Bactericidal Effect of Photolysis of H2O2 in Combination with Sonolysis of Water via Hydroxyl Radical Generation.

PubMed

Sheng, Hong; Nakamura, Keisuke; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2015-01-01

The bactericidal effect of hydroxyl radical (·OH) generated by combination of photolysis of hydrogen peroxide (H2O2) and sonolysis of water was examined under the condition in which the yield of ·OH increased additively when H2O2 aqueous solution was concomitantly irradiated with laser and ultrasound. The suspension of Staphylococcus aureus mixed with the different concentrations of H2O2 was irradiated simultaneously with a laser light (wavelength: 405 nm, irradiance: 46 and 91 mW/cm2) and ultrasound (power: 30 w, frequency: 1.65 MHz) at 20 ± 1°C of the water bulk temperature for 2 min. The combination of laser and ultrasound irradiation significantly reduced the viable bacterial count in comparison with the laser irradiation of H2O2 alone. By contrast, the ultrasound irradiation alone exerted almost no bactericidal effect. These results suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity was synergistic. A multi-way analysis of variance also revealed that the interaction of H2O2 concentration, laser power and ultrasound irradiation significantly affected the bactericidal activity. Since the result of oxidative DNA damage evaluation demonstrated that the combination of laser and ultrasound irradiation significantly induced oxidative damage of bacterial DNA in comparison with the laser irradiation of H2O2 alone, it was suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity would be exerted via oxidative damage of cellular components such as DNA.

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.

The role of direct photolysis and indirect photochemistry in the environmental fate of ethylhexyl methoxy cinnamate (EHMC) in surface waters.

PubMed

Vione, D; Calza, P; Galli, F; Fabbri, D; Santoro, V; Medana, C

2015-12-15

The aquatic environmental fate of ethylhexyl methoxy cinnamate (EHMC), one of the most used UVB filters worldwide, was studied by assessing its environmental persistence and photoinduced transformations. The role of direct and indirect photolysis was evaluated. Direct photolysis was shown to play a key role, and this process is expected to be the main attenuation route of EHMC in sunlit surface waters. In contrast, the reaction with OH radicals would be negligible and that with (3)CDOM* would at most be a secondary process. The measurement of the quantum yield of direct photolysis and of the rate constants of reaction with photogenerated transient species (or, sometimes, the use of reasonable values for the latter) allowed the prediction of the EHMC half-life time in surface waters, by means of a validated photochemical model. The predicted EHMC lifetime is of the order of hours to a few days in fair-weather summertime, and the main factors controlling the EHMC phototransformation in sunlit surface waters would be the water depth and the dissolved organic carbon (DOC) content. The formation of transformation products (TPs) was followed as well via HPLC/HRMS. Three TPs were detected in the samples exposed to UVA radiation, while one additional TP was detected in the samples exposed to UVB radiation. The detected TPs comprised 4-methoxybenzaldehyde, a hydroxylated derivative and dimeric species. Through the use of heterogeneous photocatalysis with TiO2, seven additional TPs were identified, most of them resulting from the further degradation of primary TPs formed through direct photolysis and that might be detected in aquatic systems as well. The photodegradation of EHMC in the presence of TiO2 yielded more toxic TPs than the parent compound (as determined with the Vibrio fischeri Microtox assay). The increased toxicity is partially accounted for by the formation of 4-methoxybenzaldehyde. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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.

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.

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⁺.

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.

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.

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.

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.

Removal of organic matter from a variety of water matrices by UV photolysis and UV/H2O2 method.

PubMed

Vilhunen, Sari; Vilve, Miia; Vepsäläinen, Mikko; Sillanpää, Mika

2010-07-15

A re-circulated flow-through photoreactor was used to evaluate the ultraviolet (UV) photolysis and UV/H(2)O(2) oxidation process in the purification of three different water matrices. Chemically coagulated and electrocoagulated surface water, groundwater contaminated with creosote wood preservative and 1,2-dichloroethane (DCE) containing washing water from the plant manufacturing tailor-made ion-exchange resins were used as sample waters. The organic constituents of creosote consist mainly of harmful polycyclic aromatic hydrocarbons (PAH) whereas 1,2-DCE is a toxic volatile organic compound (VOC). Besides analyzing the specific target compounds, total organic carbon (TOC) analysis and measurement of change in UV absorbance at 254 nm (UV(254)) were performed. Initial TOC, UV(254) and pH varied significantly among treated waters. Initial H(2)O(2) concentrations 0-200 mg/l were used. The UV/H(2)O(2) treatment was efficient in removing the hazardous target pollutants (PAHs and 1,2-DCE) and natural organic matter (NOM). In addition, high removal efficiency for TOC was achieved for coagulated waters and groundwater. Also, the efficiency of direct photolysis in UV(254) removal was significant except in the treatment of 1,2-DCE containing washing water. Overall, UV(254) and TOC removal rates were high, except in case of washing water, and the target pollutants were efficiently decomposed with the UV/H(2)O(2) method. 2010 Elsevier B.V. All rights reserved.

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...

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

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.

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.

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.

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.

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.

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

Synchronized flash photolysis and pulse deposition in matrix isolation experiments

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

1978-01-01

An apparatus is described which permits flash photolysis of a pulse-deposited gas mixture in a matrix isolation experiment. This technique obviates the limitations of in situ photolysis imposed by the cage effect and by secondary photolysis. The matrix is deposited in pulses at 30-s intervals and photolyzed sequentially by four synchronized flashlamps approximately 1 ms before the pulse strikes the cold surface. Pulsed deposition maintains adequate isolation and causes line narrowing, which enhances spectral sensitivity. The efficacy of flash photolysis combined with pulsed deposition for producing and trapping transient species was demonstrated by infrated detection of CF3 (from photolysis of CF3I/Ar mixtures) and of ClCO (from photolysis of Cl2/CO/Ar mixtures). The apparatus was used to study the photolytic decomposition of gaseous tricarbonylironcyclobutadiene, C4H4Fe(CO)3. The results indicate that the primary photolytic step is not elimination of C4H4, as suggested earlier, but rather of CO.

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.

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.

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%.

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...

[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.

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

How UV photolysis accelerates the biodegradation and mineralization of sulfadiazine (SD).

PubMed

Pan, Shihui; Yan, Ning; Liu, Xinyue; Wang, Wenbing; Zhang, Yongming; Liu, Rui; Rittmann, Bruce E

2014-11-01

Sulfadiazine (SD), one of broad-spectrum antibiotics, exhibits limited biodegradation in wastewater treatment due to its chemical structure, which requires initial mono-oxygenation reactions to initiate its biodegradation. Intimately coupling UV photolysis with biodegradation, realized with the internal loop photobiodegradation reactor, accelerated SD biodegradation and mineralization by 35 and 71 %, respectively. The main organic products from photolysis were 2-aminopyrimidine (2-AP), p-aminobenzenesulfonic acid (ABS), and aniline (An), and an SD-photolysis pathway could be identified using C, N, and S balances. Adding An or ABS (but not 2-AP) into the SD solution during biodegradation experiments (no UV photolysis) gave SD removal and mineralization rates similar to intimately coupled photolysis and biodegradation. An SD biodegradation pathway, based on a diverse set of the experimental results, explains how the mineralization of ABS and An (but not 2-AP) provided internal electron carriers that accelerated the initial mono-oxygenation reactions of SD biodegradation. Thus, multiple lines of evidence support that the mechanism by which intimately coupled photolysis and biodegradation accelerated SD removal and mineralization was through producing co-substrates whose oxidation produced electron equivalents that stimulated the initial mono-oxygenation reactions for SD biodegradation.

Degradation of naproxen by UV, VUV photolysis and their combination.

PubMed

Arany, Eszter; Szabó, Rita Katalin; Apáti, László; Alapi, Tünde; Ilisz, István; Mazellier, Patrick; Dombi, András; Gajda-Schrantz, Krisztina

2013-11-15

Naproxen is a widely used nonsteroidal anti-inflammatory drug. Recently, this medicine was detected both in natural waters (up to 1.5 μg L(-1)) and in sewage treatment plant effluents (up to 5.2 μg L(-1)). Moreover, naproxen is only partly eliminated by classical processes used in sewage treatment plants. Therefore, its degradation is of utmost interest. Advanced oxidation processes proved to be the most suitable methods for the elimination of persistent organic contaminants. In this work ultraviolet (UV, 254 nm), vacuum ultraviolet photolysis (VUV, 172 nm) and their combination (UV/VUV, 254/185 nm) were investigated. The efficiency of the methods increased in the following order: UV < VUV < UV/VUV photolysis. However, VUV irradiation was found to mineralize the contaminant molecule most effectively. The chemical structures of three out of four aromatic by-products and of some aliphatic carboxylic acids were presumed. The effects of dissolved O2 and the initial concentration of naproxen on the degradation were also investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Water quality parameters controlling the photodegradation of two herbicides in surface waters of the Columbia Basin, Washington.

PubMed

Furman, Olha S; Yu, Miao; Teel, Amy L; Watts, Richard J

2013-11-01

The water quality parameters nitrate-nitrogen, dissolved organic carbon, and suspended solids were correlated with photodegradation rates of the herbicides atrazine and 2,4-D in samples collected from four sites in the Columbia River Basin, Washington, USA. Surface water samples were collected in May, July, and October 2010 and analyzed for the water quality parameters. Photolysis rates for the two herbicides in the surface water samples were then evaluated under a xenon arc lamp. Photolysis rates of atrazine and 2,4-D were similar with rate constants averaging 0.025 h(-1) for atrazine and 0.039 h(-1) for 2,4-D. Based on multiple regression analysis, nitrate-nitrogen was the primary predictor of photolysis for both atrazine and 2,4-D, with dissolved organic carbon also a predictor for some sites. However, at sites where suspended solids concentrations were elevated, photolysis rates of the two herbicides were controlled by the suspended solids concentration. The results of this research provide a basis for evaluating and predicting herbicide photolysis rates in shallow surface waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

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.

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.

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).

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).

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

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

Eyring, E.M.

1992-01-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

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

Eyring, E.M.

1992-10-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

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.

Comparison of Direct and Indirect Photolysis in Imazosulfuron Photodegradation.

