser primarily for pumping an UV converter is developed. Greater than 1 J/pulse at 50 HZ PRF and pulse widths around 22 ns have been demonstrated. Higher energy, greater efficiency may be possible. Refinements are known and practical to implement. Technology Demonstration of a highly efficient, high-pulse-energy, single mode UV wavelength generation using flash lamp pumped laser has been achieved. Greater than 90% pump depletion is observed. 190 mJ extra-cavity SFG; IR to UV efficiency > 21% (> 27% for 1 mJ seed). 160 mJ intra-cavity SFG; IR to UV efficiency up to 24% Fluence < 1 J/sq cm for most beams. The pump beam quality of the Nd:YAG pump laser is being refined to match or exceed the above UV converter results. Currently the Nd:YAG pump laser development is a technology demonstration. System can be engineered for compact packaging.

Producing CCD imaging sensor with flashed backside metal film

NASA Technical Reports Server (NTRS)

Janesick, James R. (Inventor)

1988-01-01

A backside illuminated CCD imaging sensor for reading out image charges from wells of the array of pixels is significantly improved for blue, UV, far UV and low energy x-ray wavelengths (1-5000.ANG.) by so overthinning the backside as to place the depletion edge at the surface and depositing a thin transparent metal film of about 10.ANG. on a native-quality oxide film of less than about 30.ANG. grown on the thinned backside. The metal is selected to have a higher work function than that of the semiconductor to so bend the energy bands (at the interface of the semiconductor material and the oxide film) as to eliminate wells that would otherwise trap minority carriers. A bias voltage may be applied to extend the frontside depletion edge to the interface of the semiconductor material with the oxide film in the event there is not sufficient thinning. This metal film (flash gate), which improves and stabilizes the quantum efficiency of a CCD imaging sensor, will also improve the QE of any p-n junction photodetector.

Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

NASA Astrophysics Data System (ADS)

MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

2014-12-01

Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

Photolysis of natural B-triketonic herbicides in water

USDA-ARS?s Scientific Manuscript database

The fate of four natural triketones (leptospermone, isoleptospermone, grandiflorone and flavesone, pKa=4.0 to 4.5) in aqueous solution, in the dark and upon simulated solar light irradiation was investigated. In anionic form, triketones undergo oxidation in the dark, however, photolysis is much fast...

UV absorption spectrum of the ClO dimer (Cl2O2) between 200 and 420 nm.

PubMed

Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Fahey, David W; Burkholder, James B

2009-12-10

The UV photolysis of Cl(2)O(2) (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl(2)O(2) was measured using diode array spectroscopy and absolute cross sections, sigma, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl(2)O at 248 nm or Cl(2)/Cl(2)O mixtures at 351 nm at low temperature (200-228 K) and high pressure (approximately 700 Torr, He) was used to produce ClO radicals and subsequently Cl(2)O(2) via the termolecular ClO self-reaction. The Cl(2)O(2) spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl(2)O(2) spectrum. The Cl(2)O(2) UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6(-0.5)(+0.8) x 10(-18) cm(2) molecule(-1) where the quoted error limits are 2sigma and include estimated systematic errors. The Cl(2)O(2) absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl(2)O(2) spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl(2)O(2) cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of sigma(Cl(2)O(2))(lambda) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl(2)O(2) are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

UV Absorption Spectrum of the ClO Dimer (Cl2O2) between 200 and 420 nm

NASA Astrophysics Data System (ADS)

Papanastasiou, Dimitrios K.; Papadimitriou, Vassileios C.; Fahey, David W.; Burkholder, James B.

2009-11-01

The UV photolysis of Cl2O2 (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl2O2 was measured using diode array spectroscopy and absolute cross sections, σ, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl2O at 248 nm or Cl2/Cl2O mixtures at 351 nm at low temperature (200-228 K) and high pressure (˜700 Torr, He) was used to produce ClO radicals and subsequently Cl2O2 via the termolecular ClO self-reaction. The Cl2O2 spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl2O2 spectrum. The Cl2O2 UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6-0.5+0.8 × 10-18 cm2 molecule-1 where the quoted error limits are 2σ and include estimated systematic errors. The Cl2O2 absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl2O2 spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl2O2 cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of σCl2O2(λ) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl2O2 are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

NASA Astrophysics Data System (ADS)

Bouzidi, H.; Laversin, H.; Tomas, A.; Coddeville, P.; Fittschen, C.; El Dib, G.; Roth, E.; Chakir, A.

2014-12-01

Hydroxycarbonyl compounds are important secondary reaction products in the oxidation of Volatile Organic Compounds (VOCs) in the atmosphere. The atmospheric fate of these oxygenated VOCs is however poorly understood, especially the relevance of the photolytic pathway. In this work, a combined investigation of the photolysis and temperature-dependent OH radical reaction of 3-hydroxy-3-methyl-2-butanone (3H3M2B) is presented. A photolysis lifetime of about 4-5 days was estimated with a global quantum yield of 0.10. The OH reaction rate coefficient follows the Arrhenius trend (298-356 K) and could be modelled through the following expression: k3H3M2B(T) = (5.12 ± 0.07) × 10-12 exp(-563 ± 119/T) in cm3 molecule-1 s-1. A 3H3M2B atmospheric lifetime of 15 days towards the OH radical was evaluated. Our results showed that the photolysis pathway is the major degradation channel for 3H3M2B. Photolysis products were identified and quantified in the present work with a carbon balance of around 80% enabling a reaction mechanism to be proposed. The present work underlines the need for further studies on the atmospheric chemistry of oxygenated VOCs.

Phenomenology of the sound-induced flash illusion.

PubMed

Abadi, Richard V; Murphy, Jonathan S

2014-07-01

Past studies, using pairings of auditory tones and visual flashes, which were static and coincident in space but variable in time, demonstrated errors in judging the temporal patterning of the visual flashes-the sound-induced flash illusion. These errors took one of the two forms: under-reporting (sound-induced fusion) or over-reporting (sound-induced fission) of the flash numbers. Our study had three objectives: to examine the robustness of both illusions and to consider the effects of stimulus set and response bias. To this end, we used an extended range of fixed spatial location flash-tone pairings, examined stimuli that were variable in space and time and measured confidence in judging flash numbers. Our results indicated that the sound-induced flash illusion is a robust percept, a finding underpinned by the confidence measures. Sound-induced fusion was found to be more robust than sound-induced fission and a most likely outcome when high numbers of flashes were incorporated within an incongruent flash-tone pairing. Conversely, sound-induced fission was the most likely outcome for the flash-tone pairing which contained two flashes. Fission was also shown to be strongly driven by stimuli confounds such as categorical boundary conditions (e.g. flash-tone pairings with ≤2 flashes) and compressed response options. These findings suggest whilst both fission and fusion are associated with 'auditory driving', the differences in the occurrence and strength of the two illusions not only reflect the separate neuronal mechanisms underlying audio and visual signal processing, but also the test conditions that have been used to investigate the sound-induced flash illusion.

A laboratory study of the UV Absorption Spectrum of the ClO Dimer (Cl2O2) and the Implications for Polar Stratospheric Ozone Depletion

NASA Astrophysics Data System (ADS)

Papanastasiou, D. K.; Papadimitriou, V. C.; Fahey, D. W.; Burkholder, J. B.

2009-12-01

Chlorine containing species play an important role in catalytic ozone depleting cycles in the Antarctic and Arctic stratosphere. The ClO dimer (Cl2O2) catalytic ozone destruction cycle accounts for the majority of the observed polar ozone loss. A key step in this catalytic cycle is the UV photolysis of Cl2O2. The determination of the Cl2O2 UV absorption spectrum has been the subject of several studies since the late 1980’s. Recently, Pope et al. (J. Phys. Chem. A, 111, 4322, 2007) reported significantly lower absorption cross sections for Cl2O2 for the atmospherically relevant wavelength region, >300 nm, than currently recommended for use in atmospheric models. If correct, the Pope et al. results would alter our understanding of the chemistry of polar ozone depletion significantly. In this study, the UV absorption spectrum and absolute cross sections of gas-phase Cl2O2 are reported for the wavelength range 200 - 420 nm at ~200 K. Sequential pulsed laser photolysis of various precursors were used to produce the ClO radical and Cl2O2 via the subsequent ClO + ClO + M reaction under static conditions. UV absorption spectra of the reaction mixture were measured using a diode array spectrometer after completion of the gas-phase radical chemistry. The spectral analysis utilized the observed isosbestic points, reaction stoichiometry, and chlorine mass balance to determine the UV spectrum and absolute cross section of Cl2O2. A complementary experimental technique similar to that used by Pope et al. was also used in this study. We obtained consistent Cl2O2 UV absorption spectra using the two different techniques. The Cl2O2 absorption cross sections for wavelengths in the 300 - 420 nm range were found to be in very good agreement with the values reported previously by Burkholder et al. (J. Phys. Chem. A, 94, 687, 1990) and significantly greater than the Pope et al. values in this atmospherically important wavelength region. A possible explanation for the disagreement with

Statistical Evolution of the Lightning Flash

NASA Astrophysics Data System (ADS)

Zoghzoghy, F. G.; Cohen, M.; Said, R.; Inan, U. S.

2012-12-01

Natural lightning is one of the most fascinating and powerful electrical processes on Earth. To date, the physics behind this natural phenomenon are not fully understood, due primarily to the difficulty of obtaining measurements inside thunderstorms and to the wide range of timescales involved (from nanoseconds to seconds). Our aim is to use accurate lightning geo-location data from the National Lightning Detection Network (NLDN) to study statistical patterns in lightning, taking advantage of the fact that millions of lightning flashes occur around the globe every day. We present two sets of results, one involving the patterns of flashes in a storm, and a second involving the patterns of strokes in a flash. These patterns can provide a surrogate measure of the timescales and the spatial extents of the underlying physical processes. First, we study the timescales of charge buildup inside thunderstorms. We find that, following a lightning flash, the probability of another neighboring flash decreases and takes tens of seconds to recover. We find that this suppression effect is a function of flash type, stroke peak current, cloud-to-ground (CG) stroke multiplicity, and other lightning and geographical parameters. We find that the probabilities of subsequent flashes are more suppressed following oceanic lightning, or following flashes with higher peak currents and/or higher multiplicities (for CG flashes). Second, we use NLDN data to study the evolution of the strokes within a CG flash. A CG flash typically includes multiple return strokes, which can occur in the same channel or in multiple channels within a few kilometers. We cluster NLDN stroke data into flashes and produce the probability density function of subsequent strokes as a function of distance and time-delays relative to the previous stroke. Using this technique, we investigate processes which occur during the CG lightning flash with nanosecond to millisecond timescales. For instance, our results suggest

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1977-01-01

Hydrogen is produced by the solar photolysis of water in a first photooxidation vessel with a transparent wall in the presence of a water soluble photooxidizable reagent and an insoluble hydrogen recombination catalyst. Simultaneously oxygen is produced in a second photoreduction reactor with a transparent wall in the presence of an insoluble photoreduction reagent catalyst. When spent, the solution from the first reactor is fed into the second reactor. A reaction occurs in the dark in which the redox reagents are regenerated, and the regenerated photooxidation reagent solution is recycled to the first reactor. The photoreduction-catalyst is a bifunctional reagent catalyst including a transition metal salt together with a hydroxyl or chlorohydroxyl decomposition catalyst of high area.

FLASH2: Operation, beamlines, and photon diagnostics

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

Plönjes, Elke, E-mail: elke.ploenjes@desy.de; Faatz, Bart; Kuhlmann, Marion

2016-07-27

FLASH2, a major extension of the soft X-ray free-electron laser FLASH at DESY, turns FLASH into a multi-user FEL facility. A new undulator line is located in a separate accelerator tunnel and driven additionally by the FLASH linear accelerator. First lasing of FLASH2 was achieved in August 2014 with simultaneous user operation at FLASH1. The new FLASH2 experimental hall offers space for up to six experimental end stations, some of which will be installed permanently. The wide wavelength range spans from 4-60 nm and 0.8 nm in the 5{sup th} harmonic and in the future deep into the water windowmore » in the fundamental. While this is of high interest to users, it is challenging from the beamline instrumentation point of view. Online diagnostics - which are mostly pulse resolved - for beam intensity, position, wavelength, wave front, and pulse length have been to a large extent developed at FLASH(1) and have now been optimized for FLASH2. Pump-probe facilities for XUV-XUV, XUV optical and XUV-THz experiments will complete the FLASH2 user facility.« less

FLASH LIDAR Based Relative Navigation

NASA Technical Reports Server (NTRS)

Brazzel, Jack; Clark, Fred; Milenkovic, Zoran

2014-01-01

Relative navigation remains the most challenging part of spacecraft rendezvous and docking. In recent years, flash LIDARs, have been increasingly selected as the go-to sensors for proximity operations and docking. Flash LIDARS are generally lighter and require less power that scanning Lidars. Flash LIDARs do not have moving parts, and they are capable of tracking multiple targets as well as generating a 3D map of a given target. However, there are some significant drawbacks of Flash Lidars that must be resolved if their use is to be of long-term significance. Overcoming the challenges of Flash LIDARs for navigation-namely, low technology readiness level, lack of historical performance data, target identification, existence of false positives, and performance of vision processing algorithms as intermediaries between the raw sensor data and the Kalman filter-requires a world-class testing facility, such as the Lockheed Martin Space Operations Simulation Center (SOSC). Ground-based testing is a critical step for maturing the next-generation flash LIDAR-based spacecraft relative navigation. This paper will focus on the tests of an integrated relative navigation system conducted at the SOSC in January 2014. The intent of the tests was to characterize and then improve the performance of relative navigation, while addressing many of the flash LIDAR challenges mentioned above. A section on navigation performance and future recommendation completes the discussion.

Degradation of florfenicol in water by UV/Na2S 2O 8 process.

PubMed

Gao, Yu-Qiong; Gao, Nai-Yun; Deng, Yang; Yin, Da-Qiang; Zhang, Yan-Sen

2015-06-01

UV irradiation-activated sodium persulfate (UV/PS) was studied to degrade florfenicol (FLO), a phenicol antibiotic commonly used in aquaculture, in water. Compared with UV/H2O2 process, UV/PS process achieves a higher FLO degradation efficiency, greater mineralization, and less cost. The quantum yield for direct photolysis of FLO and the second-order rate constant of FLO with sulfate radicals were determined. The effects of various factors, namely PS concentration, anions (NO3 (-), Cl(-), and HCO3 (-)), ferrous ion, and humic acid (HA), on FLO degradation were investigated. The results showed that the pseudo-first-order rate constant increased linearly with increased PS concentration. The tested anions all adversely affected FLO degradation performance with the order of HCO3 (-) > Cl(-) > NO3 (-). Coexisting ferrous ions enhanced FLO degradation at a Fe(2+)/PS molar ratio under 1:1. HA significantly inhibited FLO degradation due to radical scavenging and light-screening effect. Toxicity assessment showed that it is capable of controlling the toxicity for FLO degradation. These findings indicated that UV/PS is a promising technology for water polluted by antibiotics, and the treatment is optimized only after the impacts of water characteristics are carefully considered.

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

PubMed Central

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

2014-01-01

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

UV-B Measurements in Mexico City: Comparison with Modeled UVB and Black Carbon

NASA Astrophysics Data System (ADS)

Marley, N. A.; Gaffney, J. S.; Frederick, J. E.

2004-12-01

Ultraviolet-B radiation (UV-B) represents a chemically important region of the sun's spectrum. At the earth's surface, UV-B can initiate a number of important photochemical reactions (e.g., ozone photolysis) that lead to the formation of OH radicals. Where levels of nitrogen oxides are high and reactive hydrocarbons are found, as in Mexico City and other megacities, UV-B can initiate photochemical smog formation. We used a broadband instrument to obtain UV-B measurements in Mexico City during the Mexico City Metropolitan Area 2003/Mexico City Megacity 2003 field study. We then used a simple radiation model for the Mexico City latitude, altitude, and time of year to construct UV-B contours for comparison with our results. Early morning discrepancies involve reductions in UV-B that are consistent with the presence of significant levels of BC in the Mexico City environment. During most afternoons, UV-B reductions were dominated by clouds. The results are discussed in terms of the potential impacts of BC on UV-B and downwind photochemical processes. The authors wish to thank the researchers at Centro Nacional de Investigación en Calidad Ambiental (CENICA), Mexico City. This work was supported by the U.S. Department of Energy, Atmospheric Science Program (Marley and Gaffney), and the U.S. Environmental Protection Agency (Frederick). We also wish to acknowledge Drs. Mario and Luisa Molina for their help in organizing and directing the Mexico City Metropolitan Area 2003 field study, during which these data were collected.

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

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

Hull, Emily A.; West, Aaron C.; Pestovsky, Oleg

2015-01-22

In this paper, transition metal complexes (NH 3) 5CoX2 + (X = CH 3, Cl) and L(H 2O)MX 2+, where M = Rh or Co, X = CH 3, NO, or Cl, and L is a macrocyclic N 4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH 3) 5CoCH 3 2+ and L(H 2O)M IIIX 2+ (X = CH 3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the othermore » hand, when X = halide or NO 2, visible light photolysis leads to dissociation of X – and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO 2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH 3) 5CoCH 3 2+ and L 1(H 2O)CoCH 3 2+.« less

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation.

PubMed

Hull, Emily A; West, Aaron C; Pestovsky, Oleg; Kristian, Kathleen E; Ellern, Arkady; Dunne, James F; Carraher, Jack M; Bakac, Andreja; Windus, Theresa L

2015-02-28

Transition metal complexes (NH3)5CoX(2+) (X = CH3, Cl) and L(H2O)MX(2+), where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH3(2+) and L(H2O)M(III)X(2+) (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X(-) and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH3(2+) and L(1)(H2O)CoCH3(2+).

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-03-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

NIR small arms muzzle flash

NASA Astrophysics Data System (ADS)

Montoya, Joseph; Kennerly, Stephen; Rede, Edward

2010-04-01

Utilization of Near-Infrared (NIR) spectral features in a muzzle flash will allow for small arms detection using low cost silicon (Si)-based imagers. Detection of a small arms muzzle flash in a particular wavelength region is dependent on the intensity of that emission, the efficiency of source emission transmission through the atmosphere, and the relative intensity of the background scene. The NIR muzzle flash signature exists in the relatively large Si spectral response wavelength region of 300 nm-1100 nm, which allows for use of commercial-off-the-shelf (COTS) Si-based detectors. The alkali metal origin of the NIR spectral features in the 7.62 × 39-mm round muzzle flash is discussed, and the basis for the spectral bandwidth is examined, using a calculated Voigt profile. This report will introduce a model of the 7.62 × 39-mm NIR muzzle flash signature based on predicted source characteristics. Atmospheric limitations based on NIR spectral regions are investigated in relation to the NIR muzzle flash signature. A simple signal-to-clutter ratio (SCR) metric is used to predict sensor performance based on a model of radiance for the source and solar background and pixel registered image subtraction.

Menopausal Hot Flashes and White Matter Hyperintensities

PubMed Central

Thurston, Rebecca C.; Aizenstein, Howard J.; Derby, Carol A.; Sejdić, Ervin; Maki, Pauline M.

2015-01-01

Objective Hot flashes are the classic menopausal symptom. Emerging data links hot flashes to cardiovascular disease (CVD) risk, yet how hot flashes are related to brain health is poorly understood. We examined the relationship between hot flashes - measured via physiologic monitor and self-report - and white matter hyperintensities (WMH) among midlife women. Methods Twenty midlife women ages 40-60 without clinical CVD, with their uterus and both ovaries, and not taking hormone therapy were recruited. Women underwent 24 hours of ambulatory physiologic and diary hot flash monitoring to quantify hot flashes; magnetic resonance imaging to assess WMH burden; 72 hours of actigraphy and questionnaires to quantify sleep; and a blood draw, questionnaires, and physical measures to quantify demographics and CVD risk factors. Test of a priori hypotheses regarding relations between physiologically-monitored and self-reported wake and sleep hot flashes and WMH were conducted in linear regression models. Results More physiologically-monitored hot flashes during sleep were associated with greater WMH, controlling for age, race, and body mass index [beta(standard error)=.0002 (.0001), p=.03]. Findings persisted controlling for sleep characteristics and additional CVD risk factors. No relations were observed for self-reported hot flashes. Conclusions More physiologically-monitored hot flashes during sleep were associated with greater WMH burden among midlife women free of clinical CVD. Results suggest that relations between hot flashes and CVD risk observed in the periphery may extend to the brain. Future work should consider the unique role of sleep hot flashes in brain health. PMID:26057822

H2 formation via the UV photo-processing of a-C:H nano-particles

NASA Astrophysics Data System (ADS)

Jones, A. P.; Habart, E.

2015-09-01

Context. The photolysis of hydrogenated amorphous carbon, a-C(:H), dust by UV photon-irradiation in the laboratory leads to the release of H2 as well as other molecules and radicals. This same process is also likely to be important in the interstellar medium. Aims: We investigate molecule formation arising from the photo-dissociatively-driven, regenerative processing of a-C(:H) dust. Methods: We explore the mechanism of a-C(:H) grain photolysis leading to the formation of H2 and other molecules/radicals. Results: The rate constant for the photon-driven formation of H2 from a-C(:H) grains is estimated to be 2 × 10-17 cm3 s-1. In intense radiation fields photon-driven grain decomposition will lead to fragmentation into daughter species rather than H2 formation. Conclusions: The cyclic re-structuring of arophatic a-C(:H) nano-particles appears to be a viable route to formation of H2 for low to moderate radiation field intensities (1 ≲ G0 ≲ 102), even when the dust is warm (T ~ 50-100 K).

Gun muzzle blast and flash

NASA Astrophysics Data System (ADS)

Klingenberg, Guenter; Heimerl, Joseph M.

A repository of fundamental experimental and analytical data concerning the complex phenomena associated with gun-muzzle blast and flash effects is presented, proceeding from gun muzzle signatures to modern gun-propulsion concepts, interior and transitional ballistics, and characterizations of blast-wave research and muzzle flash. Data are presented in support of a novel hypothesis which explains the ignition of secondary flash and elucidates the means for its suppression. Both chemical and mechanical (often competing) methods of flash suppression are treated. The historical work of Kesslau and Ladenburg is noted, together with French, British, Japanese and American research efforts and current techniques of experimental characterization for gun muzzle phenomena.

Ice chemistry on outer solar system bodies: Carboxylic acids, nitriles, and urea detected in refractory residues produced from the UV photolysis of N{sub 2}:CH{sub 4}:CO-containing ices

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

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.