PubMed

Rering, Caitlin; Williams, Katryn; Hengel, Matt; Tjeerdema, Ronald

2017-04-19

Imazosulfuron, a sulfonylurea herbicide used in rice cultivation, has been shown to undergo photodegradation in water, but neither the photochemical mechanism nor the role of indirect photolysis is known. The purpose of this study was to investigate the underlying processes that operate on imazosulfuron during aqueous photodegradation. Our data indicate that in the presence of oxygen, most photochemical degradation proceeds through a direct singlet-excited state pathway, whereas triplet-excited state imazosulfuron enhanced decay rates under low dissolved oxygen conditions. Oxidation by hydroxyl radical and singlet oxygen were not significant. At dissolved organic matter (DOM) concentrations representative of rice field conditions, fulvic acid solutions exhibited faster degradation than rice field water containing both humic and fulvic acid fractions. Both enhancement, via reaction with triplet-state DOM, and inhibition, via competition for photons, of degradation was observed in DOM solutions.

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.

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.

In vitro and in vivo anti-Staphylococcus aureus activities of a new disinfection system utilizing photolysis of hydrogen peroxide.

PubMed

Hayashi, Eisei; Mokudai, Takayuki; Yamada, Yasutomo; Nakamura, Keisuke; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2012-08-01

The present study aimed to evaluate in vitro and in vivo antibacterial activity of hydroxyl radical generation system by photolysis of H(2)O(2), which is a new disinfection system for the treatment of oral infection diseases such as periodontitis developed in our laboratory. Firstly, generation of the hydroxyl radical by the photolysis of H(2)O(2) in which 1 mol l(-1) H(2)O(2) was irradiated with a dual wavelength-light emitting diode (LED) at wavelengths of 400 and 465 nm was confirmed by applying an electron spin resonance-spin trapping technique. Secondly, the bactericidal effect of the system was examined under a similar condition in which Staphylococcus aureus suspended in 1 mol l(-1) H(2)O(2) was irradiated with LED light, resulting in substantial reduction of the colony forming unit (CFU) of the bacteria within a short time as 2 min. Finally, in vivo antibacterial effect of the photolysis of H(2)O(2) on a rat model of S. aureus infection was evaluated by a culture study. Since a significant reduction of recovered CFU of S. aureus was obtained, it is expected that in vitro antibacterial effect attributable to hydroxyl radicals generated by photolysis of H(2)O(2) could be well reflected in in vivo superficial bacterial infection. Copyright © 2012 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

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...

UV photolysis for enhanced phenol biodegradation in the presence of 2,4,6-trichlorophenol (TCP).

PubMed

Song, Jiaxiu; Wang, Wenbing; Li, Rongjie; Zhu, Jun; Zhang, Yongming; Liu, Rui; Rittmann, Bruce E

2016-02-01

A bacterial strain isolated from activated sludge and identified as Bacillus amyloliquefaciens could biodegrade phenol, but 2,4,6-trichlorophenol (TCP) inhibited phenol biodegradation and biomass growth. UV photolysis converted TCP into dichlorocatechol, monochlorophenol, and dichlorophenol, and this relieved inhibition by TCP. Phenol-removal and biomass-growth rates were significantly accelerated after UV photolysis: the monod maximum specific growth rate (μ(max)) increased by 9% after TCP photolysis, and the half-maximum-rate concentration (K(S)) decreased by 36%. Thus, the major benefit of UV photolysis in this case was to transform TCP into a set of much-less-inhibitory products.

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.

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.

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.

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

PubMed

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

2015-09-18

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

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.

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.

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.

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).

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.

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.

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)

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).

The aqueous photolysis of ethylene glycol adsorbed on geothite

USGS Publications Warehouse

Cunningham, Kirkwood M.; Goldberg, Marvin C.; Weiner, E.R.

1985-01-01

Suspensions of goethite (α-FeOOH) were photolyzed in aerated ethylene glycol-water solutions at pH 6.5, with ultraviolet light in the wavelength range300–400 nm. Under these conditions, formaldehyde and glycolaldehyde were detected as photoproducts. Quantum yields of formaldehyde production ranged from 1.9 7times; 10-5 to 2.9 × 10-4 over the ethylene glycol concentration range of 0.002-2.0 mol/ℓ, and gave evidence that the reaction occurred at the goethite surface. Quantum yields of glycolaldehyde were 20% less than those of formaldehyde, and displayed a concentration-dependent relationship with ethylene glycol similar to that of formaldehyde. Immediately after photolysis, Fe2+ was measured to be 4.6 × 10-7 mol/ℓ in an aerated suspension containing 1.3 mol/ℓ ethylene glycol, and 8.5 × 10-6 mol/ℓ in the corresponding deoxygenated suspension. Glycolaldehyde was not generated in the deoxygenated suspensions. These results are consistent with a mechanism involving the transfer of an electron from an adsorbed ethylene glycol molecule to an excited state of Fe3+ (Iron[III]) in the goethite lattice, to produce Fe2+ and an organic cation. In a series of reactions involving O2, FeOOH, and Fe2+, the organic cation decomposes to form formaldehyde and the intermediate radicals “OH and” CH2OH. OH reacts further with ethylene glycol in the presence of O2to yield glycolaldehyde. Aqueous photolysis of ethylene glycol sorbed onto goethite is typical of reactions that can occur in the aquatic environment.

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

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.

Novel approach to real-time flash photolysis and confocal [Ca2+] imaging

PubMed Central

Sobie, Eric A.; Kao, Joseph P.Y.; Lederer, W. J.

2008-01-01

Flash photolysis of “caged” compounds using ultraviolet light is a powerful experimental technique for producing rapid changes in concentrations of bioactive signaling molecules. Studies that employ this technique have used diverse strategies for controlling the spatial and temporal application of light to the specimen. Here we describe a new system for flash photolysis that delivers light from a pulsed, adjustable intensity laser through an optical fiber coupled into the epifluorescence port of a commercial confocal microscope. Photolysis is achieved with extremely brief (5 ns) pulses of ultraviolet light (355 nm) that can be synchronized with respect to confocal laser scanning. The system described also localizes the UV intensity spatially so that uncaging only occurs in defined sub-cellular regions; moreover, since the microscope optics are used in localization, the photolysis volume can be easily adjusted. Experiments performed on rat ventricular myocytes loaded with the Ca2+ indicator fluo-3 and the Ca2+ cage NP-EGTA demonstrate the system's capabilities. Localized intracellular increases in [Ca2+] can trigger sarcoplasmic reticular Ca2+ release events such as Ca2+ sparks and, under certain conditions, regenerative Ca2+ waves. This relatively simple and inexpensive system is therefore a useful tool for examining local signaling in heart and other tissues. PMID:17323075

Study on Control of NH4 +-N in Surface Water by Photocatalytic

NASA Astrophysics Data System (ADS)

Zuo, Xiaoran; He, Honghua; Yang, Yue; Yan, Chao; Zhou, Ying

2018-01-01

NH4 +-N has become the main pollution factor affecting the surface water quality in China. Based on the theory of photolysis, the feasibility of photolysis removing NH4 +-N in surface water is studied. The effects of pH, CaO2 content and photolysis time on removal rate of NH4 +-N are studied. The actual study is based on Laboratory studies results. Experimental results show: When the pH<7, photolysis can increase the NH4 +-N content. And when pH>8, the photolysis can greatly reduce the NH4 +-N content in water. CaO2 can greatly remove NH4 +-N. The removal rate of NH4 +-N increased with the increase of photocatalytic time. When irradiated with UV light for 108 hours or the sun is irradiated for about 40 days, NH4 +-N content can be reduced from 4mg/L to 0.5mg/L under the optimum experimental conditions. Adjusting the pH of surface water is the most important condition for controlling NH4 +-N content.

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

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 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.

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.

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues.

PubMed

Bernstein, Max P; Dworkin, Jason P; Sandford, Scott A; Cooper, George W; Allamandola, Louis J

2002-03-28

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George W.; Allamandola, Louis J.

2002-01-01

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

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.

Photodegradation of ibuprofen under UV-Vis irradiation: mechanism and toxicity of photolysis products.

PubMed

Li, Fu Hua; Yao, Kun; Lv, Wen Ying; Liu, Guo Guang; Chen, Ping; Huang, Hao Ping; Kang, Ya Pu

2015-04-01

The photodegradation of ibuprofen (IBP) in aqueous media was studied in this paper. The degradation mechanism, the reaction kinetics and toxicity of the photolysis products of IBP under UV-Vis irradiation were investigated by dissolved oxygen experiments, quenching experiments of reactive oxygen species (ROS), and toxicity evaluation utilizing Vibrio fischeri. The results demonstrated that the IBP degradation process could be fitted by the pseudo first-order kinetics model. The degradation of IBP by UV-Vis irradiation included direct photolysis and self-sensitization via ROS. The presence of dissolved oxygen inhibited the photodegradation of IBP, which indicated that direct photolysis was more rapid than the self-sensitization. The contribution rates of ·OH and (1)O2 were 21.8 % and 38.6 % in self-sensitization, respectively. Ibuprofen generated a number of intermediate products that were more toxic than the base compound during photodegradation.

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.

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.

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

Cross-bridge kinetics in the presence of MgADP investigated by photolysis of caged ATP in rabbit psoas muscle fibres.

PubMed Central

Dantzig, J A; Hibberd, M G; Trentham, D R; Goldman, Y E

1991-01-01

1. The interaction between MgADP and rigor cross-bridges in glycerol-extracted single fibres from rabbit psoas muscle has been investigated using laser pulse photolysis of caged ATP (P3-1(2-nitrophenyl)ethyladenosine 5'-triphosphate) in the presence of MgADP and following small length changes applied to the rigor fibre. 2. Addition of 465 microM-MgADP to a rigor fibre caused rigor tension to decrease by 15.3 +/- 0.7% (S.E.M., n = 24 trials in thirteen fibres). The half-saturation value for this tension reduction was 18 +/- 4 microM (n = 23, thirteen fibres). 3. Relaxation from rigor by photolysis of caged ATP in the absence of Ca2+ was markedly slowed by inclusion of 20 microM-2 mM-MgADP in the photolysis medium. 4. Four phases of tension relaxation occurred with MgADP in the medium: at, a quick partial relaxation (in pre-stretch fibres); bt, a slowing of relaxation or a rise in tension for 50-100 ms; ct, a sudden acceleration of relaxation; and dt, a final, nearly exponential relaxation. 5. Experiments at varied MgATP and MgADP concentrations suggested that phase at is due to MgATP binding to nucleotide-free cross-bridges. 6. Phase bt was abbreviated by including 1-20 mM-orthophosphate (Pi) in the photolysis medium, or by applying quick stretches before photolysis or during phase bt. These results suggest that phases bt and ct are complex processes involving ADP dissociation, cross-bridge reattachment and co-operative detachment involving filament sliding and the Ca(2+)-regulatory system. 7. Stretching relaxed muscle fibres to 3.2-3.4 microns striation spacing followed by ATP removal and release of the rigor fibre until tension fell below the relaxed level allowed investigation of the strain dependence of relaxation in the regions of negative cross-bridge strain. In the presence of 50 microM-2 mM-MgADP and either 10 mM-Pi or 20 mM-2,3-butanedione monoxime, relaxation following photolysis of caged ATP was 6- to 8-fold faster for negatively strained cross

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

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.

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.

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.

Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

PubMed

Kao, Joseph P Y; Muralidharan, Sukumaran

2013-01-01

Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter.

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.

Topical treatment of oral cavity and wounded skin with a new disinfection system utilizing photolysis of hydrogen peroxide in rats.

PubMed

Yamada, Yasutomo; Mokudai, Takayuki; Nakamura, Keisuke; Hayashi, Eisei; Kawana, Yoshiko; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

2012-01-01

The present study aimed to evaluate the acute locally injurious property of hydroxyl radical generation system by photolysis of H(2)O(2), which is a new disinfection system for the treatment of periodontitis developed in our laboratory. Firstly, generation of the hydroxyl radical by a test device utilizing the photolysis of H(2)O(2) was confirmed by applying an electron spin resonance (ESR)-spin trapping technique. Secondly, the bactericidal effect of the device was examined under a simulant condition in which Staphylococcus aureus suspended in 1 M H(2)O(2) was irradiated with laser light emitted from the test device, resulting in substantial reduction of the colony forming unit of the bacteria within a short time as 2 min. Finally, acute topical effect of the disinfection system on rat oral mucosa and wounded skin was evaluated by histological examination. No abnormal findings were observed in the buccal mucosal region treated three times with 1 M H(2)O(2) and irradiation. Similarly, no abnormal findings were observed during the healing of skin treated with 1 M H(2)O(2) and irradiation immediately after wounding. Since topical treatment with the novel disinfection technique utilizing the photolysis of H(2)O(2) had no detrimental effect on the oral mucosa and the healing of full thickness skin wounds in rats, it is expected that the acute locally injurious property of the disinfection technique is low.

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

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.

Photochemical degradation of Corexit components in ocean water.

PubMed

Glover, Caitlin M; Mezyk, Stephen P; Linden, Karl G; Rosario-Ortiz, Fernando L

2014-09-01

Due to the large quantities of dispersants used during the Deepwater Horizon spill in 2010, there were immediate concerns with regards to the fate and transport of the mixture in ocean waters. Direct and sensitized photolysis experiments were carried out for two compounds chosen as surrogates for the Corexit mixture (9500 and 9527) that were applied to surface waters during the oil spill in the Gulf of Mexico. The results showed that direct photolysis did not contribute significantly to the overall degradation (max ∼30%), therefore the focus shifted to sensitized photolysis, specifically the degradation stemming from the reaction rate with hydroxyl radical (HO). The direct photochemical degradation rates for two of the compounds, dioctyl sulfosuccinate (DOSS) and dipropylene glycol butyl ether (DGBE) were measured as 4.29×10(-6)s(-1) and 5.95×10(-6)s(-1), respectively; whereas the overall degradation rate in ocean water was 1.56×10(-5)s(-1) and 2.23×10(-5)s(-1). The formation rates and apparent quantum yields for HO formation were determined for six ocean water samples. The values ranged from 1.81×10(-5) near shore to 0.061×10(-5) for the open ocean. These degradation rates suggest the possibility for photolysis to play a role in the overall fate of Corexit. Copyright © 2014 Elsevier Ltd. All rights reserved.

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...

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.

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.

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.

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

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.

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.

Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign

NASA Technical Reports Server (NTRS)

Lloyd, Steven A.; Swartz, William H.

2001-01-01

The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the MSX/UVISI satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.

Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign

NASA Technical Reports Server (NTRS)

Lloyd, Steven A.; Swartz, William H.

2001-01-01

The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the Midcourse Space Experiment(MSX)/Ultraviolet and Visible Imagers and Spectrographic Imagers (UVISI) satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.

Degradation of methadone by the sunlight/FC process: Kinetics, radical species participation and influence of the water matrix.

PubMed

Hsieh, Ming-Chi; Panchangam, Sri Chandana; Lai, Webber Wei-Po; Lin, Angela Yu-Chen

2018-06-12

Free chlorine sunlight photolysis (sunlight/FC) markedly enhances the degradation rate of methadone, a synthetic opioid used medically, over that obtained using sunlight alone. The pseudo-first-order rate constants of methadone degradation under acidic conditions ([methadone] = 0.2 μM, [free chlorine] = 4 μM, and pH = 4) for sunlight/FC and sunlight photolysis are 7.0 ± 1.1 × 10 -2  min -1 and 1.4 ± 0.2 × 10 -2  min -1 , respectively. The improved methadone degradation can be attributed to the production of HO and reactive chlorine species (RCS) during sunlight/FC photolysis. HO and RCS predominantly accounted for degradation during sunlight/FC photolysis under acidic and neutral conditions, while direct photolysis was the major contributor towards methadone degradation in alkaline conditions. The initial pH (pH 4-11) and free chlorine concentration (1-6 μM) significantly influenced the overall degradation efficiency of methadone. The presence of HCO 3 - , Cl - and dissolved organic matters, which may competitively react with HO and RCS, retard the degradation of methadone in synthetic wastewater. Consequently, a 50% lower methadone degradation rate was observed when deionized (DI) water was replaced with tap water. These results emphasize the need to consider different water matrices when applying sunlight/FC photolysis for water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

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.

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

Modelling the photochemical attenuation pathways of the fibrate drug gemfibrozil in surface waters.

PubMed

Fabbri, Debora; Maurino, Valter; Minella, Marco; Minero, Claudio; Vione, Davide

2017-03-01

Gemfibrozil (GFZ) is a relatively persistent pollutant in surface-water environments and it is rather recalcitrant to biological degradation. The GFZ photochemical lifetimes are relatively short in shallow waters with low levels of dissolved organic carbon (DOC), but they can reach the month-year range in deep and high-DOC waters. The main reason is that GFZ undergoes negligible reaction with singlet oxygen or degradation sensitised by the triplet states of chromophoric dissolved organic matter, which are the usually prevalent photochemical pathways in deep and high-DOC sunlit waters. Nitrate and nitrite scarcely affect the overall GFZ lifetimes, but they can shift photodegradation from direct photolysis to the OH process. These two pathways are the main GFZ phototransformation routes, with the direct photolysis prevailing in shallow environments during summer. Under these conditions the GFZ photochemical lifetimes are also shorter and the environmental significance of photodegradation correspondingly higher. The direct photolysis of GFZ under UVB irradiation yielded several transformation intermediates deriving from oxidation or cleavage of the aliphatic lateral chain. A quinone derivative (2,5-dimethyl-1,4-benzoquinone), a likely oxidation product of the transformation intermediate 2,5-dimethylphenol, is expected to be the most acutely and chronically toxic compound arising from GFZ direct photolysis. Interestingly, literature evidence suggests that the same toxic intermediate would be formed upon OH reaction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photochemical attenuation of N-nitrosodimethylamine (NDMA) and other nitrosamines in surface water.

PubMed

Plumlee, Megan H; Reinhard, Martin

2007-09-01

The aqueous photolysis of seven alkyl nitrosamines was studied by irradiation in a solar simulator. Nitrosamines included N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), N-nitrosodi-n-butylamine (NDBA), N-nitrosopiperidine (NPip), and N-nitrosopyrrolidine (NPyr). Direct photolysis at irradiations of 765 W/m2, representing Southern California midsummer, midday sun, resulted in half-lives of 16 min for NDMA and 12-15 min for the other nitrosamines. The quantum yield for NDMA was determined to be phi = 0.41 and phi = 0.43-0.61 for the other nitrosamines. Quantified products of NDMA photolysis included methylamine, dimethylamine, nitrite, nitrate, and formate, with nitrogen and carbon balances exceeding 98 and 79%, respectively. Indirect photolysis of nitrosamines in surface water was not observed; increasing dissolved organic carbon (DOC) slowed the NDMA photolysis rate because of light screening. Removal of NDMA measured in tertiary treated effluent flowing in a shallow, sunlit engineered channel agreed with photolysis rates predicted based on the measured quantum yield and system parameters. Because biodegradation is relatively slow, aquatic photolysis of NDMA is generally expected to be more significant even at relatively low levels of solar irradiation (t(1/2) = 8-38 h at 244-855 W/m2, 51 degrees N latitude, 1 m depth).

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.

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.

Beverages: bottled water. Final rule.

PubMed

2009-05-29

The Food and Drug Administration (FDA) is amending its bottled water regulations to require that bottled water manufacturers test source water for total coliform, as is required for finished bottled water products, and to require, if any coliform organisms are detected in source water, that bottled water manufacturers determine whether any of the coliform organisms are Escherichia coli (E. coli), an indicator of fecal contamination. FDA also is amending its bottled water regulations to require, if any coliform organisms are detected in finished bottled water products, that bottled water manufacturers determine whether any of the coliform organisms are E. coli. FDA also is amending the adulteration provision of the bottled water standard to reflect the possibility of adulteration caused by the presence of filth. Bottled water containing E. coli will be considered adulterated, and source water containing E. coli will not be considered to be of a safe, sanitary quality and will be prohibited from use in the production of bottled water. FDA is also amending its bottled water regulations to require that, before a bottler can use source water from a source that has tested positive for E. coli, the bottler must take appropriate measures to rectify or eliminate the cause of E. coli contamination of that source, and that the bottler must keep records of such actions. Existing regulatory provisions require bottled water manufacturers to keep records of new testing required by this rule. This final rule will ensure that FDA's standards for the minimum quality of bottled water, as affected by fecal contamination, will be no less protective of the public health than those set by the Environmental Protection Agency (EPA) for public drinking water.

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.

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.

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.

Competitive removal of pharmaceuticals from environmental waters by adsorption and photocatalytic degradation.