Radiation processing of the surface ices of outer solar system bodies may result in the production of new chemical species even at low temperatures. Many of the smaller, more volatile molecules that are likely produced by the photolysis of these ices have been well characterized by laboratory experiments. However, the more complex refractory material formed in these experiments remains largely uncharacterized. In this work, we present a series of laboratory experiments in which low-temperature (15-20 K) N{sub 2}:CH{sub 4}:CO ices in relative proportions 100:1:1 are subjected to UV irradiation, and the resulting materials are studied with a variety of analyticalmore » techniques including infrared spectroscopy, X-ray absorption near-edge structure spectroscopy, gas chromatography coupled with mass spectrometry, and high-resolution mass spectroscopy. Despite the simplicity of the reactants, these experiments result in the production of a highly complex mixture of molecules from relatively low-mass volatiles (tens of daltons) to high-mass refractory materials (hundreds of daltons). These products include various carboxylic acids, nitriles, and urea, which are also expected to be present on the surface of outer solar system bodies, including Pluto and other transneptunian objects. If these compounds occur in sufficient concentrations in the ices of outer solar system bodies, their characteristic bands may be detectable in the near-infrared spectra of these objects.« less

Hold-up power supply for flash memory

NASA Technical Reports Server (NTRS)

Ott, William E. (Inventor)

2004-01-01

A hold-up power supply for flash memory systems is provided. The hold-up power supply provides the flash memory with the power needed to temporarily operate when a power loss exists. This allows the flash memory system to complete any erasures and writes, and thus allows it to shut down gracefully. The hold-up power supply detects when a power loss on a power supply bus is occurring and supplies the power needed for the flash memory system to temporally operate. The hold-up power supply stores power in at least one capacitor. During normal operation, power from a high voltage supply bus is used to charge the storage capacitors. When a power supply loss is detected, the power supply bus is disconnected from the flash memory system. A hold-up controller controls the power flow from the storage capacitors to the flash memory system. The hold-up controller uses feedback to assure that the proper voltage is provided from the storage capacitors to the flash memory system. This power supplied by the storage capacitors allows the flash memory system to complete any erasures and writes, and thus allows the flash memory system to shut down gracefully.

Impacts of cloud water droplets on the OH production rate from peroxide photolysis.

PubMed

Martins-Costa, M T C; Anglada, J M; Francisco, J S; Ruiz-López, Manuel F

2017-12-06

Understanding the difference between observed and modeled concentrations of HO x radicals in the troposphere is a current major issue in atmospheric chemistry. It is widely believed that existing atmospheric models miss a source of such radicals and several potential new sources have been proposed. In recent years, interest has increased on the role played by cloud droplets and organic aerosols. Computer modeling of ozone photolysis, for instance, has shown that atmospheric aqueous interfaces accelerate the associated OH production rate by as much as 3-4 orders of magnitude. Since methylhydroperoxide is a main source and sink of HO x radicals, especially at low NO x concentrations, it is fundamental to assess what is the influence of clouds on its chemistry and photochemistry. In this study, computer simulations for the photolysis of methylhydroperoxide at the air-water interface have been carried out showing that the OH production rate is severely enhanced, reaching a comparable level to ozone photolysis.

Degradation of pharmaceuticals in UV (LP)/H₂O₂ reactors simulated by means of kinetic modeling and computational fluid dynamics (CFD).

PubMed

Wols, B A; Harmsen, D J H; Wanders-Dijk, J; Beerendonk, E F; Hofman-Caris, C H M

2015-05-15

UV/H2O2 treatment is a well-established technique to degrade organic micropollutants. A CFD model in combination with an advanced kinetic model is presented to predict the degradation of organic micropollutants in UV (LP)/H2O2 reactors, accounting for the hydraulics, fluence rate, complex (photo)chemical reactions in the water matrix and the interactions between these processes. The model incorporates compound degradation by means of direct UV photolysis, OH radical and carbonate radical reactions. Measurements of pharmaceutical degradations in pilot-scale UV/H2O2 reactors are presented under different operating conditions. A comparison between measured and modeled degradation for a group of 35 pharmaceuticals resulted in good model predictions for most of the compounds. The research also shows that the degradation of organic micropollutants can be dependent on temperature, which is relevant for full-scale installations that are operated at different temperatures over the year. Copyright © 2015 Elsevier Ltd. All rights reserved.

49 CFR 234.217 - Flashing light units.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Flashing light units. 234.217 Section 234.217..., Inspection, and Testing Maintenance Standards § 234.217 Flashing light units. (a) Each flashing light unit.... (b) Each flashing light unit shall be maintained to prevent dust and moisture from entering the...

49 CFR 234.217 - Flashing light units.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 4 2011-10-01 2011-10-01 false Flashing light units. 234.217 Section 234.217..., Inspection, and Testing Maintenance Standards § 234.217 Flashing light units. (a) Each flashing light unit.... (b) Each flashing light unit shall be maintained to prevent dust and moisture from entering the...

Photolysis of α-KETO Acids in Model Atmospheric Water

NASA Astrophysics Data System (ADS)

Eugene, A. J.; Guzman, M. I.

2017-12-01

Recent work has reported the potential of aqueous-phase photochemistry to promote secondary organic aerosol (SOA) formation. New aqueous photochemical SOA sources may contribute to bridging the gap between field measurements of SOA and models of SOA formation. The ubiquitous α-ketocarboxylic acids pyruvic and glyoxylic acid are known products of the atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) as well as of biogenic volatile organic compounds (VOCs). The combination of a carbonyl chromophore (absorbing at wavelengths λ ≥ 300 nm) and hydrophilic functional groups makes these acids likely candidates for forming aqueous SOA by direct sunlight photolysis. We use a variety of analytical techniques including: 2,4-dinitrophenylhydrazine (DNPH) derivatization; ultra-high performance liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry;1H and 13C NMR; and 13C gCOSY NMR to probe the kinetics and mechanisms of the direct photolysis of model solutions of pyruvic acid and glyoxylic acid. The results indicate that despite the structural similarity between the two acids, they each react via very different primary photochemical pathways. Pyruvic acid undergoes a proton-coupled electron transfer (PCET) mechanism with radical recombination, resulting in CO2 and 6-8 carbon organic acids. In contrast, glyoxylic acid primarily undergoes α-cleavage to generate CO, CO2, and glyoxal which is a key species in SOA formation. This work demonstrates that aqueous photolysis is a very competitive atmospheric sink for both pyruvic and glyoxylic acid, indicating that these photoreactions are capable of contributing substantially to SOA formation.

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation.

PubMed

Ding, Shi-Ling; Wang, Xi-Kui; Jiang, Wen-Qiang; Meng, Xia; Zhao, Ru-Song; Wang, Chen; Wang, Xia

2013-05-01

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.

Measuring hot flash phenomenonology using ambulatory prospective digital diaries

PubMed Central

Fisher, William I.; Thurston, Rebecca C.

2016-01-01

Objective This study provides the description, protocol, and results from a novel prospective ambulatory digital hot flash phenomenon diary. Methods This study included 152 midlife women with daily hot flashes who completed an ambulatory electronic hot flash diary continuously for the waking hours of 3 consecutive days. In this diary, women recorded their hot flashes and accompanying characteristics and associations as the hot flashes occurred. Results Self-reported hot flash severity on the digital diaries indicated that the majority of hot flashes were rated as mild (41.3%) or moderate (43.7%). Severe (13.1%) and very severe (1.8%) hot flashes were less common. Hot flash bother ratings were rated as mild (43%), or moderate (33.5%), with fewer hot flashes reported bothersome (17.5%) or very bothersome (6%). The majority of hot flashes were reported as occurring on the on the face (78.9%), neck (74.7%), and chest (61.3%). Prickly skin was reported concurrently with 32% of hot flashes, 7% with anxiety and 5% with nausea. A novel finding, 38% of hot flashes were accompanied by a premonitory aura. Conclusion A prospective electronic digital hot flash diary allows for a more precise quantitation of hot flashes while overcoming many of the limitations of commonly employed retrospective questionnaires and paper diaries. Unique insights into the phenomenology, loci and associated characteristics of hot flashes were obtained using this device. The digital hot flash phenomenology diary is recommended for future ambulatory studies of hot flashes as a prospective measure of the hot flash experience. PMID:27404030

Measuring hot flash phenomenonology using ambulatory prospective digital diaries.

PubMed

Fisher, William I; Thurston, Rebecca C

2016-11-01

This study provides the description, protocol, and results from a novel prospective ambulatory digital hot flash phenomenon diary. This study included 152 midlife women with daily hot flashes who completed an ambulatory electronic hot flash diary continuously for the waking hours of three consecutive days. In this diary, women recorded their hot flashes and accompanying characteristics and associations as the hot flashes occurred. Self-reported hot flash severity on the digital diaries indicated that the majority of hot flashes were rated as mild (41.3%) or moderate (43.7%). Severe (13.1%) and very severe (1.8%) hot flashes were less common. Hot flash bother ratings were rated as mild (43%), or moderate (33.5%), with fewer hot flashes reported bothersome (17.5%) or very bothersome (6%). The majority of hot flashes were reported as occurring on the face (78.9%), neck (74.7%), and chest (61.3%). Of all reported hot flashes, 32% occurred concurrently with prickly skin, 7% with anxiety, and 5% with nausea. A novel finding from the study was that 38% of hot flashes were accompanied by a premonitory aura. A prospective electronic digital hot flash diary allows for a more precise quantitation of hot flashes while overcoming many of the limitations of commonly used retrospective questionnaires and paper diaries. Unique insights into the phenomenology, loci, and associated characteristics of hot flashes were obtained using this device. The digital hot flash phenomenology diary is recommended for future ambulatory studies of hot flashes as a prospective measure of the hot flash experience.

Transient spectra study on photo-dynamics of curcumin

NASA Astrophysics Data System (ADS)

Qian, Tingting; Wang, Mei; Wang, Jiao; Zhu, Rongrong; He, Xiaolie; Sun, Xiaoyu; Sun, Dongmei; Wang, Qingxiu; Wang, ShiLong

2016-09-01

A novel mechanism of DNA damage induced by photosensitized curcumin (Cur) was explored using laser flash photolysis, pulse radiolysis and gel electrophoresis. Cur neutral radical (Currad) was confirmed as an identical product in photo-sensitization of Cur by laser flash photolysis and pulse radiolysis. A series of reaction rate constants between Currad and nucleic acid bases/nucleotides were determined by pulse radiolysis. Gel electrophoresis was carried out to investigate damage induced by photosensitized Cur to biologically active DNA. The results indicate that the damage to DNA may be caused by Currad produced from the photosensitization of Cur.

Enhanced Photolysis of Nucleic Acid Monomers by Pyrophosphate in the Simulated Primitive Soup

NASA Astrophysics Data System (ADS)

Kongjiang, Wang; Zhifang, Chai; Xianming, Pan

1999-05-01

In our simulation of the photochemistry of the primitive soup, it was found that yield of chromophore loss of some nucleic acid bases, nucleosides and nucleotides [NA] undergoing ultraviolet radiation by medium pressure mercury lamp [MPML] was enhanced by pyrophosphate and triphosphate whether O2 is present or not. The yield of chromophore loss of guanosine, uracil, 5' CMP, and the derivatives of adenine and thymine was observed to rise with the increase of molar concentration of pyrophosphate in N2-saturated systems. In air-saturated samples, increase in yield of chromophore loss was observed when the concentration of pyrophosphate reaches 5×10-4 M, relative yield of chromophore loss (CLrel) coming to maximum in the range from 0.01 to 0.1 M, followed by a slight decline with the further increase of pyrophosphate concentration. The enhancement of photolysis of NA by pyrophosphate was due to the interaction between NA and pyrophosphate radicals photoionized by UV quanta of wavelength less than about 210 nm in the emission spectrum of a MPML. The relevance of this phenomenon to the origin of life has been discussed as well.

Mercury-arc photolysis: a method for examining second messenger regulation of endothelial cell monolayer integrity.

PubMed

Patton, W F; Alexander, J S; Dodge, A B; Patton, R J; Hechtman, H B; Shepro, D

1991-07-01

Cell-cell apposition in bovine pulmonary endothelial cell monolayers was modulated by inducing transient increases in intracellular adenosine 3':5'-cyclic monophosphate (cAMP) and 1,4,5-inositol triphosphate (IP3). This was accomplished by mercury-arc flash photolysis of o-nitrobenzyl derivatives of the second messengers (caged compounds). Second messenger release by the mercury-arc lamp was determined by radioimmunoassay of cAMP to have a t1/2 of approximately 8 min. Each second messenger induced the phosphorylation of a distinct subset of cytoskeletal proteins; however, both IP3 and cAMP increased vimentin phosphorylation. Actin isoform patterns were not altered by the second messengers. Intracellular pulses of IP3 in pulmonary endothelial cells caused disruption of endothelial monolayer integrity as determined by phase-contrast microscopy and by visualization of actin stress fibers with rhodamine-phalloidin. Intracellular pulses of cAMP increased cell-cell contact, cell surface area, and apposition. IP3 appeared to have its greatest effect on the actin peripheral band. In silicone rubber contractility assays this agent caused contraction of pulmonary microvascular endothelial cells as visualized by an increase in wrinkles beneath the cells. On the other hand, cAMP appeared to effect both the peripheral band and centralized actin domains. Caged cAMP caused relaxation of endothelial cells as visualized by a disappearance of wrinkles beneath the cells.

Nitryl chloride (ClNO2): UV/vis absorption spectrum between 210 and 296 K and O(3P) quantum yield at 193 and 248 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Roberts, James M; Burkholder, James B

2012-06-21

Recent studies have shown that the UV/vis photolysis of nitryl chloride (ClNO2) can be a major source of reactive chlorine in the troposphere. The present work reports measurements of the ClNO2 absorption spectrum and its temperature dependence between 210 and 296 K over the wavelength range 200–475 nm using diode array spectroscopy. The room temperature spectrum obtained in this work was found to be in good agreement with the results from Ganske et al. (J. Geophys. Res. 1992, 97, 7651) over the wavelength range common to both studies (200–370 nm) but differs systematically from the currently recommended spectrum for use in atmospheric models. The present results lead to a decrease in the calculated atmospheric ClNO2 photolysis rate by 30%. Including the temperature dependence of the ClNO2 spectrum decreases the calculated atmospheric photolysis rate at lower temperatures (higher altitudes) even further. A parametrization of the wavelength and temperature dependence of the ClNO2 spectrum is presented. O(3P) quantum yields, Φ(ClNO2)(O), in the photolysis of ClNO2 at 193 and 248 nm were measured at 296 K using pulsed laser photolysis combined with atomic resonance fluorescence detection of O(3P) atoms. Φ(ClNO2)(O)(λ) was found to be 0.67 ± 0.12 and 0.15 ± 0.03 (2σ error limits, including estimated systematic errors) at 193 and 248 nm, respectively, indicating that multiple dissociation channels are active in the photolysis of ClNO2 at these wavelengths. The Φ(ClNO2)(O)(λ) values obtained in this work are discussed in light of previous ClNO2 photodissociation studies and the differences are discussed.

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

PubMed

Wentrup, Curt

2017-03-08

Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N 2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N 2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

The role of UV-irradiation pretreatment on the degradation of 2,4-dichlorophenoxyacetic acid in water.

PubMed

Tchaikovskaya, O; Sokolova, I; Mayer, G V; Karetnikova, E; Lipatnikova, E; Kuzmina, S; Volostnov, D

2011-01-01

The degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in water by the combination process of UV-irradiation, humic acids and activated sludge treatment has been studied. The photoreaction rate of all irradiated samples was lowest for the sample irradiated at 308 nm (the XeCl excilamp) in the absence and in the presence of humic acids, and highest for the sample irradiated at 222 nm (the KrCl excilamp). Photolysis of 2,4-D has been shown to enhance the subsequent microbial degradation. Copyright © 2010 John Wiley & Sons, Ltd.

Electronic Flash In Data Acquisition

NASA Astrophysics Data System (ADS)

Miller, C. E.

1982-02-01

Photographic acquisition of data often may be simplified, or the data quality improved upon by employing electronic flash sources with traditional equipment or techniques. The relatively short flash duration compared to movie camera shutters, or to the long integration time of video camera provides improved spatial resolution through blur reduction, particularly important as image movement becomes a significant fraction of film format dimension. Greater accuracy typically is achieved in velocity and acceleration determinations by using a stroboscopic light source rather than a movie camera frame-rate control as a time standard. Electrical efficiency often is an important advantage of electronic flash sources since almost any necessary light level for exposure may be produced, yet the source typically is "off" most of the time. Various synchronization techniques greatly expand the precise control of exposure. Biomechanical and sports equipment studies may involve velocities up to 200 feet-per-second, and often will have associated very rapid actions of interest. The need for brief exposures increases H.s one "ZOOMS in on the action." In golf, for example, the swing may be examined using 100 microsecond (Us) flashes at rates of 60 or 120 flashes-per-second (FPS). Accurate determination of linear and rotational velocity of the ball requires 10 Us flashes at 500-1,000 FPS, while sub-Us flashes at 20,000-50,000 FPS are required to resolve the interaction of the ball and the club, head. Some seldom. used techniques involving streak photography are described, with enhanced results obtained by combining strobe with the usual continuous light source. The combination of strobe and a fast electro-mechanical shutter is considered for Us photography under daylight conditions.

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

Transformation efficiency and formation of transformation products during photochemical degradation of TCE and PCE at micromolar concentrations

PubMed Central

2014-01-01

Background Trichloroethene and tetrachloroethene are the most common pollutants in groundwater and two of the priority pollutants listed by the U.S. Environmental Protection Agency. In previous studies on TCE and PCE photolysis and photochemical degradation, concentration ranges exceeding environmental levels by far with millimolar concentrations of TCE and PCE have been used, and it is not clear if the obtained results can be used to explain the degradation of these contaminants at more realistic environmental concentration levels. Methods Experiments with micromolar concentrations of TCE and PCE in aqueous solution using direct photolysis and UV/H2O2 have been conducted and product formation as well as transformation efficiency have been investigated. SPME/GC/MS, HPLC/UV and ion chromatography with conductivity detection have been used to determine intermediates of degradation. Results The results showed that chloride was a major end product in both TCE and PCE photodegradation. Several intermediates such as formic acid, dichloroacetic acid, dichloroacetaldehyede, chloroform, formaldehyde and glyoxylic acid were formed during both, UV and UV/H2O2 treatment of TCE. However chloroacetaldehyde and chloroacetic acid were only detected during direct UV photolysis of TCE and oxalic acid was only formed during the UV/H2O2 process. For PCE photodegradation, formic acid, di- and trichloroacetic acids were detected in both UV and UV/H2O2 systems, but formaldehyde and glyoxylic acid were only detected during direct UV photolysis. Conclusions For water treatment UV/H2O2 seems to be favorable over direct UV photolysis because of its higher degradation efficiency and lower risk for the formation of harmful intermediates. PMID:24401763

Transformation efficiency and formation of transformation products during photochemical degradation of TCE and PCE at micromolar concentrations.

PubMed

Dobaradaran, Sina; Lutze, Holger; Mahvi, Amir Hossein; Schmidt, Torsten C

2014-01-08

Trichloroethene and tetrachloroethene are the most common pollutants in groundwater and two of the priority pollutants listed by the U.S. Environmental Protection Agency. In previous studies on TCE and PCE photolysis and photochemical degradation, concentration ranges exceeding environmental levels by far with millimolar concentrations of TCE and PCE have been used, and it is not clear if the obtained results can be used to explain the degradation of these contaminants at more realistic environmental concentration levels. Experiments with micromolar concentrations of TCE and PCE in aqueous solution using direct photolysis and UV/H2O2 have been conducted and product formation as well as transformation efficiency have been investigated. SPME/GC/MS, HPLC/UV and ion chromatography with conductivity detection have been used to determine intermediates of degradation. The results showed that chloride was a major end product in both TCE and PCE photodegradation. Several intermediates such as formic acid, dichloroacetic acid, dichloroacetaldehyede, chloroform, formaldehyde and glyoxylic acid were formed during both, UV and UV/H2O2 treatment of TCE. However chloroacetaldehyde and chloroacetic acid were only detected during direct UV photolysis of TCE and oxalic acid was only formed during the UV/H2O2 process. For PCE photodegradation, formic acid, di- and trichloroacetic acids were detected in both UV and UV/H2O2 systems, but formaldehyde and glyoxylic acid were only detected during direct UV photolysis. For water treatment UV/H2O2 seems to be favorable over direct UV photolysis because of its higher degradation efficiency and lower risk for the formation of harmful intermediates.

Conjunctival UV autofluorescence--prevalence and risk factors.

PubMed

Wolffsohn, James S; Drew, Tom; Sulley, Anna

2014-12-01

Autofluorescence of ultraviolet (UV) light has been shown to occur in localised areas of the bulbar conjunctiva, which map to active cellular changes due to UV and environmental exposure. This study examined the presence of conjunctival UV autofluorescence in eye care practitioners (ECPs) across Europe and the Middle East and its associated risk factors. Images were captured of 307 ECPs right eyes in the Czech Republic, Germany, Greece, Kuwait, Netherlands, Sweden, Switzerland, United Arab Emirates and the United Kingdom using a Nikon D100 camera and dual flash units through UV filters. UV autofluorescence was outlined using ImageJ software and the nasal and temporal area quantified. Subjects were required to complete a questionnaire on their demographics and lifestyle including general exposure to UV and refractive correction. Average age of the subjects was 38.5±12.2 years (range 19-68) and 39.7% were male. Sixty-two percent of eyes had some conjunctival damage as indicated by UV autofluorescence. The average area of damage was higher (p=0.005) nasally (2.95±4.52mm(2)) than temporally (2.19±4.17mm(2)). The area of UV damage was not related to age (r=0.03, p=0.674), gender (p=0.194), self-reported sun exposure lifestyle (p>0.05), geographical location (p=0174), sunglasses use (p>0.05) or UV-blocking contact lens use (p>0.05), although it was higher in those wearing contact lenses with minimal UV-blocking and no spectacles (p=0.015). The area of UV damage was also less nasally in those who wore contact lenses and spectacles compared to those with no refractive correction use (p=0.011 nasal; p=0.958 temporal). UV conjunctival damage is common even in Europe, Kuwait and UAE, and among ECPs. The area of damage appears to be linked with the use of refractive correction, with greater damage nasally than temporally which may be explained by the peripheral light focusing effect. Copyright © 2014 British Contact Lens Association. Published by Elsevier Ltd. All rights

The photolysis of NH3 in the presence of substituted acetylenes - A possible source of oligomers and HCN on Jupiter

NASA Technical Reports Server (NTRS)

Ferris, James P.; Jacobson, Richard R.; Guillemin, Jean C.

1992-01-01

An NMR spectral study is presently conducted of NH3 photolysis in the presence of substituted acetylenes with NMR spectra and gas chromatography. Quantum yields and percentage conversions to products are reported. It is shown that acetylenic hydrocarbons generated during methane photolysis in Jupiter's stratosphere can react with radicals formed by NH3 photolysis to yield nonvolatile, yellow-brown polymers, alkylnitriles, and in due course, HCN, as observed on Jupiter.

Photodegradation of iodinated trihalomethanes in aqueous solution by UV 254 irradiation.

PubMed

Xiao, Yongjun; Fan, Rongli; Zhang, Lifeng; Yue, Junqi; Webster, Richard D; Lim, Teik-Thye

2014-02-01

Photodegradation of 6 iodinated trihalomethanes (ITHMs) under UV irradiation at 254 nm was investigated in this study. ITHMs underwent a rapid photodegradation process through cleavage of carbon-halogen bond with first-order rate constants in the range of 0.1-0.6 min(-1). The effects of matrix species including nitrate, humic acid (HA), bicarbonate, sulfate, and chloride were evaluated. The degradation rate increased slightly in the presence of nitrate possibly due to generation of HO at a low quantum yield via direct photolysis of nitrate, while HA lowered the photodegradation rate of ITHMs due to its competitive UV absorption. Moreover, bicarbonate, sulfate, and chloride had no significant effect on photodegradation kinetics, as there is no UV absorption for these 3 species. In the study using surface water, treated water, and secondary effluent from a wastewater treatment plant, high turbidity and natural organic matters present in the water inhibited the photodegradation of ITHMs. The degradation rates of 6 ITHMs in UV/H2O2 system were rather comparable and significantly higher than those achieved in the UV system without H2O2. To develop a quantitative structure-reactivity relationship (QSAR) model, the logarithm of measured first-order rate constants was correlated with a number of molecular descriptors. The best correlation was obtained with a combination of 3 molecular descriptors, namely the bond strength of carbon-halogen to be broken in the rate-determining step, steric and electronic effects of all substituents to the carbon center. Copyright © 2013 Elsevier Ltd. All rights reserved.

Recent Progress Made in the Development of High-Energy UV Transmitter

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.; Singh, Upendra N.; Armstrong, Darrell J.

2007-01-01

In this paper, the status of an all-solid-state UV converter development for ozone sensing applications is discussed. A high energy Nd:YAG laser for pumping the UV converter arrangement was recently reported. The pump is an all-solid-state, single longitudinal mode, and conductively cooled Nd:YAG laser operating at 1064 nm wavelength. Currently, this pump laser provides an output pulse energy of greater than 1J/pulse at 50 Hz PRF and a pulsewidth of 22 ns with an electrical-to-optical system efficiency of greater than 7% and a M(sup 2) value of approx. 2. The spatial profile of the output beam is a rectangular super Gaussian. This Nd:YAG pump laser has been developed to pump the nonlinear optics based UV converter arrangement to generate 320 nm and 308 nm wavelengths by means of 532 nm wavelength. Previously, this UV converter arrangement has demonstrated IR-to-UV conversion efficiency of 24% using a flash lamp pumped laser providing a round, flat top spatial profile. Recently, the UV converter was assembled and tested at NASA LaRC for pumping with the diode pumped Nd:YAG laser. With current spatial profile, the UV converter was made operational. Current efforts to maximize the nonlinear conversion efficiency by refining its spatial profile to match RISTRA OPO requirements are progressing.

An Analysis of Total Lightning Flash Rates Over Florida

NASA Astrophysics Data System (ADS)

Mazzetti, Thomas O.; Fuelberg, Henry E.

2017-12-01

Although Florida is known as the "Sunshine State", it also contains the greatest lightning flash densities in the United States. Flash density has received considerable attention in the literature, but lightning flash rate has received much less attention. We use data from the Earth Networks Total Lightning Network (ENTLN) to produce a 5 year (2010-2014) set of statistics regarding total flash rates over Florida and adjacent regions. Instead of tracking individual storms, we superimpose a 0.2° × 0.2° grid over the study region and count both cloud-to-ground (CG) and in-cloud (IC) flashes over 5 min intervals. Results show that the distribution of total flash rates is highly skewed toward small values, whereas the greatest rate is 185 flashes min-1. Greatest average annual flash rates ( 3 flashes min-1) are located near Orlando. The southernmost peninsula, North Florida, and the Florida Panhandle exhibit smaller average annual flash rates ( 1.5 flashes min-1). Large flash rates > 100 flashes min-1 can occur during any season, at any time during the 24 h period, and at any location within the domain. However, they are most likely during the afternoon and early evening in East Central Florida during the spring and summer months.

CFCI3 (CFC-11): UV Absorption Spectrum Temperature Dependence Measurements and the Impact on Atmospheric Lifetime and Uncertainty

NASA Technical Reports Server (NTRS)

Mcgillen, Max R.; Fleming, Eric L.; Jackman, Charles H.; Burkholder, James B.

2014-01-01

CFCl3 (CFC-11) is both an atmospheric ozone-depleting and potent greenhouse gas that is removed primarily via stratospheric UV photolysis. Uncertainty in the temperature dependence of its UV absorption spectrum is a significant contributing factor to the overall uncertainty in its global lifetime and, thus, model calculations of stratospheric ozone recovery and climate change. In this work, the CFC-11 UV absorption spectrum was measured over a range of wavelength (184.95 - 230 nm) and temperature (216 - 296 K). We report a spectrum temperature dependence that is less than currently recommended for use in atmospheric models. The impact on its atmospheric lifetime was quantified using a 2-D model and the spectrum parameterization developed in this work. The obtained global annually averaged lifetime was 58.1 +- 0.7 years (2 sigma uncertainty due solely to the spectrum uncertainty). The lifetime is slightly reduced and the uncertainty significantly reduced from that obtained using current spectrum recommendations

A global flash flood forecasting system

NASA Astrophysics Data System (ADS)

Baugh, Calum; Pappenberger, Florian; Wetterhall, Fredrik; Hewson, Tim; Zsoter, Ervin

2016-04-01

The sudden and devastating nature of flash flood events means it is imperative to provide early warnings such as those derived from Numerical Weather Prediction (NWP) forecasts. Currently such systems exist on basin, national and continental scales in Europe, North America and Australia but rely on high resolution NWP forecasts or rainfall-radar nowcasting, neither of which have global coverage. To produce global flash flood forecasts this work investigates the possibility of using forecasts from a global NWP system. In particular we: (i) discuss how global NWP can be used for flash flood forecasting and discuss strengths and weaknesses; (ii) demonstrate how a robust evaluation can be performed given the rarity of the event; (iii) highlight the challenges and opportunities in communicating flash flood uncertainty to decision makers; and (iv) explore future developments which would significantly improve global flash flood forecasting. The proposed forecast system uses ensemble surface runoff forecasts from the ECMWF H-TESSEL land surface scheme. A flash flood index is generated using the ERIC (Enhanced Runoff Index based on Climatology) methodology [Raynaud et al., 2014]. This global methodology is applied to a series of flash floods across southern Europe. Results from the system are compared against warnings produced using the higher resolution COSMO-LEPS limited area model. The global system is evaluated by comparing forecasted warning locations against a flash flood database of media reports created in partnership with floodlist.com. To deal with the lack of objectivity in media reports we carefully assess the suitability of different skill scores and apply spatial uncertainty thresholds to the observations. To communicate the uncertainties of the flash flood system output we experiment with a dynamic region-growing algorithm. This automatically clusters regions of similar return period exceedence probabilities, thus presenting the at-risk areas at a spatial

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

PubMed

Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

2016-04-05

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Simulation of flashing signal operations.

DOT National Transportation Integrated Search

1982-01-01

Various guidelines that have been proposed for the operation of traffic signals in the flashing mode were reviewed. The use of existing traffic simulation procedures to evaluate flashing signals was examined and a study methodology for simulating and...

Flash Inactivation of Oxygen Evolution

PubMed Central

Frasch, Wayne D.; Cheniae, George M.

1980-01-01

Brief saturating light flashes were used to probe the mechanism of inactivation of O2 evolution by Tris in chloroplasts. Maximum inactivation with a single flash and an oscillation with period of four on subsequent flashes was observed. Analyses of the oscillations suggested that only the charge-collecting O2-evolving catalyst of photosystem II (S2-state) was a target of inactivation by Tris. This conclusion was supported by the following observations: (a) hydroxylamine preequilibration caused a three-flash delay in the inactivation pattern; (b) the lifetimes of the Tris-inactivable and S2-states were similar; and (c) reagents accelerating S2 deactivation decreased the lifetime of the inactivable state. Inactivation proved to be moderated by F, the precursor of Signal IIs, as shown by a one flash delay with chloroplasts having high abundance of F. Evidence was obtained for cooperativity effects in inactivation and NH3 was shown to be a competitive inhibitor of the Tris-induced inactivation. S2-dependent inactivation was inhibited by glutaraldehyde fixation of chloroplasts, possibly suggesting that inactivation proceeds via conformational changes of the S2-state. PMID:16661270

Micropollutants removal by full-scale UV-C/sulfate radical based Advanced Oxidation Processes.

PubMed

Rodríguez-Chueca, J; Laski, E; García-Cañibano, C; Martín de Vidales, M J; Encinas, Á; Kuch, B; Marugán, J

2018-07-15

The high chemical stability and the low biodegradability of a vast number of micropollutants (MPs) impede their correct treatment in urban wastewater treatment plants. In most cases, the chemical oxidation is the only way to abate them. Advanced Oxidation Processes (AOPs) have been experimentally proved as efficient in the removal of different micropollutants at lab-scale. However, there is not enough information about their application at full-scale. This manuscript reports the application of three different AOPs based on the addition of homogeneous oxidants [hydrogen peroxide, peroxymonosulfate (PMS) and persulfate anions (PS)], in the UV-C tertiary treatment of Estiviel wastewater treatment plant (Toledo, Spain) previously designed and installed in the facility for disinfection. AOPs based on the photolytic decomposition of oxidants have been demonstrated as more efficient than UV-C radiation alone on the removal of 25 different MPs using low dosages (0.05-0.5 mM) and very low UV-C contact time (4-18 s). Photolysis of PMS and H 2 O 2 reached similar average MPs removal in all the range of oxidant dosages, obtaining the highest efficiency with 0.5 mM and 18 s of contact time (48 and 55% respectively). Nevertheless, PMS/UV-C reached slightly higher removal than H 2 O 2 /UV-C at low dosages. So, these treatments are selective to degrade the target compounds, obtaining different removal efficiencies for each compound regarding the oxidizing agent, dosages and UV-C contact time. In all the cases, H 2 O 2 /UV-C is more efficient than PMS/UV-C, comparing the ratio cost:efficiency (€/m 3 ·order). Even H 2 O 2 /UV-C treatments are more efficient than UV-C alone. Thus, the addition of 0.5 mM of H 2 O 2 compensates the increased of UV-C contact time and therefore the increase of electrical consumption, that it should be need to increase the removal of MPs by UV-C treatments alone. Copyright © 2018 Elsevier B.V. All rights reserved.

Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton, Jr.

A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic

Energy and Emission Characteristics of a Short-Arc Xenon Flash Lamp Under "Saturated" Optical Brightness Conditions

NASA Astrophysics Data System (ADS)

Kamrukov, A. S.; Kireev, S. G.; Kozlov, N. P.; Shashkovskii, S. G.

2017-09-01

We present the results of a study of the electrical, energy, and spectral brightness characteristics of an experimental three-electrode high-pressure xenon flash lamp under conditions ensuring close to maximum possible spectral brightness for the xenon emission. We show that under saturated optical brightness conditions (brightness temperature in the visible region of the spectrum 30,000 K), emission of a pulsed discharge in xenon is quite different from the emission from an ideal blackbody: the maximum brightness temperatures are 24,000 K in the short-wavelength UV region and 19,000 K in the near IR range. The relative fraction of UV radiation in the emission spectrum of the lamp is >50%, which lets us consider such lamps as promising broadband sources of radiation with high spectral brightness for many important practical applications.

Identification of intermediates, acute toxicity removal, and kinetics investigation to the Ametryn treatment by direct photolysis (UV254), UV254/H2O2, Fenton, and photo-Fenton processes.

PubMed

de Oliveira, Dirce Martins; Cavalcante, Rodrigo Pereira; da Silva, Lucas de Melo; Sans, Carme; Esplugas, Santiago; de Oliveira, Silvio Cesar; Junior, Amilcar Machulek

2018-02-09

This paper reports the degradation of 10 mg L -1 Ametryn solution with different advanced oxidation processes and by ultraviolet (UV 254 ) irradiation alone with the main objective of reducing acute toxicity and increase biodegradability. The investigated factors included Fe 2+ and H 2 O 2 concentrations. The effectiveness of the UV 254 and UV 254 /H 2 O 2 processes were investigated using a low-pressure mercury UV lamp (254 nm). Photo-Fenton process was explored using a blacklight blue lamp (BLB, λ = 365 nm). The UV 254 irradiation process achieved complete degradation of Ametryn solution after 60 min. The degradation time of Ametryn was greatly improved by the addition of H 2 O 2 . It is worth pointing out that a high rate of Ametryn removal was attained even at low concentrations of H 2 O 2 . The kinetic constant of the reaction between Ametryn and HO ● for UV 254 /H 2 O 2 was 3.53 × 10 8  L mol -1  s -1 . The complete Ametryn degradation by the Fenton and photo-Fenton processes was observed following 10 min of reaction for various combinations of Fe 2+ and H 2 O 2 under investigation. Working with the highest concentration (150 mg L -1 H 2 O 2 and 10 mg L -1 Fe 2+ ), around 30 and 70% of TOC removal were reached within 120 min of treatment by Fenton and photo-Fenton processes, respectively. Although it did not obtain complete mineralization, the intermediates formed in the degradation processes were hydroxylated and did not promote acute toxicity of Vibrio fischeri. Furthermore, a substantial improvement of biodegradability was obtained for all studied processes.

Flash Photolysis and Its Applications: Meeting in Honour of Sir George Porter, P.R.S. held in London, England on 14-16 July 1986,

DTIC Science & Technology

1986-07-16

present the design and results from the current flash spectroscopic system at the R.I. A hybrid mode-locked, cavity dumped dye laser is used to seed a...date require a HE sum of at least three exponentials to achieve an acceptable fit. Lettuce chloroplasts exhibit decay times of 100 psec., 500-600 psec...other lettuce preparations. A PS1 preparation from the cyanobacterium Chlorogloea Fritschii, which has been thoroughly characterised previously [2

New Measurements of Methyl Ethyl Ketone (MEK) Photolysis Rates and Their Relevance to Global Oxidative Capacity

NASA Astrophysics Data System (ADS)

Brewer, J.; Ravishankara, A. R.; Mellouki, A.; Fischer, E. V.; Kukui, A.; Véronique, D.; Ait-helal, W.; Leglise, J.; Ren, Y.

2017-12-01

Methyl ethyl ketone (MEK) is one of the most abundant ketones in the atmosphere. MEK can be emitted directly into the atmosphere from both anthropogenic and natural sources, and it is also formed during the gas-phase oxidation of volatile organic compounds (VOCs). MEK is lost via reaction with OH, photolysis and deposition to the surface. Similar to the other atmospheric ketones, the photolysis of MEK may represent a source of HOx (OH + HO2) radicals in the upper troposphere. The degradation of MEK also leads to the atmospheric formation of acetaldehyde and formaldehyde. This work presents a new analysis of the temperature dependence of MEK photolysis cross-sections and a quantification of MEK photolysis rates under surface pressures using the CNRS HELIOS outdoor atmospheric chamber (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans; http://www.era-orleans.org/ERA-TOOLS/helios-project.html). Additionally, we use the GEOS-Chem 3-D CTM (version 10-01, www.geos-chem.org) to investigate the impact of these newly measured rates and cross-sections on the global distribution and seasonality of MEK, as well as its importance to the tropospheric oxidative capacity.

Millimeter-wave spectroscopy of CoNO Produced by UV laser photolysis of Co(CO){sub 3}NO

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

Sakamoto, Ai; Hayashi, Masato; Harada, Kensuke

2008-10-07

The rotational spectrum of cobalt mononitrosyl (CoNO) produced by ultraviolet photolysis of Co(CO){sub 3}NO was observed in the millimeter-wave region. Seven rotational transitions in the ground state ranging from J=6-5 to 12-11, with hyperfine splittings due to the Co nucleus (I=7/2), were detected in a supersonic jet environment, while higher-frequency transitions in the range from J=29-28 to 35-34 were measured in the ground, {nu}{sub 1}, {nu}{sub 2}, {nu}{sub 3}, and 2{nu}{sub 2} vibrational states using a free-space absorption cell. It was confirmed from the observed spectral pattern that the CoNO molecule has a linear structure with the electronic ground statemore » of {sup 1}{sigma}{sup +} symmetry. The rotational lines in the 2{nu}{sub 2}({sigma}) and {nu}{sub 3} states were observed to be perturbed by Fermi resonance. The equilibrium rotational constant B{sub e} is determined to be 4682.207(15) MHz. The CoN bond length is derived to be 1.5842 A assuming the NO bond length of 1.1823 A. A large nuclear spin-rotation interaction constant, C{sub I}=123.8(11) kHz, was determined, suggesting a {sup 1}{pi} electronic excited state lying close to the ground state.« less

Time-of-flight mass spectrometry assessment of fluconazole and climbazole UV and UV/H2O2 degradability: Kinetics study and transformation products elucidation.

PubMed

Castro, Gabriela; Casado, Jorge; Rodríguez, Isaac; Ramil, María; Ferradás, Aida; Cela, Rafael

2016-01-01

The efficiency of UV irradiation for the removal of the antimycotic drugs fluconazole (FCZ) and climbazole (CBZ) from water samples is evaluated. Degradation experiments, at laboratory scale, were carried out with spiked aliquots of ultrapure water solutions and treated wastewater samples using low-pressure mercury lamps emitting at 254 nm. Time course of precursor pollutants and identification of arising transformation products (TPs) was performed by injection of different reaction time aliquots in a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) system. Chemical structures of identified TPs were proposed from their full-product ion spectra, acquired using different collision energies. During UV irradiation experiments, the half-lives (t1/2) of FCZ and CBZ were similar in ultrapure water solutions and wastewater samples; however, the first species was more recalcitrant than the second one. Four TPs were identified in case of FCZ resulting from substitution of fluorine atoms by hydroxyl moieties and intramolecular cyclization with fluorine removal. CBZ interacted with UV radiation through reductive dechlorination, hydroxylation and cleavage of the ether bond; moreover, five additional primary TPs, with the same empirical formula as CBZ, were also noticed. Given the relatively long t1/2 of FCZ under direct photolysis (ca. 42 min), UV irradiation was combined with H2O2 addition to promote formation of reactive hydroxyl radicals. Under such conditions, the degradation rate of FCZ was enhanced significantly and no TPs were detected. These latter conditions allowed also the effective removal of CBZ TPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photodegradation of the UV filter ethylhexyl methoxycinnamate under ultraviolet light: Identification and in silico assessment of photo-transformation products in the context of grey water reuse.

PubMed

Jentzsch, F; Olsson, O; Westphal, J; Reich, M; Leder, C; Kümmerer, K

2016-12-01

To prevent water shortages in the future and to reduce domestic water consumption, decentralized grey water (GW) reuse has become increasingly important. This water has, however, to be free of pollutants. Conventional treatment of GW does not fully eliminate micropollutants such as the UV filter substance ethylhexyl methoxycinnamate (EHMC). EHMC, which is commonly used in sunscreens and personal care products, is an endocrine disruptor and shows potential to bioaccumulation, which is also reflected in its low water solubility. Photolysis has been proposed as an alternative treatment method for other micropollutants, but it is not clear yet whether it can also be used to eliminate EHMC. One goal of this study was to better understand the basic pathways involved in this process. It aimed to identify photo-transformation products (photo-TPs) by using, in the test conditions, an initial concentration of EHMC higher than those expected in the environment. Acetonitrile (ACN) was added in low concentrations to the aqueous solution to overcome the low aquatic solubility of EHMC. The influence of this co-solvent on the degradation kinetics was studied. The photolysis experiments were carried out using a medium pressure mercury lamp, which emits UV light in the range of 200-400nm. The quantum yield of the photolysis of EHMC was 0.0042 and 0.0023mol·Einstein -1 (for 0.2 and 0.5% ACN (v/v), respectively), and the relative and absolute UV photon fluxes were determined. HPLC was used to monitor the elimination kinetics of EHMC, which followed first-order kinetics. The results of LC-MS n analyses revealed that beside others, several oxidized and hydroxylized EHMC isomers were formed as photo-TPs in aqueous solution. Using a set of in silico quantitative structure-activity relationship (QSAR) models, this study also offered new insights concerning the environmental fate and toxicity of the TPs of EHMC. Copyright © 2016 Elsevier B.V. All rights reserved.

Time-kill kinetic analysis of antimicrobial chemotherapy based on hydrogen peroxide photolysis against Streptococcus mutans biofilm.

PubMed

Shirato, Midori; Nakamura, Keisuke; Kanno, Taro; Lingström, Peter; Niwano, Yoshimi; Örtengren, Ulf

2017-08-01

A recently developed antimicrobial technique utilizing hydroxyl radicals generated by hydrogen peroxide (H 2 O 2 ) photolysis represents a promising new therapy for preventing and treating dental caries. The present study compared the antimicrobial time-kill kinetics of H 2 O 2 photolysis, conventional antiseptics, and antimicrobial photodynamic therapy (aPDT) against biofilm-forming Streptococcus mutans (cariogenic bacteria) grown on hydroxyapatite disks. H 2 O 2 photolysis was performed by irradiating the biofilm immersed in 3% H 2 O 2 with 365-nm light-emitting diode (LED) light at an irradiance of 1000mW/cm 2 for up to 1.5min. Antiseptic treatments consisted of 0.2% chlorhexidine gluconate, 0.5% povidone-iodine, and 3% H 2 O 2 . The biofilm was immersed in each antiseptic for up to 4min. aPDT was performed by irradiating the biofilm immersed in 100μM methylene blue or toluidine blue O with 655-nm laser light at 1000mW/cm 2 for up to 4min. Based on the time-kill assay, the decimal reduction value (D-value) of each treatment was determined. With a D-value of 0.06min, H 2 O 2 photolysis exhibited the highest bactericidal effect against biofilm-forming S. mutans. In contrast, antiseptics and aPDT exerted a slower bactericidal effect, with D-values of 0.9-2.7min. In conclusion, the antimicrobial technique based on H 2 O 2 photolysis using 365-nm LED represents a strong adjunctive chemotherapy for dental caries treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

Optimization of droplets for UV-NIL using coarse-grain simulation of resist flow

NASA Astrophysics Data System (ADS)

Sirotkin, Vadim; Svintsov, Alexander; Zaitsev, Sergey

2009-03-01

A mathematical model and numerical method are described, which make it possible to simulate ultraviolet ("step and flash") nanoimprint lithography (UV-NIL) process adequately even using standard Personal Computers. The model is derived from 3D Navier-Stokes equations with the understanding that the resist motion is largely directed along the substrate surface and characterized by ultra-low values of the Reynolds number. By the numerical approximation of the model, a special finite difference method is applied (a coarse-grain method). A coarse-grain modeling tool for detailed analysis of resist spreading in UV-NIL at the structure-scale level is tested. The obtained results demonstrate the high ability of the tool to calculate optimal dispensing for given stamp design and process parameters. This dispensing provides uniform filled areas and a homogeneous residual layer thickness in UV-NIL.