PubMed

Rioja, N; Benguria, P; Peñas, F J; Zorita, S

2014-10-01

This work explores the competitive removal of pharmaceuticals from synthetic and environmental waters by combined adsorption-photolysis treatment. Five drugs usually present in waterways have been used as target compounds, some are pseudo-persistent pollutants (carbamazepine, clofibric acid, and sulfamethoxazole) and others are largely consumed (diclofenac and ibuprofen). The effect of the light source on adsorption of drugs onto activated carbons followed by photolysis with TiO2 was assessed, being UV-C light the most effective for drug removal in both deionized water and river water. Different composites prepared from titania nanoparticles and powdered activated carbons were tested in several combined adsorption-photocatalysis assays. The composites prepared by calcination at 400 °C exhibited much better performance than those synthesized at 500 °C, being the C400 composite the most effective one. Furthermore, some synthetic waters containing dissolved species and environmental waters were used to investigate the effect of the aqueous matrix on each drug removal. In general, photocatalyst deactivation was found in synthetic and environmental waters. This was particularly evident in the experiments performed with bicarbonate ions as well as with wastewater effluent. In contrast, tests conducted in seawater showed adsorption and photocatalytic degradation yields comparable to those obtained in deionized water. Considering the peculiarities of substrate competition in each aqueous matrix, the combined adsorption-photolysis treatment generally increased the overall elimination of drugs in water.

Environmental fate of naproxen, carbamazepine and triclosan in wastewater, surface water and wastewater irrigated soil - Results of laboratory scale experiments.

PubMed

Durán-Álvarez, J C; Prado, B; González, D; Sánchez, Y; Jiménez-Cisneros, B

2015-12-15

Lab-scale photolysis, biodegradation and transport experiments were carried out for naproxen, carbamazepine and triclosan in soil, wastewater and surface water from a region where untreated wastewater is used for agricultural irrigation. Results showed that both photolysis and biodegradation occurred for the three emerging pollutants in the tested matrices as follows: triclosan>naproxen>carbamazepine. The highest photolysis rate for the three pollutants was obtained in experiments using surface water, while biodegradation rates were higher in wastewater and soil than in surface water. Carbamazepine showed to be recalcitrant to biodegradation both in soil and water; although photolysis occurred at a higher level than biodegradation, this compound was poorly degraded by natural processes. Transport experiments showed that naproxen was the most mobile compound through the first 30cm of the soil profile; conversely, the mobility of carbamazepine and triclosan through the soil was delayed. Biodegradation of target pollutants occurred within soil columns during transport experiments. Triclosan was not detected either in leachates or the soil in columns, suggesting its complete biodegradation. Data of these experiments can be used to develop more reliable fate-on-the-field and environmental risk assessment studies. Copyright © 2015 Elsevier B.V. All rights reserved.

Degradation mechanisms of Microcystin-LR during UV-B photolysis and UV/H2O2 processes: Byproducts and pathways.

PubMed

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

2017-10-01

The removal and degradation pathways of microcystin-LR (MC-LR, [M+H] +  = 995.6) in UV-B photolysis and UV-B/H 2 O 2 processes were examined using liquid chromatography-tandem mass spectrometry. The UV/H 2 O 2 process was more efficient than UV-B photolysis for MC-LR removal. Eight by-products were newly identified in the UV-B photolysis ([M+H] +  = 414.3, 417.3, 709.6, 428.9, 608.6, 847.5, 807.4, and 823.6), and eleven by-products were identified in the UV-B/H 2 O 2 process ([M+H] +  = 707.4, 414.7, 429.3, 445.3, 608.6, 1052.0, 313.4, 823.6, 357.3, 245.2, and 805.7). Most of the MC-LR by-products had lower [M+H] + values than the MC-LR itself during both processes, except for the [M+H] + value of 1052.0 during UV-B photolysis. Based on identified by-products and peak area patterns, we proposed potential degradation pathways during the two processes. Bond cleavage and intramolecular electron rearrangement by electron pair in the nitrogen atom were the major reactions during UV-B photolysis and UV-B/H 2 O 2 processes, and hydroxylation by OH radical and the adduct formation reaction between the produced by-products were identified as additional pathways during the UV-B/H 2 O 2 process. Meanwhile, the degradation by-products identified from MC-LR during UV-B/H 2 O 2 process can be further degraded by increasing H 2 O 2 dose. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of clouds on photolysis rates and ozone formation in the unpolluted troposphere

NASA Technical Reports Server (NTRS)

Thompson, A. M.

1984-01-01

The photochemistry of the lower atmosphere is sensitive to short- and long-term meteorological effects; accurate modeling therefore requires photolysis rates for trace gases which reflect this variability. As an example, the influence of clouds on the production of tropospheric ozone has been investigated, using a modification of Luther's two-stream radiation scheme to calculate cloud-perturbed photolysis rates in a one-dimensional photochemical transport model. In the unpolluted troposphere, where stratospheric inputs of odd nitrogen appear to represent the photochemical source of O3, strong cloud reflectance increases the concentration of NO in the upper troposphere, leading to greatly enhanced rates of ozone formation. Although the rate of these processes is too slow to verify by observation, the calculation is useful in distinguishing some features of the chemistry of regions of differing mean cloudiness.

Aqueous photolysis of niclosamide

USGS Publications Warehouse

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

2004-01-01

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

Flash photolysis resonance fluorescence investigation of the reaction of O /P-3/ atoms with ClONO2

NASA Technical Reports Server (NTRS)

Kurylo, M. J.

1977-01-01

The rate constant for the reaction of O (P-3) atoms with ClONO2 at 10 torr total pressure is assessed over the temperature range 225-273 K by the flash photolysis resonance fluorescence technique. The data, taken together with results given by Molina et al. (1977), have been used to formulate an Arrhenius expression suitable for stratospheric modeling applications. Comparison of the rate of ClONO2 destruction via the oxygen atom reaction with the solar photolysis rate shows that chemical reaction accounts for less than 15% of the CLONO2 removal at altitudes between 20 and 30 km.

Impacts of aerosol direct effects on tropospheric ozone through changes in atmospheric dynamics and photolysis rates

NASA Astrophysics Data System (ADS)

Xing, Jia; Wang, Jiandong; Mathur, Rohit; Wang, Shuxiao; Sarwar, Golam; Pleim, Jonathan; Hogrefe, Christian; Zhang, Yuqiang; Jiang, Jingkun; Wong, David C.; Hao, Jiming

2017-08-01

Aerosol direct effects (ADEs), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease ozone (O3) formation in polluted areas. One the other hand, evidence also suggests that ADE-associated cooling suppresses atmospheric ventilation, thereby enhancing surface-level O3. Assessment of ADE impacts is thus important for understanding emission reduction strategies that seek co-benefits associated with reductions in both particulate matter and O3 levels. This study quantifies the impacts of ADEs on tropospheric ozone by using a two-way online coupled meteorology and atmospheric chemistry model, WRF-CMAQ, using a process analysis methodology. Two manifestations of ADE impacts on O3 including changes in atmospheric dynamics (ΔDynamics) and changes in photolysis rates (ΔPhotolysis) were assessed separately through multiple scenario simulations for January and July of 2013 over China. Results suggest that ADEs reduced surface daily maxima 1 h O3 (DM1O3) in China by up to 39 µg m-3 through the combination of ΔDynamics and ΔPhotolysis in January but enhanced surface DM1O3 by up to 4 µg m-3 in July. Increased O3 in July is largely attributed to ΔDynamics, which causes a weaker O3 sink of dry deposition and a stronger O3 source of photochemistry due to the stabilization of the atmosphere. Meanwhile, surface OH is also enhanced at noon in July, though its daytime average values are reduced in January. An increased OH chain length and a shift towards more volatile organic compound (VOC)-limited conditions are found due to ADEs in both January and July. This study suggests that reducing ADEs may have the potential risk of increasing O3 in winter, but it will benefit the reduction in maxima O3 in summer.

Isotope Fractionation in the Stratospheric Nitrous Oxide Sinks: Photolysis and "Photooxidation"

NASA Astrophysics Data System (ADS)

Chen, N.; Bianchi, T. S.; McKee, B. A.; Bland, J. M.; Kaiser, J.; Rockmann, T.; Bruhl, C.; Brenninkmeijer, C. A.

2002-05-01

N2O is an important greenhouse gas and a key factor in the ozone cycle, being the major source of stratospheric NOx. It is produced mainly at Earth's surface by microbial N conversion processes. Despite the atmospheric significance of N2O, its global budget is relatively ill-constrained: Recent estimates of the total nitrogen source flux span a range from 6.7-36.6 Tg/a as opposed to the better-quantified stratospheric losses of 9-16 Tg/a and the observed increase in the global atmospheric N2O load by 3.9 Tg/a [IPCC, 2001]. Isotope measurements have been used tentatively to improve these estimates, but without immediate success. However, spawned by the development of new spectrometric techniques which can distinguish between the isotope ratios of the terminal and central nitrogen sites in N2O, it is hoped that the global budget can now be constrained better. Detailed knowledge about the factors determining the stratospheric N2O isotope ratios is required to incorporate them into chemistry and transport models. To this end, we will present measurements of fractionation constants for N2O photolysis at different wavelengths and temperatures as well as a complete kinetic characterization of the second N2O loss reaction, N2O+O(1D), at all stratospherically relevant conditions. The intramolecular distribution of 15N is always accounted for. The laboratory measurements are interpreted in the context of stratospheric air samples which revealed strong altitude-dependent enrichments of heavy N2O isotopomers (15N14NO, 14N15NO, N218O) in the lower and middle stratosphere. Taken as a whole, these observations can be interpreted by a Rayleigh fractionation pattern in the decrease of N2O mixing ratios due to photolysis (90 % of total sink) and oxidation by O(1D) (10 % of total sink). The apparent fractionation constants are depleted in the lower stratosphere (<200 nmol/mol N2O), caused by chemistry or transport. However, even the ratio of 14N15NO and 15N14NO decreases towards the

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.

Photolysis of Pure Solid O3 and O2 Films at 193nm

NASA Technical Reports Server (NTRS)

Raut, U.; Loeffler, M. J.; Fama, M.; Baragiola, R. A.

2011-01-01

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

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

Antimicrobial activity of hydroxyl radicals generated by hydrogen peroxide photolysis against Streptococcus mutans biofilm.