The aqueous photolysis of α-pinene in solution with humic acid

USGS Publications Warehouse

Goldberg, Marvin C.; Cunningham, Kirkwood M.; Aiken, George R.; Weiner, Eugene R.; ,

1992-01-01

Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.

Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

NASA Technical Reports Server (NTRS)

Watson, R. T.; Sander, S. P.; Yung, Y. L.

1979-01-01

The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

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

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less

Bipolar cloud-to-ground lightning flash observations

NASA Astrophysics Data System (ADS)

Saba, Marcelo M. F.; Schumann, Carina; Warner, Tom A.; Helsdon, John H.; Schulz, Wolfgang; Orville, Richard E.

2013-10-01

lightning is usually defined as a lightning flash where the current waveform exhibits a polarity reversal. There are very few reported cases of cloud-to-ground (CG) bipolar flashes using only one channel in the literature. Reports on this type of bipolar flashes are not common due to the fact that in order to confirm that currents of both polarities follow the same channel to the ground, one necessarily needs video records. This study presents five clear observations of single-channel bipolar CG flashes. High-speed video and electric field measurement observations are used and analyzed. Based on the video images obtained and based on previous observations of positive CG flashes with high-speed cameras, we suggest that positive leader branches which do not participate in the initial return stroke of a positive cloud-to-ground flash later generate recoil leaders whose negative ends, upon reaching the branch point, traverse the return stroke channel path to the ground resulting in a subsequent return stroke of opposite polarity.

On Stellar Flash Echoes from Circular Rings

NASA Astrophysics Data System (ADS)

Nemiroff, Robert; Mukherjee, Oindabi

2018-01-01

A flash -- or any episode of variability -- that occurs in the vicinity of a circular ring might be seen several times later, simultaneously, as echoes on the ring. Effective images of the flash are created and annihilated in pairs, with as many as four flash images visible concurrently. Videos detailing sequences of image pair creation, tandem motion, and subsequent image annihilation are shown, given simple opacity and scattering assumptions. It is proven that, surprisingly, images from a second pair creation event always annihilate with images from the first. Caustic surfaces between flash locations yielding two and four images are computed. Although such ring echos surely occur, their practical detection might be difficult as it could require dedicated observing programs involving sensitive photometry of extended objects. Potential flash sources include planetary and interstellar gas and dust rings near and around variable stars, flare stars, novae, supernovae, and GRBs. Potentially recoverable information includes size, distance, temporal history, and angular isotropy of both the ring and flash.

Reviews Equipment: Chameleon Nano Flakes Book: Requiem for a Species Equipment: Laser Sound System Equipment: EasySense VISION Equipment: UV Flash Kit Book: The Demon-Haunted World Book: Nonsense on Stilts Book: How to Think about Weird Things Web Watch

NASA Astrophysics Data System (ADS)

2011-03-01

WE RECOMMEND Requiem for a Species This book delivers a sober message about climate change Laser Sound System Sound kit is useful for laser demonstrations EasySense VISION Data Harvest produces another easy-to-use data logger UV Flash Kit Useful equipment captures shadows on film The Demon-Haunted World World-famous astronomer attacks pseudoscience in this book Nonsense on Stilts A thought-provoking analysis of hard and soft sciences How to Think about Weird Things This book explores the credibility of astrologers and their ilk WORTH A LOOK Chameleon Nano Flakes Product lacks good instructions and guidelines WEB WATCH Amateur scientists help out researchers with a variety of online projects

The Forensic Potential of Flash Memory

DTIC Science & Technology

2009-09-01

limit range of 10 to 100 years before data is lost [12]. 5. Flash Memory Logical Structure The logical structure of flash memory from least to...area is not standardized and is manufacturer specific. This information will be used by the wear leveling algorithms and as such will be proprietary...memory cells, the manufacturers of the flash implement a wear leveling algorithm . In contrast, a magnetic disk in an overwrite operation will reuse the

Menopausal hot flashes and insulin resistance.

PubMed

Tuomikoski, Pauliina; Ylikorkala, Olavi; Mikkola, Tomi S

2012-10-01

Recent data have indicated that menopausal hot flashes may be a determinant for cardiovascular health. Therefore, we studied the impact of hot flashes on insulin resistance, one of the most powerful markers of cardiovascular health, in recently postmenopausal women. We studied 143 recently postmenopausal (amenorrhea 6-36 mo) healthy and normal-weight women without previous hormone therapy use. The women prospectively recorded the number and severity of hot flashes for 2 weeks, and a validated total symptom score, the hot flash weekly weighted score, was calculated for each woman. Insulin resistance was assessed from fasting blood levels of glucose and insulin with the homeostasis model assessment. In 12 women, the assessment of insulin (n = 11) or glucose (n = 1) failed, and they were excluded from further analysis. Thus, hot flashes were absent in 19, mild in 32, moderate in 27, and severe in 53 women. The levels of glucose or insulin, or HOMA showed no differences between these groups, nor was insulin resistance related to the number or severity of hot flashes or to the levels of C-reactive protein or sex hormone-binding globulin. Overall, insulin resistance showed a positive association with body mass index (mean difference, 0.058; 95% CI, 0.015-0.102; P = 0.009) and a negative association with level of estradiol (mean difference, -0.002; 95% CI, -0.003 to -0.001; P = 0.009). Insulin resistance may not be involved in hot flash-related changes in cardiovascular health. However, because of the small sample size, these findings need to be interpreted with caution.

Electro-optical muzzle flash detection

NASA Astrophysics Data System (ADS)

Krieg, Jürgen; Eisele, Christian; Seiffer, Dirk

2016-10-01

Localizing a shooter in a complex scenario is a difficult task. Acoustic sensors can be used to detect blast waves. Radar technology permits detection of the projectile. A third method is to detect the muzzle flash using electro-optical devices. Detection of muzzle flash events is possible with focal plane arrays, line and single element detectors. In this paper, we will show that the detection of a muzzle flash works well in the shortwave infrared spectral range. Important for the acceptance of an operational warning system in daily use is a very low false alarm rate. Using data from a detector with a high sampling rate the temporal signature of a potential muzzle flash event can be analyzed and the false alarm rate can be reduced. Another important issue is the realization of an omnidirectional view required on an operational level. It will be shown that a combination of single element detectors and simple optics in an appropriate configuration is a capable solution.

49 CFR 234.217 - Flashing light units.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 4 2012-10-01 2012-10-01 false Flashing light units. 234.217 Section 234.217... light units. (a) Each flashing light unit shall be properly positioned and aligned and shall be visible to a highway user approaching the crossing. (b) Each flashing light unit shall be maintained to...

Onset conditions for flash sintering of UO 2

DOE PAGES

Raftery, Alicia M.; Pereira da Silva, João Gustavo; Byler, Darrin D.; ...

2017-06-22

In this paper, flash sintering was demonstrated on stoichiometric and non-stoichiometric uranium dioxide pellets at temperatures ranging from room temperature (26°C) up to 600°C. The onset conditions for flash sintering were determined for three stoichiometries (UO 2.00, UO 2.08, and UO 2.16) and analyzed against an established thermal runaway model. The presence of excess oxygen was found to enhance the flash sintering onset behavior of uranium dioxide, lowering the field required to flash and shortening the time required for a flash to occur. Finally, the results from this study highlight the effect of stoichiometry on the flash sintering behavior ofmore » uranium dioxide and will serve as the foundation for future studies on this material.« less

Onset conditions for flash sintering of UO2

NASA Astrophysics Data System (ADS)

Raftery, Alicia M.; Pereira da Silva, João Gustavo; Byler, Darrin D.; Andersson, David A.; Uberuaga, Blas P.; Stanek, Christopher R.; McClellan, Kenneth J.

2017-09-01

In this work, flash sintering was demonstrated on stoichiometric and non-stoichiometric uranium dioxide pellets at temperatures ranging from room temperature (26 °C) up to 600 °C . The onset conditions for flash sintering were determined for three stoichiometries (UO2.00, UO2.08, and UO2.16) and analyzed against an established thermal runaway model. The presence of excess oxygen was found to enhance the flash sintering onset behavior of uranium dioxide, lowering the field required to flash and shortening the time required for a flash to occur. The results from this study highlight the effect of stoichiometry on the flash sintering behavior of uranium dioxide and will serve as the foundation for future studies on this material.

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

NASA Technical Reports Server (NTRS)

Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

1975-01-01

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect.

PubMed

Wohlmuth da Silva, Salatiel; Arenhart Heberle, Alan Nelson; Pereira Santos, Alexia; Siqueira Rodrigues, Marco Antônio; Pérez-Herranz, Valentín; Moura Bernardes, Andréa

2018-05-29

Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 µg/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.

Abdominal adiposity and hot flashes among midlife women.

PubMed

Thurston, Rebecca C; Sowers, MaryFran R; Sutton-Tyrrell, Kim; Everson-Rose, Susan A; Lewis, Tené T; Edmundowicz, Daniel; Matthews, Karen A

2008-01-01

Two competing hypotheses suggest how adiposity may affect menopausal hot flashes. The "thin hypothesis" asserts that aromatization of androgens to estrogens in body fat should be associated with decreased hot flashes. Conversely, thermoregulatory models argue that body fat should be associated with increased hot flashes. The study objective was to examine associations between abdominal adiposity and hot flashes, including the role of reproductive hormones in these associations. The Study of Women's Health Across the Nation Heart Study (2001-2003) is an ancillary study to the Study of Women's Health Across the Nation, a community-based cohort study. Participants were 461 women (35% African American, 65% white) ages 45 to 58 years with an intact uterus and at least one ovary. Measures included a computed tomography scan to assess abdominal adiposity; reported hot flashes over the previous 2 weeks; and a blood sample for measurement of follicle-stimulating hormone, estradiol, and sex hormone-binding globulin-adjusted estradiol (free estradiol index). Associations were evaluated within multivariable logistic and linear regression models. Every 1-SD increase in total (odds ratio [OR]=1.28; 95% CI: 1.06-1.55) and subcutaneous (OR=1.30; 95% CI: 1.07-1.58) abdominal adiposity was associated with increased odds of hot flashes in age- and site-adjusted models. Visceral adiposity was not associated with hot flashes. Associations were not reduced when models included reproductive hormone concentrations. Increased abdominal adiposity, particularly subcutaneous adiposity, is associated with increased odds of hot flashes, favoring thermoregulatory models of hot flashes. Body fat may not protect women from hot flashes as once thought.

CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41silicate sieve

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

Lin, Wenyong; Han, Hongxian; Frei, Heinz

2004-04-06

The 266 nm light-induced reaction of CO{sub 2} and H{sub 2}O gas mixtures (including isotopic modifications {sup 13}CO{sub 2}, C{sup 18}O{sub 2}, and D{sub 2}O) in framework TiMCM-41 silicate sieve was monitored by in-situ FT-IR spectroscopy at room temperature. Carbon monoxide gas was observed as the sole product by infrared, and the growth was found to depend linearly on the photolysis laser power. H{sub 2}O was confirmed as stoichiometric electron donor. The work establishes CO as the single photon, 2-electron transfer product of CO{sub 2} photoreduction by H{sub 2}O at framework Ti centers for the first time. O{sub 2} wasmore » detected as co-product by mass spectrometric analysis of the photolysis gas mixture. These results are explained by single UV photon-induced splitting of CO{sub 2} by H{sub 2}O to CO and surface OH radical.« less

VUV/UV light inducing accelerated phenol degradation with a low electric input.

PubMed

Li, Mengkai; Wen, Dong; Qiang, Zhimin; Kiwi, John

2017-01-23

This study presents the first evidence for the accelerated degradation of phenol by Fenton's reagent in a mini-fluidic VUV/UV photoreaction system (MVPS). A low-pressure mercury lamp used in the MVPS led to a complete degradation of phenol within 4-6 min. The HO˙ and HO 2 ˙ originating from both Fenton's reagent and VUV photolysis of water were identified with suitable radical scavengers. The effects of initial concentrations of phenol, H 2 O 2 and Fe 3+ as well as solution pH on phenol degradation kinetics were examined. Increasing the initial phenol concentration slowed down the phenol degradation, whereas increasing the initial H 2 O 2 or Fe 3+ concentration accelerated the phenol degradation. The optimal solution pH was 3.7. At both 254 and 185 nm, increasing phenol concentration enhanced its absorption for the incident photons. The reaction mechanism for the degradation of phenol was suggested consistent with the results obtained. This study indicates that the VUV/UV photo-Fenton process has potential applications in the treatment of industrial wastewater containing phenol and related aromatic pollutants.

"Know What to Do If You Encounter a Flash Flood": Mental Models Analysis for Improving Flash Flood Risk Communication and Public Decision Making.

PubMed

Lazrus, Heather; Morss, Rebecca E; Demuth, Julie L; Lazo, Jeffrey K; Bostrom, Ann

2016-02-01

Understanding how people view flash flood risks can help improve risk communication, ultimately improving outcomes. This article analyzes data from 26 mental models interviews about flash floods with members of the public in Boulder, Colorado, to understand their perspectives on flash flood risks and mitigation. The analysis includes a comparison between public and professional perspectives by referencing a companion mental models study of Boulder-area professionals. A mental models approach can help to diagnose what people already know about flash flood risks and responses, as well as any critical gaps in their knowledge that might be addressed through improved risk communication. A few public interviewees mentioned most of the key concepts discussed by professionals as important for flash flood warning decision making. However, most interviewees exhibited some incomplete understandings and misconceptions about aspects of flash flood development and exposure, effects, or mitigation that may lead to ineffective warning decisions when a flash flood threatens. These include important misunderstandings about the rapid evolution of flash floods, the speed of water in flash floods, the locations and times that pose the greatest flash flood risk in Boulder, the value of situational awareness and environmental cues, and the most appropriate responses when a flash flood threatens. The findings point to recommendations for ways to improve risk communication, over the long term and when an event threatens, to help people quickly recognize and understand threats, obtain needed information, and make informed decisions in complex, rapidly evolving extreme weather events such as flash floods. © 2015 Society for Risk Analysis.

OTD Observations of Continental US Ground and Cloud Flashes

NASA Technical Reports Server (NTRS)

Koshak, William

2007-01-01

Lightning optical flash parameters (e.g., radiance, area, duration, number of optical groups, and number of optical events) derived from almost five years of Optical Transient Detector (OTD) data are analyzed. Hundreds of thousands of OTD flashes occurring over the continental US are categorized according to flash type (ground or cloud flash) using US National Lightning Detection Network TM (NLDN) data. The statistics of the optical characteristics of the ground and cloud flashes are inter-compared on an overall basis, and as a function of ground flash polarity. A standard two-distribution hypothesis test is used to inter-compare the population means of a given lightning parameter for the two flash types. Given the differences in the statistics of the optical characteristics, it is suggested that statistical analyses (e.g., Bayesian Inference) of the space-based optical measurements might make it possible to successfully discriminate ground and cloud flashes a reasonable percentage of the time.

Flash sintering of ceramic materials

NASA Astrophysics Data System (ADS)

Dancer, C. E. J.

2016-10-01

During flash sintering, ceramic materials can sinter to high density in a matter of seconds while subjected to electric field and elevated temperature. This process, which occurs at lower furnace temperatures and in shorter times than both conventional ceramic sintering and field-assisted methods such as spark plasma sintering, has the potential to radically reduce the power consumption required for the densification of ceramic materials. This paper reviews the experimental work on flash sintering methods carried out to date, and compares the properties of the materials obtained to those produced by conventional sintering. The flash sintering process is described for oxides of zirconium, yttrium, aluminium, tin, zinc, and titanium; silicon and boron carbide, zirconium diboride, materials for solid oxide fuel applications, ferroelectric materials, and composite materials. While experimental observations have been made on a wide range of materials, understanding of the underlying mechanisms responsible for the onset and latter stages of flash sintering is still elusive. Elements of the proposed theories to explain the observed behaviour include extensive Joule heating throughout the material causing thermal runaway, arrested by the current limitation in the power supply, and the formation of defect avalanches which rapidly and dramatically increase the sample conductivity. Undoubtedly, the flash sintering process is affected by the electric field strength, furnace temperature and current density limit, but also by microstructural features such as the presence of second phase particles or dopants and the particle size in the starting material. While further experimental work and modelling is still required to attain a full understanding capable of predicting the success of the flash sintering process in different materials, the technique non-etheless holds great potential for exceptional control of the ceramic sintering process.

Helium shell flashes and evolution of accreting white dwarfs

NASA Astrophysics Data System (ADS)

Fujimoto, M. Y.; Sugimoto, D.

1982-06-01

The evolution of accreting white dwarfs is investigated from the onset of accretion through the helium shell flash. Properties of the helium shell flashes are studied by means of a generalized theory of shell flash and by numerical computations, and it is found that the shell flash grows up to the strength of a supernova explosion when the mass of the helium zone is large enough on a massive white dwarf. Although accretion onto a hot white dwarf causes a weaker shell flash than those onto cool ones, a strong tendency exists for the strength to be determined mainly by the accretion rate. For fast accretion, the shell flashes are weak and triggered recurrently, while for slow accretion the helium shell flash, once triggered, develops into a detonation supernova.

Evaluation of Flash Bainite in 4130 Steel

DTIC Science & Technology

2011-07-01

Technical Report ARWSB-TR-11011 Evaluation of Flash Bainite in 4130 Steel G. Vigilante M. Hespos S. Bartolucci...4. TITLE AND SUBTITLE Evaluation of Flash Bainite in 4130 Steel 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...need to be addressed, the Flash Bainite processing of 4130 steel demonstrates promise for applications needing a combination of high strength with

Intensification of UV-C tertiary treatment: Disinfection and removal of micropollutants by sulfate radical based Advanced Oxidation Processes.

PubMed

Rodríguez-Chueca, J; García-Cañibano, C; Lepistö, R-J; Encinas, Á; Pellinen, J; Marugán, J

2018-04-21

This study explores the enhancement of UV-C tertiary treatment by sulfate radical based Advanced Oxidation Processes (SR-AOPs), including photolytic activation of peroxymonosulfate (PMS) and persulfate (PS) and their photocatalytic activation using Fe(II). Their efficiency was assessed both for the inactivation of microorganisms and the removal or micropollutants (MPs) in real wastewater treatment plant effluents. Under the studied experimental range (UV-C dose 5.7-57 J/L; UV-C contact time 3 to 28 s), the photolysis of PMS and PS (0.01 mM) increased up to 25% the bacterial removal regarding to UV-C system. The photolytic activation of PMS led to the total inactivation of bacteria (≈ 5.70 log) with the highest UV-C dose (57 J/L). However, these conditions were insufficient to remove the MPs, being required oxidant's dosages of 5 mM to remove above 90% of carbamazepine, diclofenac, atenolol and triclosan. The best efficiencies were achieved by the combination of PMS or PS with Fe(II), leading to the total removal of the MPs using a low UV-C dosage (19 J/L), UV-C contact time (9 s) and reagent's dosages (0.5 mM). Finally, high mineralization was reached (>50%) with photocatalytic activation of PMS and PS even with low reagent's dosages. Copyright © 2018 Elsevier B.V. All rights reserved.

Anxiogenic CO2 Stimulus Elicits Exacerbated Hot Flash-like Responses in a Rat Menopause Model and Hot Flashes in Menopausal Women

PubMed Central

Federici, Lauren M.; Roth, Sarah Dorsey; Krier, Connie; Fitz, Stephanie D.; Skaar, Todd; Shekhar, Anantha; Carpenter, Janet S.; Johnson, Philip L.

2016-01-01

Objective Since longitudinal studies determined that anxiety is a strong risk factor for hot flashes, we hypothesized that an anxiogenic stimulus that signals air hunger (hypercapnic, normoxic gas) would trigger an exacerbated hot flash-associated increase in tail skin temperature (TST) in a rat ovariectomy (OVEX) model of surgical menopause and hot flashes in symptomatic menopausal women. We also assessed TST responses in OVEX serotonin transporter (SERT)+/− rats that models a common polymorphism that is associated with increased climacteric symptoms in menopausal women and increases in anxiety traits. Methods OVEX and sham-OVEX rats (initial experiment) and wildtype and SERT+/− OVEX rats (subsequent experiment) were exposed to a 5 min infusion of 20%CO2 normoxic gas while measuring TST. Menopausal women were given brief 20% and 35%CO2 challenges, and hot flashes were self-reported and objectively verified. Results Compared to controls, OVEX rats had exacerbated increases in TST, and SERT+/− OVEX rats had prolonged TST increases following CO2. Most women reported mild/moderate hot flashes after CO2 challenges, and the hot flash severity to CO2 was positively correlated with daily hot flash frequency. Conclusions The studies demonstrate that this anxiogenic stimulus is capable of inducing cutaneous vasomotor responses in OVEX rats, and eliciting hot flashes in menopausal women. In rats, the severity of the response was mediated by loss of ovarian function and increased anxiety traits (SERT+/−), and, in women, by daily hot flash frequency. These findings may provide insights into anxiety related triggers and genetic risk factors for hot flashes in thermoneutral environments. PMID:27465717

Post-Flash Validation of the new ACS/WFC Subarrays

NASA Astrophysics Data System (ADS)

Bellini, A.; Grogin, N. A.; Lim, P. L.; Golimowski, D.

2017-05-01

We made use of the new ACS/WFC subarray images of CAL-14410, taken taken with a large range of flash exposure times (0.1-30 seconds), to probe the temporal stability of the reference flash file and to validate the current post-flash correction pipeline of CALACS and ACS DESTRIPE PLUS on the new subarray modes. No statistically-significant deviations are found between the new post-flashed subarray exposures and the flash reference file, indicating that the LED lamp used to post-flash ACS images has been stable over several years. The current calibration pipelines (both CALACS and ACS DESTRIPE PLUS can be successfully used with the new subarray modes.

Muzzle flash issues related to the Waco FLIR analysis

NASA Astrophysics Data System (ADS)

Grant, Barbara G.; Hardy, David T.

2001-09-01

The controversy surrounding the origin of flashes on the Mt. Carmel FLIR videotape acquired on April 19, 1993, is introduced. The characteristics of muzzle flash are reviewed. A comparative weapons description is offered. The temporal, spatial, and radiance characteristics of thermal infrared muzzle flash are addressed. Data acquired from a field experiment are presented. The authors conclude that the spatial characteristics of muzzle flash enable its detection by equipment such as the FLIR in use at Mt. Carmel on April 19, 1993; that while flashes obtained in the field appear highly radiant, measurements are necessary to quantify their values; and that the temporal behavior of muzzle flash deserves further study.

Stratospheric ozone changes under solar geoengineering: implications for UV exposure and air quality

NASA Astrophysics Data System (ADS)

Nowack, Peer Johannes; Abraham, Nathan Luke; Braesicke, Peter; Pyle, John Adrian

2016-03-01

Various forms of geoengineering have been proposed to counter anthropogenic climate change. Methods which aim to modify the Earth's energy balance by reducing insolation are often subsumed under the term solar radiation management (SRM). Here, we present results of a standard SRM modelling experiment in which the incoming solar irradiance is reduced to offset the global mean warming induced by a quadrupling of atmospheric carbon dioxide. For the first time in an atmosphere-ocean coupled climate model, we include atmospheric composition feedbacks for this experiment. While the SRM scheme considered here could offset greenhouse gas induced global mean surface warming, it leads to important changes in atmospheric composition. We find large stratospheric ozone increases that induce significant reductions in surface UV-B irradiance, which would have implications for vitamin D production. In addition, the higher stratospheric ozone levels lead to decreased ozone photolysis in the troposphere. In combination with lower atmospheric specific humidity under SRM, this results in overall surface ozone concentration increases in the idealized G1 experiment. Both UV-B and surface ozone changes are important for human health. We therefore highlight that both stratospheric and tropospheric ozone changes must be considered in the assessment of any SRM scheme, due to their important roles in regulating UV exposure and air quality.

Flash LIDAR Systems for Planetary Exploration

NASA Astrophysics Data System (ADS)

Dissly, Richard; Weinberg, J.; Weimer, C.; Craig, R.; Earhart, P.; Miller, K.

2009-01-01

Ball Aerospace offers a mature, highly capable 3D flash-imaging LIDAR system for planetary exploration. Multi mission applications include orbital, standoff and surface terrain mapping, long distance and rapid close-in ranging, descent and surface navigation and rendezvous and docking. Our flash LIDAR is an optical, time-of-flight, topographic imaging system, leveraging innovations in focal plane arrays, readout integrated circuit real time processing, and compact and efficient pulsed laser sources. Due to its modular design, it can be easily tailored to satisfy a wide range of mission requirements. Flash LIDAR offers several distinct advantages over traditional scanning systems. The entire scene within the sensor's field of view is imaged with a single laser flash. This directly produces an image with each pixel already correlated in time, making the sensor resistant to the relative motion of a target subject. Additionally, images may be produced at rates much faster than are possible with a scanning system. And because the system captures a new complete image with each flash, optical glint and clutter are easily filtered and discarded. This allows for imaging under any lighting condition and makes the system virtually insensitive to stray light. Finally, because there are no moving parts, our flash LIDAR system is highly reliable and has a long life expectancy. As an industry leader in laser active sensor system development, Ball Aerospace has been working for more than four years to mature flash LIDAR systems for space applications, and is now under contract to provide the Vision Navigation System for NASA's Orion spacecraft. Our system uses heritage optics and electronics from our star tracker products, and space qualified lasers similar to those used in our CALIPSO LIDAR, which has been in continuous operation since 2006, providing more than 1.3 billion laser pulses to date.

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry.

PubMed

Wentrup, Curt

2018-05-29

There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years due to the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered. Numerous rearrangements and fragmentations have been documented. This minireview aims to give an overview of some of these developments but will not generally cover laser flash photolysis and chemical reactions in liquid solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biophysical Characterisation of Neuroglobin of the Icefish, a Natural Knockout for Hemoglobin and Myoglobin. Comparison with Human Neuroglobin

PubMed Central

Giordano, Daniela; Boron, Ignacio; Abbruzzetti, Stefania; Van Leuven, Wendy; Nicoletti, Francesco P.; Forti, Flavio; Bruno, Stefano; Cheng, C-H. Christina; Moens, Luc; di Prisco, Guido; Nadra, Alejandro D.; Estrin, Darío; Smulevich, Giulietta; Dewilde, Sylvia; Viappiani, Cristiano; Verde, Cinzia

2012-01-01

The Antarctic icefish Chaenocephalus aceratus lacks the globins common to most vertebrates, hemoglobin and myoglobin, but has retained neuroglobin in the brain. This conserved globin has been cloned, over-expressed and purified. To highlight similarities and differences, the structural features of the neuroglobin of this colourless-blooded fish were compared with those of the well characterised human neuroglobin as well as with the neuroglobin from the retina of the red blooded, hemoglobin and myoglobin-containing, closely related Antarctic notothenioid Dissostichus mawsoni. A detailed structural and functional analysis of the two Antarctic fish neuroglobins was carried out by UV-visible and Resonance Raman spectroscopies, molecular dynamics simulations and laser-flash photolysis. Similar to the human protein, Antarctic fish neuroglobins can reversibly bind oxygen and CO in the Fe2+ form, and show six-coordination by distal His in the absence of exogenous ligands. A very large and structured internal cavity, with discrete docking sites, was identified in the modelled three-dimensional structures of the Antarctic neuroglobins. Estimate of the free-energy barriers from laser-flash photolysis and Implicit Ligand Sampling showed that the cavities are accessible from the solvent in both proteins. Comparison of structural and functional properties suggests that the two Antarctic fish neuroglobins most likely preserved and possibly improved the function recently proposed for human neuroglobin in ligand multichemistry. Despite subtle differences, the adaptation of Antarctic fish neuroglobins does not seem to parallel the dramatic adaptation of the oxygen carrying globins, hemoglobin and myoglobin, in the same organisms. PMID:23226490

Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor.

PubMed

Zhang, Min; E, Wenbo; Ohkubo, Kei; Sanchez-Garcia, David; Yoon, Dae-Wi; Sessler, Jonathan L; Fukuzumi, Shunichi; Kadish, Karl M

2008-02-21

Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.

Organic flash cycles for efficient power production

DOEpatents

Ho, Tony; Mao, Samuel S.; Greif, Ralph

2016-03-15

This disclosure provides systems, methods, and apparatus related to an Organic Flash Cycle (OFC). In one aspect, a modified OFC system includes a pump, a heat exchanger, a flash evaporator, a high pressure turbine, a throttling valve, a mixer, a low pressure turbine, and a condenser. The heat exchanger is coupled to an outlet of the pump. The flash evaporator is coupled to an outlet of the heat exchanger. The high pressure turbine is coupled to a vapor outlet of the flash evaporator. The throttling valve is coupled to a liquid outlet of the flash evaporator. The mixer is coupled to an outlet of the throttling valve and to an outlet of the high pressure turbine. The low pressure turbine is coupled to an outlet of the mixer. The condenser is coupled to an outlet of the low pressure turbine and to an inlet of the pump.

Hot flashes in breast cancer survivors: Frequency, severity and impact.

PubMed

Chang, Hao-Yuan; Jotwani, Aparna C; Lai, Yeur-Hur; Jensen, Mark P; Syrjala, Karen L; Fann, Jesse R; Gralow, Julie

2016-06-01

To (1) determine the frequency and severity of hot flashes, (2) examine the associations between hot flash frequency and severity and quality of life, and (3) identify the predictors of hot flash activity in breast cancer survivors. The study used a cross-sectional design and mailed survey of 253 breast cancer survivors recruited from a cancer wellness clinic. Participants provided information regarding cancer history, hot flashes, pain intensity, sleep problems, physical functioning, and psychological functioning. About half of the survivors reported at least one hot flash in the past 24 h (45%) or past week (52%). The average frequency of hot flashes was 1.9 in the past 24 h and 1.8 in the past week. Hot flash severity was usually mild or asymptomatic. However, participants with hot flashes reported significantly more sleep problems and higher pain severity than those reporting no hot flashes. Moreover, the severity of hot flashes was associated with more sleep problems, higher pain severity, and more psychological dysfunction. History of hormonal suppression therapy and younger age predicted hot flash activity in the study sample. In breast cancer survivors, hot flashes are common and are associated with unpleasant symptoms and poor quality of life. Research is needed to determine if treatments that reduce the frequency and severity of hot flashes in breast cancer survivors also result in improvements in symptoms such as sleep problems, pain, and psychological dysfunction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hot flashes in breast cancer survivors: Frequency, severity and impact

PubMed Central

Chang, Hao-Yuan; Jotwani, Aparna C.; Lai, Yeur-Hur; Jensen, Mark P.; Syrjala, Karen L.; Fann, Jesse R.; Gralow, Julie

2018-01-01

Purposes To (1) determine the frequency and severity of hot flashes, (2) examine the associations be- tween hot flash frequency and severity and quality of life, and (3) identify the predictors of hot flash activity in breast cancer survivors. Methods The study used a cross-sectional design and mailed survey of 253 breast cancer survivors recruited from a cancer wellness clinic. Participants provided information regarding cancer history, hot flashes, pain intensity, sleep problems, physical functioning, and psychological functioning. Results About half of the survivors reported at least one hot flash in the past 24 h (45%) or past week (52%). The average frequency of hot flashes was 1.9 in the past 24 h and 1.8 in the past week. Hot flash severity was usually mild or asymptomatic. However, participants with hot flashes reported significantly more sleep problems and higher pain severity than those reporting no hot flashes. Moreover, the severity of hot flashes was associated with more sleep problems, higher pain severity, and more psychological dysfunction. History of hormonal suppression therapy and younger age predicted hot flash activity in the study sample. Conclusions In breast cancer survivors, hot flashes are common and are associated with unpleasant symptoms and poor quality of life. Research is needed to determine if treatments that reduce the frequency and severity of hot flashes in breast cancer survivors also result in improvements in symptoms such as sleep problems, pain, and psychological dysfunction. PMID:27065357

Non Volatile Flash Memory Radiation Tests

NASA Technical Reports Server (NTRS)

Irom, Farokh; Nguyen, Duc N.; Allen, Greg

2012-01-01

Commercial flash memory industry has experienced a fast growth in the recent years, because of their wide spread usage in cell phones, mp3 players and digital cameras. On the other hand, there has been increased interest in the use of high density commercial nonvolatile flash memories in space because of ever increasing data requirements and strict power requirements. Because of flash memories complex structure; they cannot be treated as just simple memories in regards to testing and analysis. It becomes quite challenging to determine how they will respond in radiation environments.

Spectroscopic measurements of muzzle flash plasma

NASA Astrophysics Data System (ADS)

Uglum, J. R.

1986-11-01

The experimental apparatus and sample data for the muzzle flash plasma of a laboratory-scale railgun are described. Theoretical predictions for the railgun system configuration used indicated that 24 kJ of energy would be dissipated by the muzzle flash. Spectral data were recorded with a spectrograph sensing through a slit and a PIN diode, the latter to obtain temporal resolution in the data. The tests featured a plastic projectile with an Al foil armature. The measurements identified Cu as the dominant flash material, ablated from the rails in the barrel.

Hot Flashes and Quality of Life Among Breast Cancer Patients

DTIC Science & Technology

2006-08-01

hot flashes, 40.7% report at baseline, having used HRT and 26.8% used exercise to control hot flashes. The 12-month data indicates that 26.5% of the...entire sample who are experiencing hot flashes, tried or are using some form of HRT to control hot flashes with exercise still the most frequently...used approach to manage hot flashes with 44.2% of sample currently exercising . 15. SUBJECT TERMS Breast Cancer, Hot Flashes, Quality of Life

Karst flash floods: an example from the Dinaric karst (Croatia)

NASA Astrophysics Data System (ADS)

Bonacci, O.; Ljubenkov, I.; Roje-Bonacci, T.

2006-03-01

Flash floods constitute one of the deadliest and costliest natural disasters worldwide. This paper explains the karst flash flood phenomenon, which represents a special kind of flash flood. As the majority of flash floods karst flash floods are caused by intensive short-term precipitation in an area whose surface rarely exceeds a few square kilometres. The characteristics of all flash floods are their short duration, small areal extent, high flood peaks and rapid flows, and heavy loss of life and property. Karst flash floods have specific characteristics due to special conditions for water circulation, which exist in karst terrains. During karst flash floods a sudden rise of groundwater levels occurs, which causes the appearance of numerous, unexpected, abundant and temporary karst springs. This paper presents in detail an example of a karst flash flood in the Marina bay (Dinaric karst region of Croatia), which occurred in December 2004.

Physiologically assessed hot flashes and endothelial function among midlife women.

PubMed

Thurston, Rebecca C; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J Richard; von Känel, Roland; Landsittel, Doug P; Matthews, Karen A

2017-08-01

Hot flashes are experienced by most midlife women. Emerging data indicate that they may be associated with endothelial dysfunction. No studies have tested whether hot flashes are associated with endothelial function using physiologic measures of hot flashes. We tested whether physiologically assessed hot flashes were associated with poorer endothelial function. We also considered whether age modified associations. Two hundred seventy-two nonsmoking women reporting either daily hot flashes or no hot flashes, aged 40 to 60 years, and free of clinical cardiovascular disease, underwent ambulatory physiologic hot flash and diary hot flash monitoring; a blood draw; and ultrasound measurement of brachial artery flow-mediated dilation to assess endothelial function. Associations between hot flashes and flow-mediated dilation were tested in linear regression models controlling for lumen diameter, demographics, cardiovascular disease risk factors, and estradiol. In multivariable models incorporating cardiovascular disease risk factors, significant interactions by age (P < 0.05) indicated that among the younger tertile of women in the sample (age 40-53 years), the presence of hot flashes (beta [standard error] = -2.07 [0.79], P = 0.01), and more frequent physiologic hot flashes (for each hot flash: beta [standard error] = -0.10 [0.05], P = 0.03, multivariable) were associated with lower flow-mediated dilation. Associations were not accounted for by estradiol. Associations were not observed among the older women (age 54-60 years) or for self-reported hot flash frequency, severity, or bother. Among the younger women, hot flashes explained more variance in flow-mediated dilation than standard cardiovascular disease risk factors or estradiol. Among younger midlife women, frequent hot flashes were associated with poorer endothelial function and may provide information about women's vascular status beyond cardiovascular disease risk factors and estradiol.

Hot Flashes and Carotid Intima Media Thickness among Midlife Women

PubMed Central

Thurston, Rebecca C.; Sutton-Tyrrell, Kim; Everson-Rose, Susan A.; Hess, Rachel; Powell, Lynda H.; Matthews, Karen A.

2010-01-01

Objective Emerging evidence suggests associations between menopausal hot flashes and cardiovascular risk. Whether hot flashes are associated with intima media thickness (IMT) or IMT changes over time is unknown. We hypothesized that reported hot flashes would be associated with greater IMT cross-sectionally and with greater IMT progression over two years. Methods Participants were 432 women ages 45-58 at baseline participating in SWAN Heart, an ancillary study to the Study of Women's Health Across the Nation. Measures at the SWAN Heart baseline and follow-up visit two years later included a carotid artery ultrasound, reported hot flashes (past two weeks: none, 1-5, ≥6 days), and a blood sample for measurement of estradiol. Results Women reporting hot flashes ≥6 days in the prior two weeks had significantly higher IMT than women without hot flashes at baseline (mean difference(SE), mm =0.02(0.01), p=0.03) and follow-up (mean difference(SE), mm =0.02(0.01), p=0.04) visits, controlling for demographic factors and cardiovascular risk factors. Reporting hot flashes at both study visits was associated with higher follow-up IMT relative to reporting hot flashes at neither visit (mean difference(SE), mm=0.03(0.01), p=0.03). Associations between hot flashes and IMT largely remained after adjusting for estradiol. An interaction between hot flashes and obesity status was observed (p=0.05) such that relations between hot flashes and IMT were observed principally among overweight/obese women. Hot flashes were not associated with IMT progression. Conclusions These findings provided some indication that women reporting hot flashes ≥6 days in the prior two weeks may have higher IMT than women without hot flashes, particularly for women who are overweight or obese. Further work should determine whether hot flashes mark adverse underlying vascular changes. PMID:21242820

Algorithms for Lunar Flash Video Search, Measurement, and Archiving

NASA Technical Reports Server (NTRS)

Swift, Wesley; Suggs, Robert; Cooke, Bill

2007-01-01

Lunar meteoroid impact flashes provide a method to estimate the flux of the large meteoroid flux and thus their hazard to spacecraft. Although meteoroid impacts on the Moon have been detected using video methods for over a decade, the difficulty of manually searching hours of video for the rare, extremely brief impact flashes has discouraged the technique's systematic implementation. A prototype has been developed for the purpose of automatically searching lunar video records for impact flashes, eliminating false detections, editing the returned possible flashes, Z and archiving and documenting the results. The theory and organization of the program is discussed with emphasis on the filtering out of several classes of false detections and retaining the brief portions of the raw video necessary for in depth analysis of the flashes detected. Several utilities for measurement, analysis, and location of the flashes on the moon included in the program are demonstrated. Application of the program to a year's worth of lunar observations is discussed along with examples of impact flashes as well as several classes of false impact flashes.

Algorithms for Lunar Flash Video Search, Measurement, and Archiving

NASA Technical Reports Server (NTRS)

Swift, Wesley; Suggs, Robert; Cooke, William

2007-01-01

Lunar meteoroid impact flashes provide a method to estimate the flux of the large meteoroid flux and thus their hazard to spacecraft. Although meteoroid impacts on the Moon have been detected using video methods for over a decade, the difficulty of manually searching hours of video for the rare, extremely brief impact flashes has discouraged the technique's systematic implementation. A prototype has been developed for the purpose of automatically searching Lunar video records for impact flashes, eliminating false detections, editing the returned possible flashes, and archiving and documenting the results. The theory and organization of the program is discussed with emphasis on the filtering out of several classes of false detections and retaining the brief portions of the raw video necessary for in depth analysis of the flashes detected. Several utilities for measurement, analysis, and location of the flashes on the moon included in the program are demonstrated. Application of the program to a year's worth of Lunar observations is discussed along with examples of impact flashes as well as several classes of false impact flashes.

Calcium released by photolysis of DM-nitrophen stimulates transmitter release at squid giant synapse.

PubMed

Delaney, K R; Zucker, R S

1990-07-01

1. Transmitter release at the squid giant synapse was stimulated by photolytic release of Ca2+ from the 'caged' Ca2+ compound DM-nitrophen (Kaplan & Ellis-Davies, 1988) inserted into presynaptic terminals. 2. Competing binding reactions cause the amount of Ca2+ released by DM-nitrophen photolysis to depend on the concentrations of DM-nitrophen, total Ca2+, Mg+, ATP and native cytoplasmic Ca2+ buffer. Measurements of presynaptic [Ca2+] changes by co-injection of the fluorescent indicator dye Fura-2 show that DM-nitrophen photolysis causes a transient rise in Ca2+ followed by decay within about 150 ms to an increased steady-state level. 3. Rapid photolysis of Ca2(+)-loaded nitrophen within the presynaptic terminal was followed in less than a millisecond by depolarization of the postsynaptic membrane. As with action potential-evoked excitatory postsynaptic potentials (EPSPs), the light-evoked response was partially and reversibly blocked by 1-3 mM-kainic acid which desensitizes postsynaptic glutamate receptors. 4. Release was similar in magnitude and rate to normal action potential-mediated EPSPs. 5. The release of transmitter by photolysis of Ca2(+)-loaded DM-nitrophen was not affected by removal of Ca2+ from the saline or addition of tetrodotoxin. Photolysis of DM-nitrophen injected into presynaptic terminals without added Ca2+ did not stimulate release of transmitter nor did it interfere with normal action potential-mediated release. 6. Stimulation of presynaptic action potentials in Ca2(+)-free saline during the light-evoked response did not elicit increased release of transmitter if the ganglion was bathed in Ca2(+)-free saline, i.e. in the absence of Ca2+ influx. Increasing the intensity of the light or stimulating presynaptic action potentials in Ca2(+)-containing saline increased the release of transmitter. Therefore the failure of presynaptic voltage change to increase transmitter release resulting from release of caged Ca2+ was not due to saturation or

The Evolution and Structure of Extreme Optical Lightning Flashes.

PubMed

Peterson, Michael; Rudlosky, Scott; Deierling, Wiebke

2017-12-27

This study documents the composition, morphology, and motion of extreme optical lightning flashes observed by the Lightning Imaging Sensor (LIS). The furthest separation of LIS events (groups) in any flash is 135 km (89 km), the flash with the largest footprint had an illuminated area of 10,604 km 2 , and the most dendritic flash has 234 visible branches. The longest-duration convective LIS flash lasted 28 s and is overgrouped and not physical. The longest-duration convective-to-stratiform propagating flash lasted 7.4 s, while the longest-duration entirely stratiform flash lasted 4.3 s. The longest series of nearly consecutive groups in time lasted 242 ms. The most radiant recorded LIS group (i.e., "superbolt") is 735 times more radiant than the average group. Factors that impact these optical measures of flash morphology and evolution are discussed. While it is apparent that LIS can record the horizontal development of the lightning channel in some cases, radiative transfer within the cloud limits the flash extent and level of detail measured from orbit. These analyses nonetheless suggest that lightning imagers such as LIS and Geostationary Lightning Mapper can complement ground-based lightning locating systems for studying physical lightning phenomena across large geospatial domains.

The Evolution and Structure of Extreme Optical Lightning Flashes

PubMed Central

Peterson, Michael; Rudlosky, Scott; Deierling, Wiebke

2018-01-01

This study documents the composition, morphology, and motion of extreme optical lightning flashes observed by the Lightning Imaging Sensor (LIS). The furthest separation of LIS events (groups) in any flash is 135 km (89 km), the flash with the largest footprint had an illuminated area of 10,604 km2, and the most dendritic flash has 234 visible branches. The longest-duration convective LIS flash lasted 28 s and is overgrouped and not physical. The longest-duration convective-to-stratiform propagating flash lasted 7.4 s, while the longest-duration entirely stratiform flash lasted 4.3 s. The longest series of nearly consecutive groups in time lasted 242 ms. The most radiant recorded LIS group (i.e., “superbolt”) is 735 times more radiant than the average group. Factors that impact these optical measures of flash morphology and evolution are discussed. While it is apparent that LIS can record the horizontal development of the lightning channel in some cases, radiative transfer within the cloud limits the flash extent and level of detail measured from orbit. These analyses nonetheless suggest that lightning imagers such as LIS and Geostationary Lightning Mapper can complement ground-based lightning locating systems for studying physical lightning phenomena across large geospatial domains. PMID:29527425

Timing in a FLASH

NASA Astrophysics Data System (ADS)

Hoek, M.; Cardinali, M.; Corell, O.; Dickescheid, M.; Ferretti B., M. I.; Lauth, W.; Schlimme, B. S.; Sfienti, C.; Thiel, M.

2017-12-01

A prototype detector, called FLASH (Fast Light Acquiring Start Hodoscope), was built to provide precise Time-of-Flight (TOF) measurements and reference timestamps for detector setups at external beam lines. Radiator bars, made of synthetic fused silica, were coupled to a fast MCP-PMT with 64 channels and read out with custom electronics using Time-over-Threshold (TOT) for signal characterization. The TRB3 system, a high-precision TDC implemented in an FPGA, was used as data acquisition system. The performance of a system consisting of two FLASH units was investigated at a dedicated test experiment at the Mainz Microtron (MAMI) accelerator using its 855 MeV electron beam. The TOT measurement enabled time walk corrections and an overall TOF resolution of ∼70 ps could be achieved which translates into a resolution of ∼50 ps per FLASH unit. The intrinsic resolution of the frontend electronics including the TDC was measured to be less than 25 ps.

Development of template and mask replication using jet and flash imprint lithography

NASA Astrophysics Data System (ADS)

Brooks, Cynthia; Selinidis, Kosta; Doyle, Gary; Brown, Laura; LaBrake, Dwayne; Resnick, Douglas J.; Sreenivasan, S. V.