PubMed

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

2016-10-01

Prevention of dental caries with maximum conservation of intact tooth substance remains a challenge in dentistry. The present study aimed to evaluate the antimicrobial effect of H2O2 photolysis on Streptococcus mutans biofilm, which may be a novel antimicrobial chemotherapy for treating caries. S. mutans biofilm was grown on disk-shaped hydroxyapatite specimens. After 1-24 h of incubation, growth was assessed by confocal laser scanning microscopy and viable bacterial counting. Resistance to antibiotics (amoxicillin and erythromycin) was evaluated by comparing bactericidal effects on the biofilm with those on planktonic bacteria. To evaluate the effect of the antimicrobial technique, the biofilm was immersed in 3% H2O2 and was irradiated with an LED at 365 nm for 1 min. Viable bacterial counts in the biofilm were determined by colony counting. The thickness and surface coverage of S. mutans biofilm increased with time, whereas viable bacterial counts plateaued after 6 h. When 12- and 24-h-old biofilms were treated with the minimum concentration of antibiotics that killed viable planktonic bacteria with 3 log reduction, their viable counts were not significantly decreased, suggesting the biofilm acquired antibiotic resistance by increasing its thickness. By contrast, hydroxyl radicals generated by photolysis of 3% H2O2 effectively killed S. mutans in 24-h-old biofilm, with greater than 5 log reduction. The technique based on H2O2 photolysis is a potentially powerful adjunctive antimicrobial chemotherapy for caries treatment. Copyright © 2016 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

Transformation products of amoxicillin and ampicillin after photolysis in aqueous matrices: Identification and kinetics.

PubMed

Arsand, Juliana Bazzan; Hoff, Rodrigo Barcellos; Jank, Louise; Meirelles, Lucas N; Silvia Díaz-Cruz, M; Pizzolato, Tânia Mara; Barceló, Damià

2018-06-18

Antibiotics are widely used in human medicine and veterinary production. Residues of these compounds reach the water sources through waste or direct application (e.g. aquaculture). The constant input of the parent drugs and their transformation products into the environment leads these pharmaceuticals to be considered as emerging pollutants. For some molecules, the pathway of degradation and formation in products is less known. To assess the impact of these substances in the environment and in the human health, it is necessary to elucidate the transformation products and their kinetic of degradation to evaluate the possible risks. In the present report, the characterization and the degradation kinetic of two widely used β-lactams antibiotics - amoxicillin and ampicillin - was evaluated. Surface water samples containing these antibiotics were submitted to photolysis and analyzed by liquid chromatography coupled to mass spectrometry with Orbitrap detection in order to establish the profile of degradation and the formation of transformation products. Results showed that the degradation of amoxicillin and ampicillin is almost complete and reach their maximum at 48 h in river water. Moreover, a database containing >65 transformation products of amoxicillin and ampicillin was build and real samples of industrial wastewater were analyzed to investigate the occurrence of amoxicillin, ampicillin and their transformation products. Copyright © 2018. Published by Elsevier B.V.

Dependence of upper atmosphere photochemistry on the shape of the diurnal cycle of the photolysis rates

NASA Astrophysics Data System (ADS)

Montecinos, S.; Barrientos, P.

2006-03-01

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

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

PubMed

Xing, Rui; Zheng, Zhongyuan; Wen, Donghui

2015-03-01

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%-35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD5/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%-47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH4+-N), 17% more nitrite nitrogen (NO2--N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO3--N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent. Copyright © 2015. Published by Elsevier B.V.

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

PubMed

Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

2012-11-20

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

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.

Photolysis frequency and cloud dynamics during DC3 and SEAC4RS

NASA Astrophysics Data System (ADS)

Hall, S. R.; Ullmann, K.; Madronich, S.; Hair, J. W.; Butler, C. F.; Fenn, M. A.

2013-12-01

Cloud shading plays a critical role in extending the lifetime of short-lived chemical species. During convection, photochemistry is reduced such that short-lived species may be transported from the boundary layer to the upper troposphere/ lower stratosphere. In the anvil outflow, shading continues within and below the cloud. However, near the highly scattering cloud top, the chemistry is greatly accelerated. In this rapidly evolving environment, accurate photolysis frequencies are required to study photochemical evolution of the complex composition. During the Deep Convective Clouds and Chemistry (DC3, 2012) and the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, 2013) campaigns, photolysis frequencies were determined by measurement of spectrally resolved actinic flux by the Charge-coupled device Actinic Flux Spectroradiometer (CAFS) on the NASA DC-8 and the HIAPER Airborne Radiation Package (HARP) on the NCAR G-V aircraft. Vertical flight profiles allowed in situ characterization of the radiation environment. Input of geometrical cloud characteristics into the Tropospheric Ultraviolet and Visible (TUV) Radiation was used to constrain cloud optical depths for more spatially and temporally stable conditions.

The photolysis of CH3ONO

NASA Technical Reports Server (NTRS)

Wiebe, H. A.; Heicklen, J.

1972-01-01

The photolysis of CH3ONO, alone and in the presence of NO, NO-N2 mixtures, and NO-CO mixtures was studied between 25 and 150 C. The major products are CH2O, N2O, and H2O. The quantum yields of N2O were measured. The N2O yield is large at low pressures but approaches a high-pressure limiting value of 0.055 at all temperatures as the excited CH3O produced in the primary step is stabilized by collision. In the presence of excess CO, and N2O yield drops, and CO2 is produced (though not in sufficient amounts to account for the drop in N2O). When pure CH2ONO is photolyzed, CO is produced and NO accumulates in the system. Both products are formed in related processes and result from CH3O attack on CH2O.

The Production of NO subscript 2 from the Photolysis of Peroxyacetyl Nitrate

NASA Technical Reports Server (NTRS)

Mazely, T.; Friedl, R.; Sander, S.

1994-01-01

PAN vapor was photolyzed at 248 nm and the NO subscript 2 photoproduct was detected by laser induced fluorescence (LIF). By comparison to the NO subscript 2 production from the photolysis of HNO subscript 3 under identical experimental conditions, we have obtained a relative quantum yield for the production of NO subscript 2. The implications of these results for atmospheric PAN chemistry will be discussed.

Pulsed laser photolysis kinetics study of the O(3P) + ClO reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Wine, P. H.; Ravishankara, A. R.

1988-01-01

A pulsed laser photolysis technique was used to investigate the kinetics of the important stratospheric reaction O + ClO yields Cl + O2 in buffer gas over the temperature and pressure ranges of 231-367 K and 25-500 torr. The results indicate a lack of pressure dependence at 298 K over the 25-500 torr range.

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

Laser photolysis of caged calcium: rates of calcium release by nitrophenyl-EGTA and DM-nitrophen.

PubMed Central

Ellis-Davies, G C; Kaplan, J H; Barsotti, R J

1996-01-01

Nitrophenyl-EGTA and DM-nitrophen are Ca2+ cages that release Ca2+ when cleaved upon illumination with near-ultraviolet light. Laser photolysis of nitrophenyl-EGTA produced transient intermediates that decayed biexponentially with rates of 500,000 s-1 and 100,000 s-1 in the presence of saturating Ca2+ and 290,000 s-1 and 68,000 s-1 in the absence of Ca2+ at pH 7.2 and 25 degrees C. Laser photolysis of nitrophenyl-EGTA in the presence of Ca2+ and the Ca2+ indicator Ca-orange-5N produced a monotonic increase in the indicator fluorescence, which had a rate of 68,000 s-1 at pH 7.2 and 25 degrees C. Irradiation of DM-nitrophen produced similar results with somewhat slower kinetics. The transient intermediates decayed with rates of 80,000 s-1 and 11,000 s-1 in the presence of Ca2+ and 59,000 s-1 and 3,600 s-1 in the absence of Ca2+ at pH 7.2 and 25 degrees C. The rate of increase in Ca(2+)-indicator fluorescence produced upon photolysis of the DM-nitrophen: Ca2+ complex was 38,000 s-1 at pH 7.2 and 25 degrees C. In contrast, pulses in Ca2+ concentration were generated when the chelator concentrations were more than the total Ca2+ concentration. Photoreleased Ca2+ concentration stabilized under these circumstances to a steady state within 1-2 ms. PMID:8789118

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.

77 FR 17082 - Standards for Living Organisms in Ships' Ballast Water Discharged in U.S. Waters: Final...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-23

... Organisms in Ships' Ballast Water Discharged in U.S. Waters: Final Programmatic Environmental Impact... entitled ``Standards for Living Organisms in Ships' Ballast Water Discharged in U.S. Waters'' (Docket No... impacts associated with the establishment of a ballast water discharge standard for the allowable...

The effect of Cu(2+) chelation on the direct photolysis of oxytetracycline: A study assisted by spectroscopy analysis and DFT calculation.

PubMed

Jin, Xin; Qiu, Shanshan; Wu, Ke; Jia, Mingyun; Wang, Fang; Gu, Chenggang; Zhang, Aiqian; Jiang, Xin

2016-07-01

The extensive usage of OTC and Cu(2+) in livestock and poultry industry caused high residues in natural environment. Co-contamination of OTC and Cu(2+) was a considerable environmental problem in surface waters. In this study, Cu(2+) mediated direct photolysis of OTC was studied. Cu(2+) chelating with OTC was found to greatly inhibit OTC photodegradation. To reveal the chelation mechanism of OTC-Cu complexes, multiple methods including UV-Vis absorption spectra, Infrared (IR) spectra, mass spectroscopy, and density functional theoretical (DFT) modeling were performed. Four OTC-Cu complexes were proposed. Cu(2+) preferably bond to O11O12 site with the binding constants logK = 8.19 and 7.86 for CuHL+ and CuL±, respectively. The second chelating site was suggested to be O2O3 with the binding constants of logK = 4.41 and 4.62 for Cu2HL3+ and Cu2L2+, respectively. The suppressed quantum yield of OTC by Cu2+ chelation was accused for their intra-/inter-molecular electron transfer, by which the energy in activated states was distributed. The occurrence of electron transfer between BCD ring and A ring also from BCD ring to Cu was evidenced by the TD-DFT result only for the OTC-Cu complexes. Besides, the cyclic voltammetry measurement also suggested one OTC-Cu(II)/OTC-Cu(I) redox couple. These results suggested that the persistence of OTC in environmental surface waters will probably be underestimated for neglecting the chelating effect of Cu2+. The photolysis quantum yield of OTC-Cu complexes, as well as the specific molar absorption constants, the equilibrium binding constants of Cu2+ with OTC could contribute to more accurate kinetic models of OTC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Measurement of total organic concentration in water

NASA Technical Reports Server (NTRS)

Winkler, E.

1978-01-01

Instrument for determining total organic concentration in water uses no corrosive reagents or gases. Instead continuous ultraviolet photolysis process converts organic compounds to carbon dioxide (CO2). CO2 electrode is used to measure CO2 content. Only reagent necessary is oxygen, generated in situ by electrolyzing some water. In addition to application in aerospace industry, system has potential uses in pollution monitoring and in laboratory analyses.

Impacts of aerosol direct effects on tropospheric ozone through changes in atmospheric dynamics and photolysis rates

EPA Science Inventory

Aerosol direct effects (ADE), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease O3 formation in polluted areas. One the other hand, evidence also suggests that ADE associated coo...

Solar photolysis of ozone to singlet D oxygen atoms

NASA Technical Reports Server (NTRS)

Blackburn, Thomas E.; Bairai, Solomon T.; Stedman, Donald H.

1992-01-01

The ground-level photolysis frequency of ozone J(O3) to produce metastable singlet D oxygen atoms (O (D-1)) is measured using a novel instrumental technique involving electrical conductivity. The O(D-1) atoms produced react with nitrous oxide (N2O) carrier gas to form higher oxides of nitrogen (NO(x)). These oxides were detected by mixing with methanol and determining the increase in electrical conductivity with a continuous-flow dual conductivity cell. Over 70 days of data were collected under varying sky conditions. The effect of temperature on J(O3) was measured. The results agree with model predictions. The effects of atmospheric aerosols, changes in overhead ozone column, and local cloudiness are discussed.

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.

Photolysis of pure solid O{sub 3} and O{sub 2} films at 193 nm

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

Raut, U.; Loeffler, M. J.; Fama, M.

2011-05-21

We studied quantitatively the photochemistry of solid O{sub 3} and O{sub 2} films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O{sub 3}, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O{sub 2} produced O{sub 3} in an amount that increased with photon fluence to a stationary level. For both O{sub 2} and O{sub 3} films, the O{sub 3}:O{sub 2} ratio at large fluences is {approx}0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed tomore » the increased photodissociation of O{sub 2} due to photoabsorption by O{sub 2} dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, {Phi}(O{sub 3}) = 0.24 {+-} 0.06, and quantum yields for destruction of O{sub 3} and O{sub 2} in their parent solids, {Phi}(-O{sub 3}) = 1.0 {+-} 0.2 and {Phi}(-O{sub 2}) = 0.36 {+-} 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 {+-} 0.1 for O{sub 3} fragments and 0.88 {+-} 0.03 for oxygen atoms from O{sub 2} dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O{sub 2} vs. O{sub 3} to be 0.1-0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.« less

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

NASA Astrophysics Data System (ADS)

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

2011-10-01

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

Nitrate photolysis in salty snow

NASA Astrophysics Data System (ADS)

Donaldson, D. J.; Morenz, K.; Shi, Q.; Murphy, J. G.

2016-12-01

Nitrate photolysis from snow can have a significant impact on the oxidative capacity of the local atmosphere, but the factors affecting the release of gas phase products are not well understood. Here, we report the first systematic study of the amounts of NO, NO2, and total nitrogen oxides (NOy) emitted from illuminated snow samples as a function of both nitrate and total salt (NaCl and Instant Ocean) concentration. We show that the release of nitrogen oxides to the gas phase is directly related to the expected nitrate concentration in the brine at the surface of the snow crystals, increasing to a plateau value with increasing nitrate, and generally decreasing with increasing NaCl or Instant Ocean (I.O.). In frozen mixed nitrate (25 mM) - salt (0-500 mM) solutions, there is an increase in gas phase NO2 seen at low added salt amounts: NO2 production is enhanced by 35% at low prefreezing [NaCl] and by 70% at similar prefreezing [I.O.]. Raman microscopy of frozen nitrate-salt solutions shows evidence of stronger nitrate exclusion to the air interface in the presence of I.O. than with added NaCl. The enhancement in nitrogen oxides emission in the presence of salts may prove to be important to the atmospheric oxidative capacity in polar regions.

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.

Stabilizing effect of citrate buffer on the photolysis of riboflavin in aqueous solution

PubMed Central

Ahmad, Iqbal; Sheraz, Muhammad Ali; Ahmed, Sofia; Kazi, Sadia Hafeez; Mirza, Tania; Aminuddin, Mohammad

2011-01-01

In the present investigation the photolysis of riboflavin (RF) in the presence of citrate species at pH 4.0–7.0 has been studied. A specific multicomponent spectrophotometric method has been used to assay RF in the presence of photoproducts during the reactions. The overall first-order rate constants (kobs) for the photolysis of RF range from 0.42 to 1.08×10–2 min−1 in the region. The values of kobs have been found to decrease with an increase in citrate concentration indicating an inhibitory effect of these species on the rate of reaction. The second-order rate constants for the interaction of RF with total citrate species causing inhibition range from 1.79 to 5.65×10–3 M−1 min−1 at pH 4.0–7.0. The log k–pH profiles for the reactions at 0.2–1.0 M citrate concentration show a gradual decrease in kobs and the value at 1.0 M is more than half compared to that of k0, i.e., in the absence of buffer, at pH 5.0. Divalent citrate ions cause a decrease in RF fluorescence due to the quenching of the excited singlet state resulting in a decrease in the rate of reaction and consequently leading to the stabilization of RF solutions. The greater quenching of fluorescence at pH 4.0 compared to that of 7.0 is in accordance with the greater concentration of divalent citrate ions (99.6%) at that pH. The trivalent citrate ions exert a greater inhibitory effect on the rate of RF photolysis compared to that of the divalent citrate ions probably as a result of excited triplet state quenching. The values of second-order rate constants for the interaction of divalent and trivalent citrate ions are 0.44×10–2 and 1.06×10–3 M–1 min–1, respectively, indicating that the trivalent ions exert a greater stabilizing effect, compared to the divalent ions, on RF solutions. PMID:25755977

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.

Direct and indirect photolysis of seven micropollutants in secondary effluent from a wastewater lagoon.

PubMed

Wang, Yufei; Roddick, Felicity A; Fan, Linhua

2017-10-01

The photodegradation of seven micropollutants commonly found in municipal wastewater, namely caffeine, carbamazepine, diuron, simazine, sulfamethoxazole, triclosan and 2,4-D, was investigated in pure water and secondary effluent to understand the direct and indirect photolysis of these compounds under natural sunlight irradiation. Sulfamethoxazole and triclosan were readily photodegraded with half-lives of 5.8 and 1.8 h, respectively, whilst the others were relatively resistant towards sunlight irradiation. Enhanced degradation was observed in secondary effluent compared with in the pure water matrix for all compounds, except for triclosan. It was confirmed that hydroxyl radicals played an important role in the photodegradation of the micropollutants while singlet oxygen may also play a role. The contribution of hydroxyl radical to the overall degradation of the five compounds that were resistant to direct sunlight accounted for 32%-70%. The impact of humic acid and nitrate, two known photosensitisers and wastewater components, on the photodegradation of the seven micropollutants in pure water was investigated under simulated solar radiation. The presence of nitrate promoted the photochemical loss of all seven micropollutants, however, humic acid caused promotion or inhibition, depending on the characteristics of the micropollutant. Humic acid enhanced the photolytic degradation of caffeine, sulfamethoxazole and diuron, while it hindered the photodegradation of the other four compounds by absorbing the available irradiation energy and/or reforming the parent compound. Furthermore, it was shown that there was only a small increase (up to 15%) in photodegradation of the compounds at 25 °C compared with that at 10 °C in the simulated system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Base-catalyzed hydrolysis and speciation-dependent photolysis of two cephalosporin antibiotics, ceftiofur and cefapirin.

PubMed

Ribeiro, Alyson R; Lutze, Holger V; Schmidt, Torsten C

2018-05-01

Lately, special attention has been given to veterinary cephalosporin antibiotics due to their broad activity spectrum and significant consumption. Indeed, the determination of hydrolytic and photolytic kinetics provides a better comprehension of the undesired persistence of cephalosporins in aqueous matrices. In this work, the two widely used veterinary antibiotics ceftiofur (CEF) and cefapirin (CEPA) showed high instability under alkaline conditions, degrading in few minutes at pH > 11. In buffered solutions at neutral pH and natural temperature (T = 22 ± 1 °C), both drugs presented moderate stability (t½ = 3 d, CEPA and 1.4 d, CEF). Our study also demonstrated that CEPA and CEF speciation did not significantly influence the direct photolysis rates. Using a simulated water disinfection set-up (λ = 254 nm), all ionic species of CEF and CEPA presented fast and similar pseudo-first order degradation rates, k app 0.0095 ± 0.0004 and 0.0092 ± 0.001 cm 2 mJ -1 , respectively. Furthermore, using surface water in hydrolysis experiments, CEF demonstrated significant matrix-dependent stability with a half-life (t½ = 14.7 d) tenfold higher than in buffered solutions. In contrast, CEPA presented a very similar hydrolysis rate in river water (t½ = 4.2 d) and a subtle faster photo-degradation rate in this same matrix (k app 0.0128 ± 0.001 cm 2 mJ -1 ), highlighting the importance of disinfection radiation for cephalosporin depletion in aqueous environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

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

Yang Chunfan; Su Hongmei; Sun Xuezhong

2012-05-28

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing themore » photodissociation and depopulating the excited S{sub 2} or S{sub 3} state molecules to the lowest T{sub 1} state with a rate of {approx}2.5 ps after a delayed onset of {approx}3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T{sub 1} excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T{sub 1} excited state. The measured ultrafast formation of T{sub 1} excited state supports the existence of the surface intersections of S{sub 2}/S{sub 1}, S{sub 2}/T{sub 2}, and S{sub 1}/T{sub 1}/T{sub 2}, and the large T{sub 1} quantum yield of {approx}0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.« less

Constraints on the photolysis and the equilibrium constant of ClO-dimer from airborne and balloon-borne measurements of chlorine compounds

NASA Astrophysics Data System (ADS)

Kleinboehl, A.; Canty, T. P.; Salawitch, R. J.; Khosravi, M.; Urban, J.; Toon, G. C.; Kuellmann, H.; Notholt, J.