2010-09-01

The Jet and Flash Imprint Lithography (J-FILTM)1-7 process uses drop dispensing of UV curable resists to assist high resolution patterning for subsequent dry etch pattern transfer. The technology is actively being used to develop solutions for memory markets including Flash memory and patterned media for hard disk drives. It is anticipated that the lifetime of a single template (for patterned media) or mask (for semiconductor) will be on the order of 104 - 105 imprints. This suggests that tens of thousands of templates/masks will be required. It is not feasible to employ electronbeam patterning directly to deliver these volumes. Instead, a "master" template - created by directly patterning with an electron-beam tool - will be replicated many times with an imprint lithography tool to produce the required supply of "working" templates/masks. In this paper, we review the development of the pattern transfer process for both template and mask replicas. Pattern transfer of resolutions down to 25nm has been demonstrated for bit patterned media replication. In addition, final resolution on a semiconductor mask of 28nm has been confirmed. The early results on both etch depth and CD uniformity are promising, but more extensive work is required to characterize the pattern transfer process.

Quantifying soil surface photolysis under conditions simulating water movement in the field: a new laboratory test design.

PubMed

Hand, Laurence H; Nichols, Carol; Kuet, Sui F; Oliver, Robin G; Harbourt, Christopher M; El-Naggar, Essam M

2015-10-01

Soil surface photolysis can be a significant dissipation pathway for agrochemicals under field conditions, although it is assumed that such degradation ceases once the agrochemical is transported away from the surface following rainfall or irrigation and subsequent drainage of soil porewater. However, as both downward and upward water movements occur under field conditions, relatively mobile compounds may return to the surface, prolonging exposure to ultraviolet light and increasing the potential for degradation by photolysis. To test this hypothesis, a novel experimental system was used to quantify the contribution of photolysis to the overall dissipation of a new herbicide, bicyclopyrone, under conditions that mimicked field studies more closely than the standard laboratory test guidance. Soil cores were taken from 3 US field study sites, and the surfaces were treated with [(14) C]-bicyclopyrone. The radioactivity was redistributed throughout the cores using a simulated rainfall event, following which the cores were incubated under a xenon-arc lamp with continuous provision of moisture from below and a wind simulator to induce evaporation. After only 2 d, most of the test compound had returned to the soil surface. Significantly more degradation was observed in the irradiated samples than in a parallel dark control sample. Degradation rates were very similar to those observed in both the thin layer photolysis study and the field dissipation studies and significantly faster than in the soil metabolism studies conducted in the dark. Thus, for highly soluble, mobile agrochemicals, such as bicyclopyrone, photolysis is not terminated permanently by rainfall or irrigation but can resume following transport to the surface in evaporating water. © 2015 SETAC.

An Experimental and Master Equation Study of the Kinetics of OH/OD + SO2: The Limiting High-Pressure Rate Coefficients.

PubMed

Blitz, Mark A; Salter, Robert J; Heard, Dwayne E; Seakins, Paul W

2017-05-04

The kinetics of the reaction OH/OD + SO 2 were studied using a laser flash photolysis/laser-induced fluorescence technique. Evidence for two-photon photolysis of SO 2 at 248 nm is presented and quantified, and which appears to have been evident to some extent in most previous photolysis studies, potentially leading to values for the rate coefficient k 1 that are too large. The kinetics of the reaction OH(v = 0) + SO 2 (T = 295 K, p = 25-300 torr) were measured under conditions where SO 2 photolysis was taken into account. These results, together with literature data, were modeled using a master equation analysis. This analysis highlighted problems with the literature data: the rate coefficients derived from flash photolysis data were generally too high and from the flow tube data too low. Our best estimate of the high-pressure limiting rate coefficient k 1 ∞ was obtained from selected data and gives a value of (7.8 ± 2.2) × 10 -13 cm 3 molecule -1 s -1 , which is lower than that recommended in the literature. A parametrized form of k 1 ([N 2 ],T) is provided. The OD(v = 0) + SO 2 (T = 295 K, p = 25-300 torr) data are reported for the first time, and master equation analysis reinforces our assignment of k 1 ∞ .

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

PubMed

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

2016-03-01

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

An unusual characteristic "flower-like" pattern: flash suppressor burns.

PubMed

Gurcan, Altun

2012-04-01

The case on contact shots from firearms with a flash suppressor is rare. When a rifle fitted with a flash suppressor is fired, the emerging soot-laden gas in the barrel escapes from the slits of the flash suppressor. If the shot is contact or near contact, the flash suppressor will produce a characteristic "flower-like" pattern of seared, blackened zones around the entrance. This paper presents the injury pattern of the flash suppressor in a 29-year-old man who committed suicide with a G3 automatic infantry rifle.

INFLUENCE OF HUMIC SUBSTANCES ON PHOTOLYSIS OF NITROAROMATIC COMPOUNDS IN AQUEOUS SYSTEMS

EPA Science Inventory

Results are reported for kinetic studies of the photolysis of 19 nitroaromatic compounds in water. The results indicate that dissolved humic substances in natural waters enhance the sunlight-induced photodegradation rates of nitrobenzenes, nitrotoluenes, and nitroxylenes compared...

Impacts of Brown Carbon from Biomass Burning on Surface UV and Ozone Photochemistry in the Amazon Basin

NASA Technical Reports Server (NTRS)

Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhangqing; Dickerson, Russell R.;

Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin.

PubMed

Mok, Jungbin; Krotkov, Nickolay A; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F; Li, Zhanqing; Dickerson, Russell R; Stenchikov, Georgiy L; Osipov, Sergey; Ren, Xinrong

2016-11-11

The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or "brown" carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305-368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO 2 , and RO 2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

Photolysis of Caged Ca2+ But Not Receptor-Mediated Ca2+ Signaling Triggers Astrocytic Glutamate Release

PubMed Central

Smith, Nathan A.; Xu, Qiwu; Goldman, Siri; Peng, Weiguo; Huang, Jason H.; Takano, Takahiro; Nedergaard, Maiken

2013-01-01

Astrocytes in hippocampal slices can dynamically regulate synaptic transmission in a process mediated by increases in intracellular Ca2+. However, it is debated whether astrocytic Ca2+ signals result in release of glutamate. We here compared astrocytic Ca2+ signaling triggered by agonist exposure versus photolysis side by side. Using transgenic mice in which astrocytes selectively express the MrgA1 receptor, we found that receptor-mediated astrocytic Ca2+ signaling consistently triggered neuronal hyperpolarization and decreased the frequency of miniature excitatory postsynaptic currents (EPSCs). In contrast, photolysis of caged Ca2+ (o-nitrophenyl–EGTA) in astrocytes led to neuronal depolarization and increased the frequency of mEPSCs through a metabotropic glutamate receptor-mediated pathway. Analysis of transgenic mice in which astrocytic vesicular release is suppressed (dominant-negative SNARE mice) and pharmacological manipulations suggested that glutamate is primarily released by opening of anion channels rather than exocytosis. Combined, these studies show that photolysis but not by agonists induced astrocytic Ca2+ signaling triggers glutamate release. PMID:24174673

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process

NASA Astrophysics Data System (ADS)

Abidin, Che Zulzikrami Azner; Fahmi, Muhammad Ridwan; Fazara, Md Ali Umi; Nadhirah, Siti Nurfatin

2014-10-01

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV / H2O2 experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV / H2O2 process is meaningful with respect to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H2O2 photolysis.

Degradation pathways of aniline in aqueous solutions during electro-oxidation with BDD electrodes and UV/H2O2 treatment.

PubMed

Benito, Aleix; Penadés, Aida; Lliberia, Josep Lluis; Gonzalez-Olmos, Rafael

2017-01-01

In this work, it has been studied the mineralization of aniline, a toxic substance of low biodegradability typically found in many industrial wastewaters, through electro-oxidation using boron doped diamond (BDD) electrodes and photo-oxidation (UV photolysis and UV/H 2 O 2 treatments). It was observed that in electro-oxidation and UV/H 2 O 2 , it was feasible to reach aniline mineralizations higher than 85%. Two different degradation routes have been observed during the aniline oxidation in these two treatments. The first route was the mineralization pathway, in which aniline was oxidized to CO 2 , water and nitrate. The second route was the polyaniline pathway in which polyanilines of high molecular weight are formed. The intermediate compounds involved in both degradation routes are different depending on the treatment used. In the electro-oxidation, denitrification processes were also observed. From an economical point of view, electro-oxidation of aniline using BDD electrodes is more interesting than UV/H 2 O 2 due it has an 87% lower operational cost. So, electro-oxidation using BDD electrodes seems to be a more suitable technique for the mineralization of wastewater containing aniline than UV or H 2 O 2 based technologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

A spatially collocated sound thrusts a flash into awareness

PubMed Central

Aller, Máté; Giani, Anette; Conrad, Verena; Watanabe, Masataka; Noppeney, Uta

2015-01-01

To interact effectively with the environment the brain integrates signals from multiple senses. It is currently unclear to what extent spatial information can be integrated across different senses in the absence of awareness. Combining dynamic continuous flash suppression (CFS) and spatial audiovisual stimulation, the current study investigated whether a sound facilitates a concurrent visual flash to elude flash suppression and enter perceptual awareness depending on audiovisual spatial congruency. Our results demonstrate that a concurrent sound boosts unaware visual signals into perceptual awareness. Critically, this process depended on the spatial congruency of the auditory and visual signals pointing towards low level mechanisms of audiovisual integration. Moreover, the concurrent sound biased the reported location of the flash as a function of flash visibility. The spatial bias of sounds on reported flash location was strongest for flashes that were judged invisible. Our results suggest that multisensory integration is a critical mechanism that enables signals to enter conscious perception. PMID:25774126

Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

PubMed

Orge, C A; Faria, J L; Pereira, M F R

2015-01-01

Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays.

PubMed

Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Petersen, Paul Michael; Pedersen, Christian

2016-09-19

We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng/L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED excitation for time-resolved fluorimetry. Optimization of the suggested key parameters of the LED promises significant increase of the signal-to-noise ratio and hence of the sensitivity of immunoassay systems.

Light-Flash Wind-Direction Indicator

NASA Technical Reports Server (NTRS)

Zysko, Jan A.

1993-01-01

Proposed wind-direction indicator read easily by distant observers. Indicator emits bright flashes of light separated by interval of time proportional to angle between true north and direction from which wind blowing. Timing of flashes indicates direction of wind. Flashes, from high-intensity stroboscopic lights seen by viewers at distances up to 5 miles or more. Also seen more easily through rain and fog. Indicator self-contained, requiring no connections to other equipment. Power demand satisfied by battery or solar power or both. Set up quickly to provide local surface-wind data for aircraft pilots during landing or hovering, for safety officers establishing hazard zones and safety corridors during handling of toxic materials, for foresters and firefighters conducting controlled burns, and for real-time wind observations during any of variety of wind-sensitive operations.

Normalized Temperature Contrast Processing in Infrared Flash Thermography

NASA Technical Reports Server (NTRS)

Koshti, Ajay M.

2016-01-01

The paper presents further development in normalized contrast processing used in flash infrared thermography method. Method of computing normalized image or pixel intensity contrast, and normalized temperature contrast are provided. Methods of converting image contrast to temperature contrast and vice versa are provided. Normalized contrast processing in flash thermography is useful in quantitative analysis of flash thermography data including flaw characterization and comparison of experimental results with simulation. Computation of normalized temperature contrast involves use of flash thermography data acquisition set-up with high reflectivity foil and high emissivity tape such that the foil, tape and test object are imaged simultaneously. Methods of assessing other quantitative parameters such as emissivity of object, afterglow heat flux, reflection temperature change and surface temperature during flash thermography are also provided. Temperature imaging and normalized temperature contrast processing provide certain advantages over normalized image contrast processing by reducing effect of reflected energy in images and measurements, therefore providing better quantitative data. Examples of incorporating afterglow heat-flux and reflection temperature evolution in flash thermography simulation are also discussed.

Application of AOPs for Removal of Stable Cyanide Compounds

NASA Astrophysics Data System (ADS)

Tsybikova, B.

2017-11-01

The main kinetic regularities of the photochemical oxidation of stable cyanide compounds (exemplified by hexacyanoferrates) by combined treatments involving direct photolysis and persulfate (oxidative system UV/S2O8 2-) and direct photolysis and hydrogen peroxide (oxidative system UV/H2O2) were studied. The possibility to perform oxidation processes within a wide pH range was shown. Based on to the energy efficiency, the rate of reaction and duration of the treatment, the considered oxidative systems can be arranged in the following order: {UV/S2O8 2-}>{UV/H2O2}>{UV}. The enhanced efficiency of hexacyanoferrates’ degradation by the combined system {UV/S2O8 2-} is due to the high oxidative capacity of sulfate anion radicals SO4 -· formed as a result of persulfate photolysis and its further disproportionation by Fe3+ and Fe2+ released through the decomposition of [Fe(CN)6]3-. Furthermore, the formation of ·OH radicals as a result of SO4 -· reacting with water also contributes to the enhanced oxidation efficiency. The combined method of {UV/S2O8 2-} treatment could be applied for the treatment of cyanide-containing wastewater and recycled water of different industries.

Are menopausal hot flashes an evolutionary byproduct of postpartum warming?

PubMed

Sievert, Lynnette Leidy; Masley, Allison

2015-04-01

Hot flashes are commonly associated with menopause, and some researchers have questioned whether the widespread phenomenon may somehow be adaptive. It has been hypothesized that hot flashes were selected to occur during the hypoestrogenic postpartum period as a mechanism to warm infants. The purpose of this study was to test whether postpartum hot flashes are similar to hot flashes associated with menopause and whether postpartum hot flashes are concordant with breast-feeding episodes. Women who gave birth within the past year (n = 20) and a comparison group of women who had not given birth in the past 2 years (n = 14) participated in interviews and anthropometric measures. All wore ambulatory skin conductance monitors for a mean of 6.5 hours during afternoons and early evenings. New mothers also recorded breast-feeding episodes. Objectively measured and subjectively reported hot flashes were compared between groups and in relation to breast-feeding and other variables. Age of infants ranged from 4 days to 11 months. New mothers were more likely to report feeling warmer than the comparison group (100% vs 7%) but were not significantly more likely to demonstrate hot flashes (35% vs 50%) or to report hot flashes (30% vs 21%) during the study period. Of 75 breast-feeding episodes, only 4% were concurrent with an objective hot flash, and only 9% were concurrent with a subjective hot flash. This study does not support the hypothesis that menopausal-like hot flashes evolved to warm infants during the postpartum period.

Menopausal Hot Flashes and Carotid Intima Media Thickness Among Midlife Women.

PubMed

Thurston, Rebecca C; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J Richard; Landsittel, Doug P; Santoro, Nanette; von Känel, Roland; Matthews, Karen A

2016-12-01

There has been a longstanding interest in the role of menopause and its correlates in the development of cardiovascular disease (CVD) in women. Menopausal hot flashes are experienced by most midlife women; emerging data link hot flashes to CVD risk indicators. We tested whether hot flashes, measured via state-of-the-art physiologic methods, were associated with greater subclinical atherosclerosis as assessed by carotid ultrasound. We considered the role of CVD risk factors and estradiol concentrations in these associations. A total of 295 nonsmoking women free of clinical CVD underwent ambulatory physiologic hot flash assessments; a blood draw; and carotid ultrasound measurement of intima media thickness and plaque. Associations between hot flashes and subclinical atherosclerosis were tested in regression models controlling for CVD risk factors and estradiol. More frequent physiologic hot flashes were associated with higher carotid intima media thickness (for each additional hot flash: β [SE]=0.004 [0.001]; P=0.0001; reported hot flash: β [SE]=0.008 [0.002]; P=0.002, multivariable) and plaque (eg, for each additional hot flash, odds ratio [95% confidence interval] plaque index ≥2=1.07 [1.003-1.14]; P=0.04, relative to no plaque, multivariable] among women reporting daily hot flashes; associations were not accounted for by CVD risk factors or by estradiol. Among women reporting hot flashes, hot flashes accounted for more variance in intima media thickness than most CVD risk factors. Among women reporting daily hot flashes, frequent hot flashes may provide information about a woman's vascular status beyond standard CVD risk factors and estradiol. Frequent hot flashes may mark a vulnerable vascular phenotype among midlife women. © 2016 American Heart Association, Inc.

Menopausal Hot Flashes and Carotid Intima Media Thickness among Midlife Women

PubMed Central

Thurston, Rebecca C.; Chang, Yuefang; Barinas-Mitchell, Emma; Jennings, J. Richard; Landsittel, Doug P.; Santoro, Nanette; von Känel, Roland; Matthews, Karen A.

2016-01-01

Background and Purpose There has been a longstanding interest in the role of menopause and its correlates in the development of cardiovascular disease (CVD) in women. Menopausal hot flashes are experienced by most midlife women; emerging data link hot flashes to CVD risk indicators. We tested whether hot flashes, measured via state-of-the-art physiologic methods, were associated with greater subclinical atherosclerosis as assessed by carotid ultrasound. We considered the role of CVD risk factors and estradiol concentrations in these associations. Methods 295 nonsmoking women free of clinical CVD underwent ambulatory physiologic hot flash assessments; a blood draw; and carotid ultrasound measurement of IMT and plaque. Associations between hot flashes and subclinical atherosclerosis were tested in regression models controlling for CVD risk factors and estradiol. Results More frequent physiologic hot flashes were associated with higher carotid intima media thickness [IMT; for each additional hot flash: beta (standard error)=.004(.001), p=.0001; reported hot flash: beta (standard error)=.008(.002), p=.002, multivariable] and plaque [e.g., for each additional hot flash, odds ratio (95% confidence interval) plaque index ≥2=1.07(1.003–1.14, p=.04), relative to no plaque, multivariable] among women reporting daily hot flashes; associations were not accounted for by CVD risk factors or by estradiol. Among women reporting hot flashes, hot flashes accounted for more variance in IMT than most CVD risk factors. Conclusions Among women reporting daily hot flashes, frequent hot flashes may provide information about a woman’s vascular status beyond standard CVD risk factors and estradiol. Frequent hot flashes may mark a vulnerable vascular phenotype among midlife women. PMID:27834746

Spatial-temporal characteristics of lightning flash size in a supercell storm

NASA Astrophysics Data System (ADS)

Zhang, Zhixiao; Zheng, Dong; Zhang, Yijun; Lu, Gaopeng

2017-11-01

The flash sizes of a supercell storm, in New Mexico on October 5, 2004, are studied using the observations from the New Mexico Lightning Mapping Array and the Albuquerque, New Mexico, Doppler radar (KABX). First, during the temporal evolution of the supercell, the mean flash size is anti-correlated with the flash rate, following a unary power function, with a correlation coefficient of - 0.87. In addition, the mean flash size is linearly correlated with the area of reflectivity > 30 dBZ at 5 km normalized by the flash rate, with a correlation coefficient of 0.88. Second, in the horizontal, flash size increases along the direction from the region near the convection zone to the adjacent forward anvil. The region of minimum flash size usually corresponds to the region of maximum flash initiation and extent density. The horizontal correspondence between the mean flash size and the flash extent density can also be fitted by a unary power function, and the correlation coefficient is > 0.5 in 50% of the radar volume scans. Furthermore, the quality of fit is positively correlated to the convective intensity. Third, in the vertical direction, the height of the maximum flash initiation density is close to the height of maximum flash extent density, but corresponds to the height where the mean flash size is relatively small. In the discussion, the distribution of the small and dense charge regions when and where convection is vigorous in the storm, is deduced to be responsible for the relationship that flash size is temporally and spatially anti-correlated with flash rate and density, and the convective intensity.

Flood hazard assessment in areas prone to flash flooding

NASA Astrophysics Data System (ADS)

Kvočka, Davor; Falconer, Roger A.; Bray, Michaela

2016-04-01

Contemporary climate projections suggest that there will be an increase in the occurrence of high-intensity rainfall events in the future. These precipitation extremes are usually the main cause for the emergence of extreme flooding, such as flash flooding. Flash floods are among the most unpredictable, violent and fatal natural hazards in the world. Furthermore, it is expected that flash flooding will occur even more frequently in the future due to more frequent development of extreme weather events, which will greatly increase the danger to people caused by flash flooding. This being the case, there will be a need for high resolution flood hazard maps in areas susceptible to flash flooding. This study investigates what type of flood hazard assessment methods should be used for assessing the flood hazard to people caused by flash flooding. Two different types of flood hazard assessment methods were tested: (i) a widely used method based on an empirical analysis, and (ii) a new, physically based and experimentally calibrated method. Two flash flood events were considered herein, namely: the 2004 Boscastle flash flood and the 2007 Železniki flash flood. The results obtained in this study suggest that in the areas susceptible to extreme flooding, the flood hazard assessment should be conducted using methods based on a mechanics-based analysis. In comparison to standard flood hazard assessment methods, these physically based methods: (i) take into account all of the physical forces, which act on a human body in floodwater, (ii) successfully adapt to abrupt changes in the flow regime, which often occur for flash flood events, and (iii) rapidly assess a flood hazard index in a relatively short period of time.

Flash (Ultra-Rapid) Spark-Plasma Sintering of Silicon Carbide

PubMed Central

Olevsky, Eugene A.; Rolfing, Stephen M.; Maximenko, Andrey L.

2016-01-01

A new ultra-rapid process of flash spark plasma sintering is developed. The idea of flash spark plasma sintering (or flash hot pressing - FHP) stems from the conducted theoretical analysis of the role of thermal runaway phenomena for material processing by flash sintering. The major purpose of the present study is to theoretically analyze the thermal runaway nature of flash sintering and to experimentally address the challenge of uncontrollable thermal conditions by the stabilization of the flash sintering process through the application of the external pressure. The effectiveness of the developed FHP technique is demonstrated by the few seconds–long consolidation of SiC powder in an industrial spark plasma sintering device. Specially designed sacrificial dies heat the pre-compacted SiC powder specimens to a critical temperature before applying any voltage to the powder volume and allowing the electrode-punches of the SPS device setup to contact the specimens and pass electric current through them under elevated temperatures. The experimental results demonstrate that flash sintering phenomena can be realized using conventional SPS devices. The usage of hybrid heating SPS devices is pointed out as the mainstream direction for the future studies and utilization of the new flash hot pressing (ultra-rapid spark plasma sintering) technique. PMID:27624641

Flash (Ultra-Rapid) Spark-Plasma Sintering of Silicon Carbide

DOE PAGES

Olevsky, Eugene A.; Rolfing, Stephen M.; Maximenko, Andrey L.