2011-12-01

Significant differences exist between different laboratory measurements of the photolysis cross-sections of ClO-dimer, and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. This leads to uncertainties in the calculations of stratospheric ozone loss in the winter polar regions. One way to constrain the plausibility of these parameters is the measurement of ClO across the terminator in the activated polar vortex. Here we analyze measurements of ClO taken by the airborne submillimeter radiometer ASUR in the Arctic winter of 1999/2000. We use measured ClO at low solar zenith angles (SZA) to estimate the total active chlorine (ClOx). We estimate total available inorganic chlorine (Cly) using ASUR measurements of N2O in January 2000 and a N2O-Cly correlation established by a balloon measurement of the MarkIV interferometer in December 1999. We compare the ClOx estimates based on different photolysis rates of ClO-Dimer. Our results show that cross-sections leading to fast photolysis rates like the ones by Burkholder et al. [1990] or Papanastasiou et al. [2009] give ClOx mixing ratios that overlap with our estimated range of available Cly. Slower photolysis rates like the ones by von Hobe et al. [2009] and Pope et al. [2007] lead to ClOx values that are significantly higher than the available Cly. We use the calculated ClOx from low SZA to estimate the ClO in darkness with different equilibrium constants, and compare it with ASUR ClO measurements before sunrise (SZA > 95). We find that calculations with equilibrium constants published in the JPL evaluation of the last few years all give good agreement with observed ClO mixing ratios. The equilibrium constant estimated by von Hobe et al. [2005] yields ClO values that are higher than the ones observed.

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.

Reference News Release: EPA Finalizes Rule to Modernize Clean Water Act Reporting

EPA Pesticide Factsheets

Today, the U.S. Environmental Protection Agency (EPA) finalized a rule to modernize Clean Water Act reporting for municipalities, industries, and other facilities. The final rule will require regulated entities and state and federal regulators to use exist

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction-Diffusion Approach.

PubMed

Dóka, Éva; Lente, Gábor

2017-04-13

This work presents a rigorous mathematical study of the effect of unavoidable inhomogeneities in laser flash photolysis experiments. There are two different kinds of inhomegenities: the first arises from diffusion, whereas the second one has geometric origins (the shapes of the excitation and detection light beams). Both of these are taken into account in our reported model, which gives rise to a set of reaction-diffusion type partial differential equations. These equations are solved by a specially developed finite volume method. As an example, the aqueous reaction between the sulfate ion radical and iodide ion is used, for which sufficiently detailed experimental data are available from an earlier publication. The results showed that diffusion itself is in general too slow to influence the kinetic curves on the usual time scales of laser flash photolysis experiments. However, the use of the absorbances measured (e.g., to calculate the molar absorption coefficients of transient species) requires very detailed mathematical consideration and full knowledge of the geometrical shapes of the excitation laser beam and the separate detection light beam. It is also noted that the usual pseudo-first-order approach to evaluating the kinetic traces can be used successfully even if the usual large excess condition is not rigorously met in the reaction cell locally.

Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

PubMed

Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Erickson, Paul R; Bolotin, Jakov; Hofstetter, Thomas B

2015-04-07

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

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.

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.

[Influence of CNTs on Photodegradation of Salbutamol in Water Environment].

PubMed

Wang, Qi; Han, Jia-rui; Wei, Bo-fan; Zhou, Lei; Zhang, Ya; Yang, Xi

2015-08-01

The influence of CNTs on the photolysis of organic pollutant was investigated by studying the photodegradation kinetics of SAL under 1000 W Xenon lamp, in the presence of three kinds of CNTs (SCNT, MWNT-COOH, MWNT-OH). In addition, the interaction between CNTs and Fe3" was also investigated. The results showed that the photodegradation of salbutamol followed pseudo-first-order kinetics, which could be inhibited by all three kinds of CNTs through light screening effect. Formation of singlet oxygen was detected during the photolysis, using the molecular probe furfuryl alcohol. All three kinds of CNTs could absorb electrons through competition, i.e., inhibit SAL photodegradation by light screening effect; meanwhile, the CNTs could generate singlet oxygen through photoexcitation to promote the photodegradation reaction. Both mechanisms coexisted, and in most cases, the inhibition effect was dominant. In addition, CNTs could inactivate the photoactive substance Fe3 in the water body by electrostatic adsorption, and affect the photochemical behavior of organic pollutants in natural water body.

The examination of berberine excited state by laser flash photolysis

NASA Astrophysics Data System (ADS)

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

2009-07-01

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

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

PubMed

Copeland, G; Lee, E P F; Williams, R G; Archibald, A T; Shallcross, D E; Dyke, J M

2014-01-01

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

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.

Imidazolium-Based Ionic Liquids in Water: Assessment of Photocatalytic and Photochemical Transformation.

PubMed

Calza, Paola; Vione, Davide; Fabbri, Debora; Aigotti, Riccardo; Medana, Claudio

2015-09-15

The photoinduced transformation of two ionic liquids, 1-methylimidazolium hydrogensulfate (HMIM) and 1-ethyl-3-methylimidazolium hydrogensulfate (EMIM), was investigated under photocatalytic conditions in the presence of irradiated TiO2. We monitored substrate disappearance, transformation products (TPs), degree of mineralization, and toxicity of the irradiated systems. Acute toxicity measures suggested in both cases the occurrence of more toxic TPs than the parent molecules. A total of five TPs were detected by HPLC-HRMS from HMIM and nine from EMIM. Complete mineralization and stoichiometric release of nitrogen was achieved for both compounds within 4 h of irradiation. The photochemical transformation kinetics and pathways in surface waters (direct photolysis and indirect photoreactions) were studied for EMIM, to assess its persistence in sunlit water bodies such as rivers or lakes. Environmental phototransformation would be dominated by direct photolysis, with half-life times of up to one month under fine-weather conditions.

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

PubMed

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

2015-09-02

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

Effective scheme of photolysis of GFP in live cell as revealed with confocal fluorescence microscopy

NASA Astrophysics Data System (ADS)

Glazachev, Yu I.; Orlova, D. Y.; Řezníčková, P.; Bártová, E.

2018-05-01

We proposed an effective kinetics scheme of photolysis of green fluorescent protein (GFP) observed in live cells with a commercial confocal fluorescence microscope. We investigated the photolysis of GFP-tagged heterochromatin protein, HP1β-GFP, in live nucleus with the pulse position modulation approach, which has several advantages over the classical pump-and-probe method. At the basis of the proposed scheme lies a process of photoswitching from the native fluorescence state to the intermediate fluorescence state, which has a lower fluorescence yield and recovers back to native state in the dark. This kinetics scheme includes four effective parameters (photoswitching, reverse switching, photodegradation rate constants, and relative brightness of the intermediate state) and covers the time scale from dozens of milliseconds to minutes of the experimental fluorescence kinetics. Additionally, the applicability of the scheme was demonstrated in the cases of continuous irradiation and the classical pump-and-probe approach using numerical calculations and analytical solutions. An interesting finding of experimental data analysis was that the overall photodegradation of GFP proceeds dominantly from the intermediate state, and demonstrated approximately the second-order reaction versus irradiation power. As a practical example, the proposed scheme elucidates the artifacts of fluorescence recovery after the photobleaching method, and allows us to propose some suggestions on how to diminish them.

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.

Effective scheme of photolysis of GFP in live cell as revealed with confocal fluorescence microscopy.

PubMed

Glazachev, Yu I; Orlova, D Y; Řezníčková, P; Bártová, E

2018-03-23

We proposed an effective kinetics scheme of photolysis of green fluorescent protein (GFP) observed in live cells with a commercial confocal fluorescence microscope. We investigated the photolysis of GFP-tagged heterochromatin protein, HP1β-GFP, in live nucleus with the pulse position modulation approach, which has several advantages over the classical pump-and-probe method. At the basis of the proposed scheme lies a process of photoswitching from the native fluorescence state to the intermediate fluorescence state, which has a lower fluorescence yield and recovers back to native state in the dark. This kinetics scheme includes four effective parameters (photoswitching, reverse switching, photodegradation rate constants, and relative brightness of the intermediate state) and covers the time scale from dozens of milliseconds to minutes of the experimental fluorescence kinetics. Additionally, the applicability of the scheme was demonstrated in the cases of continuous irradiation and the classical pump-and-probe approach using numerical calculations and analytical solutions. An interesting finding of experimental data analysis was that the overall photodegradation of GFP proceeds dominantly from the intermediate state, and demonstrated approximately the second-order reaction versus irradiation power. As a practical example, the proposed scheme elucidates the artifacts of fluorescence recovery after the photobleaching method, and allows us to propose some suggestions on how to diminish them.

Assessing cloud radiative effects on tropospheric photolysis rates and key oxidants during aircraft campaigns using satellite cloud observations and a global chemical transport model

NASA Astrophysics Data System (ADS)

Zhang, B.; Liu, H.; Crawford, J. H.; Chen, G.; Voulgarakis, A.; Fairlie, T. D.; Duncan, B. N.; Ham, S. H.; Kato, S.; Payer Sulprizio, M.; Yantosca, R.

2017-12-01

Clouds affect tropospheric photochemistry through modifying solar radiation that determines photolysis rates. Observational and modeling studies have indicated that photolysis rates are enhanced above and in the upper portion of cloud layers and are reduced below optically thick clouds due to their dominant backscattering effect. However, large uncertainties exist in the representation of cloud spatiotemporal (especially vertical) distributions in global models, which makes understanding of cloud radiative effects on tropospheric chemistry challenging. Our previous study using a global 3-D chemical transport model (GEOS-Chem) driven by various meteorological data sets showed that the radiative effects of clouds on photochemistry are more sensitive to the differences in the vertical distribution of clouds than to those in the magnitude of column cloud optical depths. In this work, we evaluate monthly mean cloud optical properties and distributions in the MERRA-2 reanalysis with those in C3M, a 3-D cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We conduct tropospheric chemistry simulations for the periods of several aircraft campaigns, including ARCTAS (April, June-July, 2008), DC3 (May-June, 2012), and SEAC4RS (August-September, 2013) with GEOS-Chem driven by MERRA-2. We compare model simulations with and without constraints of cloud optical properties and distributions from C3M, and evaluate model photolysis rates (J[O1D] and J[NO2]) and key oxidants (e.g., OH and ozone) with aircraft profile measurements. We will assess whether the constraints provided by C3M improve model simulations of photolysis rates and oxidants as well as their variabilities.

Algae-mediated removal of selected pharmaceutical and personal care products (PPCPs) from Lake Mead water.