2016-09-14

A new ultra-rapid process of flash spark plasma sintering is developed. The idea of flash spark plasma sintering (or flash hot pressing - FHP) stems from the conducted theoretical analysis of the role of thermal runaway phenomena for material processing by flash sintering. The major purpose of the present study is to theoretically analyze the thermal runaway nature of flash sintering and to experimentally address the challenge of uncontrollable thermal conditions by the stabilization of the flash sintering process through the application of the external pressure. The effectiveness of the developed FHP technique is demonstrated by the few seconds–long consolidationmore » of SiC powder in an industrial spark plasma sintering device. Specially designed sacrificial dies heat the pre-compacted SiC powder specimens to a critical temperature before applying any voltage to the powder volume and allowing the electrode-punches of the SPS device setup to contact the specimens and pass electric current through them under elevated temperatures. The experimental results demonstrate that flash sintering phenomena can be realized using conventional SPS devices. The usage of hybrid heating SPS devices is pointed out as the mainstream direction for the future studies and utilization of the new flash hot pressing (ultra-rapid spark plasma sintering) technique.« less

Positive cloud-to-ground lightning flashes in severe storms

NASA Technical Reports Server (NTRS)

Rust, W. D.; Macgorman, D. R.; Arnold, R. T.

1981-01-01

The occurrence of cloud-to-ground flashes that effectively lower positive charge to earth (+CG flash) over flat terrain has been documented in the mature stage of severe thunderstorms. Of the 31 documented +CG flashes, most had only one return stroke. Zero-to-peak rise times for the strokes averaged 7 microsec. The +CG flashes averaged 520 ms in duration, with 25 percent lasting more than 800 ms. Many of these had field changes suggestive of continuing current. Positive flashes have been observed to emanate from several regions of severe storms: high on the back of the main storm tower, through the wall cloud, and from the downshear anvil. Visually most of these positive flashes have emanated from high in the storm, and acoustic mapping of two shows thunder sources to a height of about 15 km.

Flash memory management system and method utilizing multiple block list windows

NASA Technical Reports Server (NTRS)

Chow, James (Inventor); Gender, Thomas K. (Inventor)

2005-01-01

The present invention provides a flash memory management system and method with increased performance. The flash memory management system provides the ability to efficiently manage and allocate flash memory use in a way that improves reliability and longevity, while maintaining good performance levels. The flash memory management system includes a free block mechanism, a disk maintenance mechanism, and a bad block detection mechanism. The free block mechanism provides efficient sorting of free blocks to facilitate selecting low use blocks for writing. The disk maintenance mechanism provides for the ability to efficiently clean flash memory blocks during processor idle times. The bad block detection mechanism provides the ability to better detect when a block of flash memory is likely to go bad. The flash status mechanism stores information in fast access memory that describes the content and status of the data in the flash disk. The new bank detection mechanism provides the ability to automatically detect when new banks of flash memory are added to the system. Together, these mechanisms provide a flash memory management system that can improve the operational efficiency of systems that utilize flash memory.

Photoinduced reduction of the medial FeS center in the hydrogenase small subunit HupS from Nostoc punctiforme.

PubMed

Raleiras, Patrícia; Hammarström, Leif; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

2015-07-01

The small subunit from the NiFe uptake hydrogenase, HupSL, in the cyanobacterium Nostoc punctiforme ATCC 29133, has been isolated in the absence of the large subunit (P. Raleiras, P. Kellers, P. Lindblad, S. Styring, A. Magnuson, J. Biol. Chem. 288 (2013) 18,345-18,352). Here, we have used flash photolysis to reduce the iron-sulfur clusters in the isolated small subunit, HupS. We used ascorbate as electron donor to the photogenerated excited state of Ru(II)-trisbipyridine (Ru(bpy)3), to generate Ru(I)(bpy)3 as reducing agent. Our results show that the isolated small subunit can be reduced by the Ru(I)(bpy)3 generated through flash photolysis. Copyright © 2015 Elsevier Inc. All rights reserved.

(CH3)3COOH (tert-butyl hydroperoxide): OH reaction rate coefficients between 206 and 375 K and the OH photolysis quantum yield at 248 nm.

PubMed

Baasandorj, Munkhbayar; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Hasson, Alam S; Burkholder, James B

2010-10-14

Rate coefficients, k, for the gas-phase reaction of the OH radical with (CH(3))(3)COOH (tert-butyl hydroperoxide) were measured as a function of temperature (206-375 K) and pressure (25-200 Torr (He, N(2))). Rate coefficients were measured under pseudo-first-order conditions using pulsed laser photolysis to produce OH and laser induced fluorescence (PLP-LIF) to measure the OH temporal profile. Two independent methods were used to determine the gas-phase infrared cross sections of (CH(3))(3)COOH, absolute pressure and chemical titration, that were used to determine the (CH(3))(3)COOH concentration in the LIF reactor. The temperature dependence of the rate coefficients is described, within the measurement precision, by the Arrhenius expression k(1)(T) = (7.0 ± 1.0) × 10(-13) exp[(485 ± 20)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (3.58 ± 0.54) × 10(-12) cm(3) molecule(-1) s(-1). The uncertainties are 2σ (95% confidence level) and include estimated systematic errors. UV absorption cross sections of (CH(3))(3)COOH were determined at 185, 214, 228, and 254 nm and over the wavelength range 210-300 nm. The OH quantum yield following the 248 nm pulsed laser photolysis of (CH(3))(3)COOH was measured relative to the OH quantum yields of H(2)O(2) and HNO(3) using PLP-LIF and found to be near unity.

Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg2+ Effects by Quantum Chemical Calculations.

PubMed

Wang, Se; Wang, Zhuang

2017-11-11

The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg 2+ effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR 2+ < NOR⁰ < NOR⁺) and showed different photolysis reactivity. Analysis of transition states (TS) and reaction activation energies ( E a ) indicated NOR⁺ generally underwent loss of the piperazine ring (C10-N13 bond cleavage) and damage to piperazine ring (N13-C14 bond cleavage). For NOR 2+ , the main direct photolysis pathways were de-ethylation (N7-C8 bond cleavage) and decarboxylation (C2-C5 bond cleavage). Furthermore, the presence of Mg 2+ changed the order of the wavelength at maximum electronic absorbance (NOR⁺-Mg 2+ < NOR⁰-Mg 2+ < NOR 2+ -Mg 2+ ) and increased the intensities of absorbance peaks of all three dissociation species of NOR, implying that Mg 2+ played an important role in the direct photolysis of NOR⁰, NOR⁺, and NOR 2+ . The calculated TS results indicated that the presence of Mg 2+ increased E a for most direct photolysis pathways of NOR, while it decreased E a for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR⁰ and the defluorination of NOR⁺.

Characteristics of flash initiations in a supercell cluster with tornadoes

NASA Astrophysics Data System (ADS)

Zheng, Dong; MacGorman, Donald R.

2016-01-01

Flash initiations within a supercell cluster during 10-11 May 2010 in Oklahoma were investigated based on observations from the Oklahoma Lightning Mapping Array and the Norman, Oklahoma, polarimetric radar (KOUN). The flash initiations at positions dominated by graupel, dry snow, small hail and crystals accounted for 44.3%, 44.1%, 8.0% and 3.0% of the total flashes, respectively. During the tornadic stage of the southern supercell in the cluster, flash initiations associated with graupel occupied the main body, the right flank and the forward flank of the supercell, while those associated with dry snow dominated the outskirts of the adjacent forward anvil, right anvil and rear anvil. The flash initiations associated with small hail were concentrated around the main updraft, particularly toward its front side. Highly dense flash initiations were located in the regions overlying the differential reflectivity (ZDR) arc and right anvil. The average initial height of the flashes decreased gradually from the rear to the front and from the right to the left flanks, while the height range over which initiations occurred reached a maximum at the front of the updraft. The flashes that were initiated in the adjacent forward anvils were largest on average, followed by those in the regions ahead of the updraft and near the ZDR arc. This study supports the concept of charge pockets and further deduces that the pockets in the right anvil are the most abundant and compact due to the frequent flash initiations, small-sized flashes and thin layers including flash initiations.

Study of the simulated sunlight photolysis mechanism of ketoprofen: the role of superoxide anion radicals, transformation byproducts, and ecotoxicity assessment.

PubMed

Wang, Yingfei; Deng, Wen; Wang, Fengliang; Su, Yuehan; Feng, Yiping; Chen, Ping; Ma, Jingshuai; Su, Haiying; Yao, Kun; Liu, Yang; Lv, Wenying; Liu, Guoguang

2017-09-20

The aim of this study was to investigate the photolysis mechanism of ketoprofen (KET) under simulated sunlight. The results demonstrated that the photolysis of KET aligned well with pseudo first-order kinetics. Radical scavenging experiments and dissolved oxygen experiments revealed that the superoxide anion radical (O 2 ˙ - ) played a primary role in the photolytic process in pure water. Bicarbonate slightly increased the photodegradation of KET through generating carbonate radicals, while DOM inhibited the photolysis via both attenuating light and competing radicals. Moreover, Zhujiang river water inhibited KET phototransformation. Potential KET degradation pathways were proposed based on the identification of products using LC/MS/MS and GC/MS techniques. The theoretical prediction of reaction sites was derived from Frontier Electron Densities (FEDs), which primarily involved the KET decarboxylation reaction. The ecotoxicity of the treated solutions was evaluated by employing Daphnia magna and V. fischeri as biological indicators. Ecotoxicity was also hypothetically predicted through the "ecological structure-activity relationship" (ECOSAR) program, which revealed that toxic products might be generated during the photolysis process.

Automated Studies of Continuing Current in Lightning Flashes

NASA Astrophysics Data System (ADS)

Martinez-Claros, Jose

Continuing current (CC) is a continuous luminosity in the lightning channel that lasts longer than 10 ms following a lightning return stroke to ground. Lightning flashes following CC are associated with direct damage to power lines and are thought to be responsible for causing lightning-induced forest fires. The development of an algorithm that automates continuing current detection by combining NLDN (National Lightning Detection Network) and LEFA (Langmuir Electric Field Array) datasets for CG flashes will be discussed. The algorithm was applied to thousands of cloud-to-ground (CG) flashes within 40 km of Langmuir Lab, New Mexico measured during the 2013 monsoon season. It counts the number of flashes in a single minute of data and the number of return strokes of an individual lightning flash; records the time and location of each return stroke; performs peak analysis on E-field data, and uses the slope of interstroke interval (ISI) E-field data fits to recognize whether continuing current (CC) exists within the interval. Following CC detection, duration and magnitude are measured. The longest observed C in 5588 flashes was 631 ms. The performance of the algorithm (vs. human judgement) was checked on 100 flashes. At best, the reported algorithm is "correct" 80% of the time, where correct means that multiple stations agree with each other and with a human on both the presence and duration of CC. Of the 100 flashes that were validated against human judgement, 62% were hybrid. Automated analysis detects the first but misses the second return stroke in many cases where the second return stroke is followed by long CC. This problem is also present in human interpretation of field change records.

Flash Bulletin: Fireflies

ERIC Educational Resources Information Center

Brown, Debbie

1984-01-01

Explains the flashes of light emitted by fireflies as competition, species-specific code, species identification and mating behavior and ecology. Suggests activities to conduct to study the insects and their behavior. (ERB)

Weak positive cloud-to-ground flashes in Northeastern Colorado

NASA Technical Reports Server (NTRS)

Lopez, Raul E.; Maier, Michael W.; Garcia-Miguel, Juan A.; Holle, Ronald L.

1991-01-01

The frequency distributions of the peak magnetic field associated with the first detected return stroke of positive and negative cloud-to-ground (CG) flashes were studied using lightning data from northeastern Colorado. These data were obtained during 1985 with a medium-to-high gain network of three direction finders (DF's). The median signal strength of positive flashes was almost two times that of the negatives for flashes within 300 km of the DF's, which have an inherent detection-threshold bias that tends to discriminate against weak signals. This bias increases with range, and affects the detection of positive and negative flashes in different ways, because of the differing character of their distributions. Positive flashes appear to have a large percentage of signals clustered around very weak values that are lost to the medium-to-high gain Colorado Detection System very quickly with increasing range. The resulting median for positive signals could thus appear to be much larger than the median for negative signals, which are more clustered around intermediate values. When only flashes very close to the DF's are considered, however, the two distributions have almost identical medians. The large percentage of weak positive signals detected close to the DF's has not been explored previously. They have been suggested to come from intracloud discharges and thus are improperly classified as CG flashes. Evidence in hand, points to their being real positive, albeit weak CG flashes. Whether or not they are real positive ground flashes, it is important to be aware of their presence in data from magnetic DF networks.

An Improved B+ Tree for Flash File Systems

NASA Astrophysics Data System (ADS)

Havasi, Ferenc

Nowadays mobile devices such as mobile phones, mp3 players and PDAs are becoming evermore common. Most of them use flash chips as storage. To store data efficiently on flash, it is necessary to adapt ordinary file systems because they are designed for use on hard disks. Most of the file systems use some kind of search tree to store index information, which is very important from a performance aspect. Here we improved the B+ search tree algorithm so as to make flash devices more efficient. Our implementation of this solution saves 98%-99% of the flash operations, and is now the part of the Linux kernel.

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

NASA Technical Reports Server (NTRS)

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.

SUMO regulates proteasome-dependent degradation of FLASH/Casp8AP2

PubMed Central

Vennemann, Astrid; Hofmann, Thomas G.

2013-01-01

FLASH/Casp8AP2 is a huge multifunctional protein involved in multiple cellular processes, reaching from death receptor signaling to regulation of histone gene transcription and histone mRNA processing. Previous work has shown that FLASH localizes to Cajal bodies and promyelocytic leukemia (PML) bodies. However, the function of its nuclear body association remains unclear. Here we demonstrate that murine FLASH is covalently modified by SUMO at Lys residue 1792. Interestingly, ectopic expression of SUMO results in proteasome-dependent degradation of FLASH. A point mutant of FLASH with a mutated SUMO acceptor lysine residue, FLASHK1792R, is resistant to SUMO-induced degradation. Finally, we show that arsenic trioxide, a drug known to potentiate SUMO modification and degradation of PML, triggers recruitment of FLASH to PML bodies and concomitant loss of FLASH protein. Our data suggest that SUMO targets FLASH for proteasome-dependent degradation, which is associated with recruitment of FLASH to PML bodies. PMID:23673342

Diminished CAGE Effect in {p}-H2: Infrared Spectra of CH3S Observed from Photolysis of CH3SH, CH3SCH3, and CH3SSCH3 Isolated in {p}-H2

NASA Astrophysics Data System (ADS)

Lee, Yuan-Pern; Bahou, Mohammed

2010-06-01

We report infrared absorption spectrum of the methylthio (or thiomethoxy) radical, CH3S, isolated in solid {p}-H2. CH3S was produced by in situ UV photodissociation of three precursors: CH3SH, CH3SH3, and CH3SSCH3 isolated in solid {p}-H2. New absorption features commonly observed with similar intensity ratios in experiments using these precursors are assigned as absorption of CH3S. In Addition to the previously assigned transitions of ν 3 (a1) at 727.1 cm-1, fundamental transitions ν 6 (a1) at 771.1, ν 6 (e) at 1056.6, ν 5 (a1) at 1400.0, and &nu 4 (a1) at 2898.0 cm-1 were observed. The wavenumbers of these features agree satisfactorily with those predicted with a spin-vibronic Hamiltonian accounting for the anharmonic effects and the Jahn-Teller effects to the qu rtic term; the corresponding wavenumbers predicted from theory are ν 6 (a1) at 793, ν 6 (e) at 1105, ν 5 (a1) at 1436, and ν 4 (a1) at 2938 cm-1, with deviations of 14-4.6 % from experiments. Previous attempts of UV photolysis of CH3SCH3 and CH3SSCH3 isolated in an Ar matrix failed to produce CH3S. These results serve as an excellent example that the diminished cae effect of solid {p}-H2 makes production of free radicals via photolysis in situ feasible. If time permits, other examples will be discussed. A. V. Marenich and J. E. Boggs, J. Chem. Theory Comput., 1, 1162 (2005).

Improving Flash Flood Prediction in Multiple Environments

NASA Astrophysics Data System (ADS)

Broxton, P. D.; Troch, P. A.; Schaffner, M.; Unkrich, C.; Goodrich, D.; Wagener, T.; Yatheendradas, S.

2009-12-01

Flash flooding is a major concern in many fast responding headwater catchments . There are many efforts to model and to predict these flood events, though it is not currently possible to adequately predict the nature of flash flood events with a single model, and furthermore, many of these efforts do not even consider snow, which can, by itself, or in combination with rainfall events, cause destructive floods. The current research is aimed at broadening the applicability of flash flood modeling. Specifically, we will take a state of the art flash flood model that is designed to work with warm season precipitation in arid environments, the KINematic runoff and EROSion model (KINEROS2), and combine it with a continuous subsurface flow model and an energy balance snow model. This should improve its predictive capacity in humid environments where lateral subsurface flow significantly contributes to streamflow, and it will make possible the prediction of flooding events that involve rain-on-snow or rapid snowmelt. By modeling changes in the hydrologic state of a catchment before a flood begins, we can also better understand the factors or combination of factors that are necessary to produce large floods. Broadening the applicability of an already state of the art flash flood model, such as KINEROS2, is logical because flash floods can occur in all types of environments, and it may lead to better predictions, which are necessary to preserve life and property.

New developments in flash radiography

NASA Astrophysics Data System (ADS)

Mattsson, Arne

2007-01-01

The paper will review some of the latest developments in flash radiography. A series of multi anode tubes has been developed. These are tubes with several x-ray sources within the same vacuum enclosure. The x-ray sources are closely spaced, to come as close as possible to a single source. The x-ray sources are sequentially pulsed, at times that can be independently chosen. Tubes for voltages in the range 150 - 500 kV, with up to eight x-ray sources, will be described. Combining a multi anode tube with an intensified CCD camera, will make it possible to generate short "x-ray movies". A new flash x-ray control system has been developed. The system is operated from a PC or Laptop. All parameters of a multi channel flash x-ray system can be remotely set and monitored. The system will automatically store important operation parameters.

Flashing light in microalgae biotechnology.

PubMed

Abu-Ghosh, Said; Fixler, Dror; Dubinsky, Zvy; Iluz, David

2016-03-01

Flashing light can enhance photosynthesis and improve the quality and quantity of microalgal biomass, as it can increase the products of interest by magnitudes. Therefore, the integration of flashing light effect into microalgal cultivation systems should be considered. However, microalgae require a balanced mix of the light/dark cycle for higher growth rates, and respond to light intensity differently according to the pigments acquired or lost during the growth. This review highlights recently published results on flashing light effect on microalgae and its applications in biotechnology, as well as the recently developed bioreactors designed to fulfill this effect. It also discusses how this knowledge can be applied in selecting the optimal light frequencies and intensities with specific technical properties for increasing biomass production and/or the yield of the chemicals of interest by microalgae belonging to different genera. Copyright © 2015 Elsevier Ltd. All rights reserved.

An unusual characteristic “flower-like” pattern: flash suppressor burns

PubMed Central

Gurcan, Altun

2012-01-01

The case on contact shots from firearms with a flash suppressor is rare. When a rifle fitted with a flash suppressor is fired, the emerging soot-laden gas in the barrel escapes from the slits of the flash suppressor. If the shot is contact or near contact, the flash suppressor will produce a characteristic “flower-like” pattern of seared, blackened zones around the entrance. This paper presents the injury pattern of the flash suppressor in a 29-year-old man who committed suicide with a G3 automatic infantry rifle. PMID:23935280

Effect of Escitalopram on Hot Flash Interference: A Randomized, Controlled Trial

PubMed Central

Carpenter, Janet S.; Guthrie, Katherine A.; Larson, Joseph C.; Freeman, Ellen W.; Joffe, Hadine; Reed, Susan D.; Ensrud, Kristine E.; LaCroix, Andrea Z.

2012-01-01

Objectives To estimate the effect of escitalopram 10–20 mg/day versus placebo for reducing hot flash interference in daily life and understand correlates and predictors of reductions in hot flash interference, a key measure of quality of life. Design Multi-site, randomized, double-blind, placebo-controlled clinical trial. Patients 205 midlife women (46% African-American) who met criteria participated. Setting MsFLASH clinical sites in Boston, Indianapolis, Oakland, and Philadelphia. Intervention After baseline, women were randomized to 1 pill of escitalopram 10 mg/day (n=104) or placebo (n=101) with follow-up at 4- and 8-weeks. At week 4, those not achieving 50% fewer hot flashes were increased to 2 pills daily (20 mg/day or 2 placebo pills). Main outcome measures The Hot Flash Related Daily Interference Scale; Correlates were variables from hot flash diaries; Predictors were baseline demographics, clinical variables, depression, anxiety, sleep quality, and hot flashes. Results Compared to placebo, escitalopram significantly reduced hot flash interference by 6.0 points at week 4 and 3.4 points at week 8 more than placebo (p=0.012). Reductions in hot flash interference correlated with changes in hot flash diary variables. However, baseline variables did not significantly predict reductions in hot flash interference. Conclusions Escitalopram 10–20mg/day for 8 weeks improves women’s quality of life and this benefit did not vary by demographic, clinical, mood, sleep, or hot flash variables. PMID:22480818

Disinfection of Spacecraft Potable Water Systems by Photocatalytic Oxidation Using UV-A Light Emitting Diodes

NASA Technical Reports Server (NTRS)

Birmele, Michele N.; O'Neal, Jeremy A.; Roberts, Michael S.

2011-01-01

Ultraviolet (UV) light has long been used in terrestrial water treatment systems for photodisinfection and the removal of organic compounds by several processes including photoadsorption, photolysis, and photocatalytic oxidation/reduction. Despite its effectiveness for water treatment, UV has not been explored for spacecraft applications because of concerns about the safety and reliability of mercury-containing UV lamps. However, recent advances in ultraviolet light emitting diodes (UV LEDs) have enabled the utilization of nanomaterials that possess the appropriate optical properties for the manufacture of LEDs capable of producing monochromatic light at germicidal wavelengths. This report describes the testing of a commercial-off-the-shelf, high power Nichia UV-A LED (250mW A365nnJ for the excitation of titanium dioxide as a point-of-use (POD) disinfection device in a potable water system. The combination of an immobilized, high surface area photocatalyst with a UV-A LED is promising for potable water system disinfection since toxic chemicals and resupply requirements are reduced. No additional consumables like chemical biocides, absorption columns, or filters are required to disinfect and/or remove potentially toxic disinfectants from the potable water prior to use. Experiments were conducted in a static test stand consisting of a polypropylene microtiter plate containing 3mm glass balls coated with titanium dioxide. Wells filled with water were exposed to ultraviolet light from an actively-cooled UV-A LED positioned above each well and inoculated with six individual challenge microorganisms recovered from the International Space Station (ISS): Burkholderia cepacia, Cupriavidus metallidurans, Methylobacterium fujisawaense, Pseudomonas aeruginosa, Sphingomonas paucimobilis and Wautersia basilensis. Exposure to the Nichia UV-A LED with photocatalytic oxidation resulted in a complete (>7-log) reduction of each challenge bacteria population in <180 minutes of contact

NELIOTA: First temperature measurement of lunar impact flashes

NASA Astrophysics Data System (ADS)

Bonanos, A. Z.; Avdellidou, C.; Liakos, A.; Xilouris, E. M.; Dapergolas, A.; Koschny, D.; Bellas-Velidis, I.; Boumis, P.; Charmandaris, V.; Fytsilis, A.; Maroussis, A.

2018-04-01

We report the first scientific results from the NELIOTA (NEO Lunar Impacts and Optical TrAnsients) project, which has recently begun lunar monitoring observations with the 1.2-m Kryoneri telescope. NELIOTA aims to detect faint impact flashes produced by near-Earth meteoroids and asteroids and thereby help constrain the size-frequency distribution of near-Earth objects in the decimeter to meter range. The NELIOTA setup, consisting of two fast-frame cameras observing simultaneously in the R and I bands, enables - for the first time - direct analytical calculation of the flash temperatures. We present the first ten flashes detected, for which we find temperatures in the range 1600 to 3100 K, in agreement with theoretical values. Two of these flashes were detected on multiple frames in both filters and therefore yield the first measurements of the temperature drop for lunar flashes. In addition, we compute the impactor masses, which range between 100 g and 50 kg.

A Facile in Situ and UV Printing Process for Bioinspired Self-Cleaning Surfaces

PubMed Central

González Lazo, Marina A.; Katrantzis, Ioannis; Dalle Vacche, Sara; Karasu, Feyza; Leterrier, Yves

2016-01-01

A facile in situ and UV printing process was demonstrated to create self-cleaning synthetic replica of natural petals and leaves. The process relied on the spontaneous migration of a fluorinated acrylate surfactant (PFUA) within a low-shrinkage acrylated hyperbranched polymer (HBP) and its chemical immobilization at the polymer-air interface. Dilute concentrations of 1 wt. % PFUA saturated the polymer-air interface within 30 min, leading to a ten-fold increase of fluorine concentration at the surface compared with the initial bulk concentration and a water contact angle (WCA) of 108°. A 200 ms flash of UV light was used to chemically crosslink the PFUA at the HBP surface prior to UV printing with a polydimethylsiloxane (PDMS) negative template of red and yellow rose petals and lotus leaves. This flash immobilization hindered the reverse migration of PFUA within the bulk HBP upon contacting the PDMS template, and enabled to produce texturized surfaces with WCA well above 108°. The synthetic red rose petal was hydrophobic (WCA of 125°) and exhibited the adhesive petal effect. It was not superhydrophobic due to insufficient concentration of fluorine at its surface, a result of the very large increase of the surface of the printed texture. The synthetic yellow rose petal was quasi-superhydrophobic (WCA of 143°, roll-off angle of 10°) and its self-cleaning ability was not good also due to lack of fluorine. The synthetic lotus leaf did not accurately replicate the intricate nanotubular crystal structures of the plant. In spite of this, the fluorine concentration at the surface was high enough and the leaf was superhydrophobic (WCA of 151°, roll-off angle below 5°) and also featured self-cleaning properties. PMID:28773860

Why is the Great Red Spot Red? The Exogenic, Photolytic Origin of the UV/Blue-Absorbing Chromophores of Jupiter’s Great Red Spot as Determined by Spectral Analysis of Cassini/VIMS Observations using New Laboratory Optical Coefficients

NASA Astrophysics Data System (ADS)

Baines, Kevin H.; Carlson, Robert W.; Momary, Thomas W.

2014-11-01

For centuries, a major question for Jupiter has been: Why is the Great Red Spot red? In particular, two major theories have been proposed: (1) that the coloring is due to photolytic processes in the upper cloud layer, or (2) it is due to the upwellimg of red materials processed relatively deep within the troposphere. Utilizing indices of refraction for red choromophores generated by the photolysis of ammonia and acetylene in the laboratory, we present results of a spectral analysis of the core of Jupiter’s Great Red Spot (GRS) as observed by the visual channel of the Cassini/Visual Infrared Mapping Spectrometer (VIMS). Consistent with the physical origin of such laboratory-generated chromophores in Jupiter - i.e., by solar-driven UV photolysis within the upper levels of the GRS structure near ~ 0.3 bar - our spectral modeling yields satisfactory results for such Mie scattering chromophores only when they are confined to the upper ~ 100 mbar of the GRS. Beneath this reddish upper cloud layer, our models indicate that the remainder of the GRS cloud - assumed to extend down to at least the ammonia condensation level near 0.6 bar - must be relatively spectrally bright throughout the UV-red spectrum; that is, they must be predominantly a whitish or grey color at depth. Thus, our 0.35-1.0 micron spectral models of the GRS are inconsistent with an endogenic origin of the reddish coloring originating in the depths of Jupiter, but are consistent with a photolytic origin due to the photolysis of ammonia and acetylene in the upper troposphere.

Cardiac autonomic function and hot flashes among perimenopausal and postmenopausal women.

PubMed

Gibson, Carolyn J; Mendes, Wendy Berry; Schembri, Michael; Grady, Deborah; Huang, Alison J

2017-07-01

Abnormalities in autonomic function are posited to play a pathophysiologic role in menopausal hot flashes. We examined relationships between resting cardiac autonomic activity and hot flashes in perimenopausal and postmenopausal women. Autonomic function was assessed at baseline and 12 weeks among perimenopausal and postmenopausal women (n = 121, mean age 53 years) in a randomized trial of slow-paced respiration for hot flashes. Pre-ejection period (PEP), a marker of sympathetic activation, was measured with impedance cardiography. Respiratory sinus arrhythmia (RSA), a marker of parasympathetic activation, was measured with electrocardiography. Participants self-reported hot flash frequency and severity in 7-day symptom diaries. Analysis of covariance models were used to relate autonomic function and hot flash frequency and severity at baseline, and to relate changes in autonomic function to changes in hot flash frequency and severity over 12 weeks, adjusting for age, body mass index, and intervention assignment. PEP was not associated with hot flash frequency or severity at baseline or over 12 weeks (P > 0.05 for all). In contrast, there was a trend toward greater frequency of moderate-to-severe hot flashes with higher RSA at baseline (β = 0.43, P = 0.06), and a positive association between change in RSA and change in frequency of moderate-to-severe hot flashes over 12 weeks (β = 0.63, P = 0.04). Among perimenopausal and postmenopausal women with hot flashes, variations in hot flash frequency and severity were not explained by variations in resting sympathetic activation. Greater parasympathetic activation was associated with more frequent moderate-to-severe hot flashes, which may reflect increased sensitivity to perceiving hot flashes.

Naked-eye optical flash from gamma-ray burst 080319B: Tracing the decaying neutrons in the outflow

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

Fan Yizhong; Zhang Bing; Wei Daming

For an unsteady baryonic gamma-ray burst (GRB) outflow, the fast and slow proton shells collide with each other and produce energetic soft gamma-ray emission. If the outflow has a significant neutron component, the ultrarelativistic neutrons initially expand freely until decaying at a larger radius. The late-time proton shells ejected from the GRB central engine, after powering the regular internal shocks, will sweep these {beta}-decay products and give rise to very bright UV/optical emission. The naked-eye optical flash from GRB 080319B, an energetic explosion in the distant Universe, can be well explained in this way.

Photodegradation of Mefenamic Acid in Aqueous Media: Kinetics, Toxicity and Photolysis Products.

PubMed

Chen, Ping; Wang, Feng Liang; Yao, Kun; Ma, Jing Shuai; Li, Fu Hua; Lv, Wen Ying; Liu, Guo Guang

2016-02-01

The present study investigated the photolytic behavior and photodegradation products of mefenamic acid (MEF) under ultraviolet-C irradiation. The results demonstrated that the photodegradation of MEF followed pseudo-first-order kinetics and the direct photolysis quantum yield of mefenamic acid was observed to be 2.63 ± 0.28 × 10⁻³. Photodegradation of MEF included degradation by direct photolysis and by self-sensitization that the contribution rates of self-sensitized photodegradation were 5.70, 11.25 and 18.96 % for ·OH, ¹O₂ and O·₂⁻ , respectively. Primary transformation products of MEF were identified using ultra performance liquid chromatography and quadrupole time-of-flight mass spectrometer (UPLC-Q-TOF-MS). The identified transformation products suggested three possible pathways of MEF photodegradation: dehydrogenation, hydroxylation, and ketonized reactions. Toxicity of phototransformation products were evaluated using the Microtox test, which revealed that photodegradation likely provides a critical pathway for MEF toxicity reduction in drinking water and wastewater treatment facilities.

High-density patterned media fabrication using jet and flash imprint lithography

NASA Astrophysics Data System (ADS)

Ye, Zhengmao; Ramos, Rick; Brooks, Cynthia; Simpson, Logan; Fretwell, John; Carden, Scott; Hellebrekers, Paul; LaBrake, Dwayne; Resnick, Douglas J.; Sreenivasan, S. V.

2011-04-01

The Jet and Flash Imprint Lithography (J-FIL®) process uses drop dispensing of UV curable resists for high resolution patterning. Several applications, including patterned media, are better, and more economically served by a full substrate patterning process since the alignment requirements are minimal. Patterned media is particularly challenging because of the aggressive feature sizes necessary to achieve storage densities required for manufacturing beyond the current technology of perpendicular recording. In this paper, the key process steps for the application of J-FIL to pattern media fabrication are reviewed with special attention to substrate cleaning, vapor adhesion of the adhesion layer and imprint performance at >300 disk per hour. Also discussed are recent results for imprinting discrete track patterns at half pitches of 24nm and bit patterned media patterns at densities of 1 Tb/in2.

Long-term Stability of the Post-Flash LED Lamp

NASA Astrophysics Data System (ADS)

Martlin, Catherine; Baggett, Sylvia

2017-02-01

We report the results of a study of the long-term stability of the LED lamp used in post-flashing WFC3/UVIS images. We analyze 644 sub-array exposures taken over the course of just over 3 years and find no significant long-term trends in the LED lamp brightness. The average percentage change per year over all FLASH level and shutter combinations is found to be 0.15% per year with an uncertainty of ± 0.24% per year. The maximum measured percentage change per year was 0.39% for the highest FLASH level of 20 e- on shutter A which would indicate a change of less than 1 e-/pixel over the roughly 3 years since post-flashing began. There are, however, occasional short-term deviations in the LED output. The average minimum and maximum outliers over all FLASH level and shutter combination subsets are 4.1% below and 3.5% above, respectively, the mean of that subset. The maximum outlier over all the sets is 5.8% above the normalized mean value, for FLASH level 3/shutter A. The minimum outlier over all sets is also for FLASH level 3/shutter A and is 8.9% below the normalized mean value. Investigation of these outliers has revealed no systematic cause for the excursions and we recommend that users continue using the post-flash as they would have previously.

Some Improvements in Utilization of Flash Memory Devices

NASA Technical Reports Server (NTRS)

Gender, Thomas K.; Chow, James; Ott, William E.

2009-01-01

Two developments improve the utilization of flash memory devices in the face of the following limitations: (1) a flash write element (page) differs in size from a flash erase element (block), (2) a block must be erased before its is rewritten, (3) lifetime of a flash memory is typically limited to about 1,000,000 erases, (4) as many as 2 percent of the blocks of a given device may fail before the expected end of its life, and (5) to ensure reliability of reading and writing, power must not be interrupted during minimum specified reading and writing times. The first development comprises interrelated software components that regulate reading, writing, and erasure operations to minimize migration of data and unevenness in wear; perform erasures during idle times; quickly make erased blocks available for writing; detect and report failed blocks; maintain the overall state of a flash memory to satisfy real-time performance requirements; and detect and initialize a new flash memory device. The second development is a combination of hardware and software that senses the failure of a main power supply and draws power from a capacitive storage circuit designed to hold enough energy to sustain operation until reading or writing is completed.

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process

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

Abidin, Che Zulzikrami Azner, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fahmi, Muhammad Ridwan, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fazara, Md Ali Umi, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com

2014-10-24

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV/H{sub 2}O{sub 2} experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV/H{sub 2}O{sub 2} process is meaningful with respectmore » to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H{sub 2}O{sub 2} photolysis.« less

Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin

PubMed Central

Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhanqing; Dickerson, Russell R.; Stenchikov, Georgiy L.; Osipov, Sergey; Ren, Xinrong

2016-01-01

The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or “brown” carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305–368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning. PMID:27833145

UV-light-driven prebiotic synthesis of iron-sulfur clusters

NASA Astrophysics Data System (ADS)

Bonfio, Claudia; Valer, Luca; Scintilla, Simone; Shah, Sachin; Evans, David J.; Jin, Lin; Szostak, Jack W.; Sasselov, Dimitar D.; Sutherland, John D.; Mansy, Sheref S.

2017-12-01

Iron-sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron-sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron-sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe-2S] and [4Fe-4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron-sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron-sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron-sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron-sulfur-cluster-dependent metabolism.

Photolysis Rate Coefficient Calculations in Support of SOLVE II

NASA Technical Reports Server (NTRS)

Swartz, William H.

2005-01-01

A quantitative understanding of photolysis rate coefficients (or "j-values") is essential to determining the photochemical reaction rates that define ozone loss and other crucial processes in the atmosphere. j-Values can be calculated with radiative transfer models, derived from actinic flux observations, or inferred from trace gas measurements. The primary objective of the present effort was the accurate calculation of j-values in the Arctic twilight along NASA DC-8 flight tracks during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II), based in Kiruna, Sweden (68 degrees N, 20 degrees E) during January-February 2003. The JHU/APL radiative transfer model was utilized to produce a large suite of j-values for photolysis processes (over 70 reactions) relevant to the upper troposphere and lower stratosphere. The calculations take into account the actual changes in ozone abundance and apparent albedo of clouds and the Earth surface along the aircraft flight tracks as observed by in situ and remote sensing platforms (e.g., EP-TOMS). A secondary objective was to analyze solar irradiance data from NCAR s Direct beam Irradiance Atmospheric Spectrometer (DIAS) on-board the NASA DC-8 and to start the development of a flexible, multi-species spectral fitting technique for the independent retrieval of O3,O2.02, and aerosol optical properties.

Effect of UV irradiation on aflatoxin reduction: a cytotoxicity evaluation study using human hepatoma cell line.

PubMed

Patras, Ankit; Julakanti, Sharath; Yannam, Sudheer; Bansode, Rishipal R; Burns, Mallory; Vergne, Matthew J

2017-11-01

In this proof-of-concept study, the efficacy of a medium-pressure UV (MPUV) lamp source to reduce the concentrations of aflatoxin B 1 , aflatoxin B 2 , and aflatoxin G 1 (AFB 1, AFB 2 , and AFG 1 ) in pure water is investigated. Irradiation experiments were conducted using a collimated beam system operating between 200 to 360 nm. The optical absorbance of the solution and the irradiance of the lamp are considered in calculating the average fluence rate. Based on these factors, the UV dose was quantified as a product of average fluence rate and treatment time. Known concentrations of aflatoxins were spiked in water and irradiated at UV doses ranging from 0, 1.22, 2.44, 3.66, and 4.88 J cm -2 . The concentration of aflatoxins was determined by HPLC with fluorescence detection. LC-MS/MS product ion scans were used to identify and semi-quantify degraded products of AFB 1 , AFB 2 , and AFG 1 . It was observed that UV irradiation significantly reduced aflatoxins in pure water (p < 0.05). Irradiation doses of 4.88 J cm -2 reduced concentrations 67.22% for AFG 1 , 29.77% for AFB 2 , and 98.25% for AFB 1 (p < 0.05). Using this technique, an overall reduction of total aflatoxin content of ≈95% (p < 0.05) was achieved. We hypothesize that the formation of ˙OH radicals initiated by UV light may have caused photolysis of AFB 1 , AFB 2 , and AFG 1 molecules. In cell culture studies, our results demonstrated that the increase of UV dosage decreased the aflatoxin-induced cytotoxicity in HepG 2 cells. Therefore, our research finding suggests that UV irradiation can be used as an effective technique for the reduction of aflatoxins.

Photolysis of Low-Brominated Diphenyl Ethers and Their Reactive Oxygen Species-Related Reaction Mechanisms in an Aqueous System

PubMed Central

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. PMID:26274605

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter.

PubMed

Luning Prak, Dianne J; Breuer, James E T; Rios, Evelyn A; Jedlicka, Erin E; O'Sullivan, Daniel W

2017-01-30

The influence of salinity, pH, temperature, and dissolved organic matter on the photolysis rate of 2,4,6-trinitrotoluene (TNT) in marine, estuary, and laboratory-prepared waters was studied using a Suntest CPS+® solar simulator equipped with optical filters. TNT degradation rates were determined using HPLC analysis, and products were identified using LC/MS. Minimal or no TNT photolysis occurred under a 395-nm long pass filter, but under a 295-nm filter, first-order TNT degradation rate constants and apparent quantum yields increased with increasing salinity in both natural and artificial seawater. TNT rate constants increased slightly with increasing temperature (10 to 32°C) but did not change significantly with pH (6.4 to 8.1). The addition of dissolved organic matter (up to 5mg/L) to ultrapure water, artificial seawater, and natural seawater increased the TNT photolysis rate constant. Products formed by TNT photolysis in natural seawater were determined to be 2,4,6-trinitrobenzaldehyde, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzoic acid, and 2-amino-4,6-dinitrobenzoic acid. Published by Elsevier Ltd.

Understanding the complex relationships underlying hot flashes: a Bayesian network approach.

PubMed

Smith, Rebecca L; Gallicchio, Lisa M; Flaws, Jodi A

2018-02-01

The mechanism underlying hot flashes is not well-understood, primarily because of complex relationships between and among hot flashes and their risk factors. We explored those relationships using a Bayesian network approach based on a 2006 to 2015 cohort study of hot flashes among 776 female residents, 45 to 54 years old, in the Baltimore area. Bayesian networks were fit for each outcome (current hot flashes, hot flashes before the end of the study, hot flash severity, hot flash frequency, and age at first hot flashes) separately and together with a list of risk factors (estrogen, progesterone, testosterone, body mass index and obesity, race, income level, education level, smoking history, drinking history, and activity level). Each fitting was conducted separately on all women and only perimenopausal women, at enrollment and 4 years after enrollment. Hormone levels, almost always interrelated, were the most common variable linked to hot flashes; hormone levels were sometimes related to body mass index, but were not directly related to any other risk factors. Smoking was also frequently associated with increased likelihood of severe symptoms, but not through an antiestrogenic pathway. The age at first hot flashes was related only to race. All other factors were either not related to outcomes or were mediated entirely by race, hormone levels, or smoking. These models can serve as a guide for design of studies into the causal network underlying hot flashes.

A hybrid ferroelectric-flash memory cells

NASA Astrophysics Data System (ADS)

Park, Jae Hyo; Byun, Chang Woo; Seok, Ki Hwan; Kim, Hyung Yoon; Chae, Hee Jae; Lee, Sol Kyu; Son, Se Wan; Ahn, Donghwan; Joo, Seung Ki

2014-09-01

A ferroelectric-flash (F-flash) memory cells having a metal-ferroelectric-nitride-oxynitride-silicon structure are demonstrated, and the ferroelectric materials were perovskite-dominated Pb(Zr,Ti)O3 (PZT) crystallized by Pt gate electrode. The PZT thin-film as a blocking layer improves electrical and memorial performance where programming and erasing mechanism are different from the metal-ferroelectric-insulator-semiconductor device or the conventional silicon-oxide-nitride-oxide-silicon device. F-flash cells exhibit not only the excellent electrical transistor performance, having 442.7 cm2 V-1 s-1 of field-effect mobility, 190 mV dec-1 of substhreshold slope, and 8 × 105 on/off drain current ratio, but also a high reliable memory characteristics, having a large memory window (6.5 V), low-operating voltage (0 to -5 V), faster P/E switching speed (50/500 μs), long retention time (>10 years), and excellent fatigue P/E cycle (>105) due to the boosting effect, amplification effect, and energy band distortion of nitride from the large polarization. All these characteristics correspond to the best performances among conventional flash cells reported so far.

High-Fidelity Flash Lidar Model Development

NASA Technical Reports Server (NTRS)

Hines, Glenn D.; Pierrottet, Diego F.; Amzajerdian, Farzin

2014-01-01

NASA's Autonomous Landing and Hazard Avoidance Technologies (ALHAT) project is currently developing the critical technologies to safely and precisely navigate and land crew, cargo and robotic spacecraft vehicles on and around planetary bodies. One key element of this project is a high-fidelity Flash Lidar sensor that can generate three-dimensional (3-D) images of the planetary surface. These images are processed with hazard detection and avoidance and hazard relative navigation algorithms, and then are subsequently used by the Guidance, Navigation and Control subsystem to generate an optimal navigation solution. A complex, high-fidelity model of the Flash Lidar was developed in order to evaluate the performance of the sensor and its interaction with the interfacing ALHAT components on vehicles with different configurations and under different flight trajectories. The model contains a parameterized, general approach to Flash Lidar detection and reflects physical attributes such as range and electronic noise sources, and laser pulse temporal and spatial profiles. It also provides the realistic interaction of the laser pulse with terrain features that include varying albedo, boulders, craters slopes and shadows. This paper gives a description of the Flash Lidar model and presents results from the Lidar operating under different scenarios.

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

USGS Publications Warehouse

Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

1993-01-01

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Kappa Agonists as a Novel Therapy for Menopausal Hot Flashes

PubMed Central

Oakley, Amy E.; Steiner, Robert A.; Chavkin, Charles; Clifton, Donald K.; Ferrara, Laura K.; Reed, Susan D.

2015-01-01

Objective Postmenopausal hot flash etiology is poorly understood, making it difficult to develop and target ideal therapies. A network of hypothalamic estrogen-sensitive neurons producing Kisspeptin, Neurokinin B, and Dynorphin (KNDy neurons), located adjacent to the thermoregulatory center, regulate pulsatile secretion of GnRH and LH. Dynorphin may inhibit this system by binding kappa opioid receptors within the vicinity of KNDy neurons. We hypothesize that hot flashes are reduced by KNDy neuron manipulation. Methods A double-blind, cross-over, placebo-controlled pilot study evaluated the effect of a kappa agonist (KA).Hot flash frequency was the primary outcome. Twelve healthy postmenopausal women with moderate-severe hot flashes, ages 48-60 years, were randomized. Eight women with sufficient baseline hot flashes for statistical analysis completed all 3 interventions: placebo, standard Pentazocine/Naloxone (50/0.5 mg) or low-dose Pentazocine/Naloxone (25/0.25 mg). In an inpatient research setting, each participant received the 3 interventions, in randomized order, on 3 separate days. On each day, an intravenous catheter was inserted for luteinizing hormone (LH) blood sampling, and skin conductance and Holter monitors were placed. Subjective hot flash frequency and severity were recorded. Results Mean hot flash frequency 2-7 hours following therapy initiation was lower than that for placebo (KA standard-dose: 4.75 ± 0.67; KA low-dose: 4.50 ± 0.57; and placebo: 5.94 ± 0.78 hot flashes/5 hours; p =0.025). Hot flash intensity did not vary between interventions. LH pulsatility mirrored objective hot flashes in some, but not all women. Conclusions This pilot suggests that kappa agonists may affect menopausal vasomotor symptoms. PMID:25988798