PubMed

Bai, Xuelian; Acharya, Kumud

2017-03-01

The persistence and fate of pharmaceutical and personal care products (PPCPs) in the Lake Mead ecosystem are particularly important considering the potential ecological risks and human health impacts. This study evaluated the removal of five common PPCPs (i.e., trimethoprim, sulfamethoxazole, carbamazepine, ciprofloxacin, and triclosan) from Lake Mead water mediated by the green alga Nannochloris sp. The results from the incubation studies showed that trimethoprim and carbamazepine were highly resistant to uptake in the algal cultural medium and were measured at approximately 90%-100% of the applied dose after 14days of incubation. Sulfamethoxazole was found relatively persistent, with >60% of the applied dose remaining in the water after 14days, and its removal was mainly caused by algae-mediated photolysis. However, ciprofloxacin and triclosan dissipated significantly and nearly 100% of the compounds were removed from the water after 7days of incubation under 24h of light. Ciprofloxacin and triclosan were highly susceptible to light, and their estimated half-lives were 12.7hours for ciprofloxacin and 31.2hours for triclosan. Algae-mediated sorption contributed to 11% of the removal of trimethoprim and sulfamethoxazole, 13% of the removal of carbamazepine, and 27% of the removal of triclosan from the lake water. This research showed that 1) trimethoprim, sulfamethoxazole, and carbamazepine are quite persistent in aquatic environments and may potentially affect human health via drinking water intake; 2) photolysis is the dominant pathway to remove ciprofloxacin from aquatic ecosystems, which indicates that ciprofloxacin may have lower ecological risks compared with other PPCPs; and 3) triclosan can undergo photolysis as well as algae-mediated uptake and it may potentially affect the food web because of its high toxicity to aquatic species. Copyright © 2017 Elsevier B.V. All rights reserved.

Nitrogen-Containing, Light-Absorbing Oligomers Produced in Aerosol Particles Exposed to Methylglyoxal, Photolysis, and Cloud Cycling.

PubMed

De Haan, David O; Tapavicza, Enrico; Riva, Matthieu; Cui, Tianqu; Surratt, Jason D; Smith, Adam C; Jordan, Mary-Caitlin; Nilakantan, Shiva; Almodovar, Marisol; Stewart, Tiffany N; de Loera, Alexia; De Haan, Audrey C; Cazaunau, Mathieu; Gratien, Aline; Pangui, Edouard; Doussin, Jean-François

2018-04-03

Aqueous methylglyoxal chemistry has often been implicated as an important source of oligomers in atmospheric aerosol. Here we report on chemical analysis of brown carbon aerosol particles collected from cloud cycling/photolysis chamber experiments, where gaseous methylglyoxal and methylamine interacted with glycine, ammonium, or methylammonium sulfate seed particles. Eighteen N-containing oligomers were identified in the particulate phase by liquid chromatography/diode array detection/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. Chemical formulas were determined and, for 6 major oligomer products, MS 2 fragmentation spectra were used to propose tentative structures and mechanisms. Electronic absorption spectra were calculated for six tentative product structures by an ab initio second order algebraic-diagrammatic-construction/density functional theory approach. For five structures, matching calculated and measured absorption spectra suggest that they are dominant light-absorbing species at their chromatographic retention times. Detected oligomers incorporated methylglyoxal and amines, as expected, but also pyruvic acid, hydroxyacetone, and significant quantities of acetaldehyde. The finding that ∼80% (by mass) of detected oligomers contained acetaldehyde, a methylglyoxal photolysis product, suggests that daytime methylglyoxal oligomer formation is dominated by radical addition mechanisms involving CH 3 CO*. These mechanisms are evidently responsible for enhanced browning observed during photolytic cloud events.

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

Pulsed laser photolysis and quantum chemical-statistical rate study of the reaction of the ethynyl radical with water vapor

NASA Astrophysics Data System (ADS)

Carl, Shaun A.; Minh Thi Nguyen, Hue; Elsamra, Rehab M. I.; Tho Nguyen, Minh; Peeters, Jozef

2005-03-01

The rate coefficient of the gas-phase reaction C2H+H2O→products has been experimentally determined over the temperature range 500-825K using a pulsed laser photolysis-chemiluminescence (PLP-CL) technique. Ethynyl radicals (C2H) were generated by pulsed 193nm photolysis of C2H2 in the presence of H2O vapor and buffer gas N2 at 15Torr. The relative concentration of C2H radicals was monitored as a function of time using a CH * chemiluminescence method. The rate constant determinations for C2H+H2O were k1(550K)=(2.3±1.3)×10-13cm3s-1, k1(770cm3s-1, and k1(825cm3s-1. The error in the only other measurement of this rate constant is also discussed. We have also characterized the reaction theoretically using quantum chemical computations. The relevant portion of the potential energy surface of C2H3O in its doublet electronic ground state has been investigated using density functional theory B3LYP /6-311++G(3df,2p) and molecular orbital computations at the unrestricted coupled-cluster level of theory that incorporates all single and double excitations plus perturbative corrections for the triple excitations, along with the 6-311++G(3df,2p) basis set [(U)CCSD(T)/6-311++G(3df,2p)] and using UCCSD(T )/6-31G(d,p) optimized geometries. Five isomers, six dissociation products, and sixteen transition structures were characterized. The results confirm that the hydrogen abstraction producing C2H2+OH is the most facile reaction channel. For this channel, refined computations using (U)CCSD(T)/6-311++G(3df,2p)//(U)CCSD(T)/6-311++G(d,p) and complete-active-space second-order perturbation theory/complete-active-space self-consistent-field theory (CASPT2/CASSCF) [B. O. Roos, Adv. Chem. Phys. 69, 399 (1987)] using the contracted atomic natural orbitals basis set (ANO-L) [J. Almlöf and P. R. Taylor, J. Chem. Phys.86, 4070 (1987)] were performed, yielding zero-point energy-corrected potential energy barriers of 17kJmol-1 and 15kJmol-1, respectively. Transition-state theory rate constant

Combustion Processes Indoors: a Source of High OH Radical Concentrations Through the Photolysis of Hono

NASA Astrophysics Data System (ADS)

Bartolomei, V.; Gomez Alvarez, E.; Glor, M.; Gligorovski, S.; Temime-Roussel, B.; Quivet, E.; Strekowski, R.; Zetzsch, C.; Held, A. B.; Wortham, H.

2013-12-01

Hydroxyl radical (OH) is one of the most important oxidant species in the atmosphere controlling its self-oxidizing capacity. The main sources of OH radicals are photolysis of ozone and photolysis of nitrous acid (HONO), among the others. In the indoor air, the ozonolysis of alkenes has been suggested as the main OH formation pathway. The possibility for OH formation through photolytic pathways in the indoor environment has been, up to now, ignored (Gómez Alvarez et al., 2012). Models and indirect measurements to the present time predicted concentrations of OH radicals in the order of 104 -105 cm-3. Recently, by direct measurements we have detected high OH radical concentrations of 1.8 106 cm-3 in a classroom in Marseille and we demonstrated that its main source is the photolysis of HONO (Gómez Alvarez et al., 2013). The concentrations of HONO are quite high indoors, reaching levels in the order of a few tens of ppbV (Gómez Alvarez et al., 2013). This is mainly due to 1) direct combustion sources and 2) heterogeneous reactions of NO2 on the numerous surfaces present in the indoor environment. HONO levels of 30 ppb were measured in a previous campaign carried out in Bayreuth in July 2012 as direct emissions from the combustion of a candle. The combination between so high concentrations of HONO and higher than expected light transmissions indoors (or indoor artificial lighting) could have a significant impact on the OH concentrations indoors which could feasibly become considerably higher than we measured in our school campaign (Gomez Alvarez et al., 2013). In order to evaluate these upper limits under combustion conditions in the indoor environment, we have carried out a campaign in the LOTASC chamber (Bayreuth, Germany). For this aim, the exhaust fumes from the burning of a commonly used domestic candle have been introduced in the chamber. The chamber was irradiated under well research indoor lighting conditions. A thorough characterization of light intensities

Flash photolysis of rhodopsin in the cat retina

PubMed Central

1981-01-01

The bleaching of rhodopsin by short-duration flashes of a xenon discharge lamp was studied in vivo in the cat retina with the aid of a rapid, spectral-scan fundus reflectometer. Difference spectra recorded over a broad range of intensities showed that the bleaching efficacy of high-intensity flashes was less than that of longer duration, steady lights delivering the same amount of energy. Both the empirical results and those derived from a theoretical analysis of flash photolysis indicate that, under the conditions of these experiments, the upper limit of the flash bleaching of rhodopsin in cat is approximately 90%. Although the fact that a full bleach could not be attained is attributable to photoreversal, i.e., the photic regeneration of rhodopsin from its light-sensitive intermediates, the 90% limit is considerably higher than the 50% (or lower) value obtained under other experimental circumstances. Thus, it appears that the duration (approximately 1 ms) and spectral composition of the flash, coupled with the kinetic parameters of the thermal and photic reactions in the cat retina, reduce the light-induced regeneration of rhodopsin to approximately 10%. PMID:7252476

Ablation of lens epithelial cells with a laser photolysis system: Histopathology, ultrastructure, and immunochemistry

PubMed Central

Mamalis, Nick; Grossniklaus, Hans E.; Waring, George O.; Werner, Liliana; Brubaker, Jacob; Davis, Don; Espandar, Ladan; Walker, Rudolf; Thyzel, Reinhardt

2010-01-01

PURPOSE To evaluate efficacy of a neodymium:YAG (Nd:YAG) laser photolysis system in removing lens epithelial cells (LECs) and characterize the effect of the laser on laminin and fibronectin involved in LEC adhesion and migration. METHODS Cadaver eyes were evaluated using the Miyake technique. The lenses were removed with phacoemulsification. The modified Nd:YAG laser was used to clean the LECs from the capsule. Only the fornix was cleaned in some eyes and the anterior subcapsular area in other eyes. Some areas were not treated and acted as controls. Standard irrigation/aspiration (I/A) removal of LECs was performed in additional eyes. The eyes were analyzed using light microscopy and immunohistochemical staining. RESULTS Histopathologic evaluation showed that the laser removed the LECs from the anterior lens capsule and from the fornix. Immunohistochemical staining showed fibronectin and laminin staining in the untreated areas that was absent in the treated areas. Standard I/A removal of the LECs showed absence of cells but persistent laminin and fibronectin. Electron microscopy showed epithelial cells in untreated areas with an absence of the LECs and debris in treated areas. CONCLUSIONS The laser photolysis system removed LECs from the anterior lens capsule and capsule fornix. Along with the cells, laminin, fibronectin, and cell debris remained in the untreated areas but were removed by the treatment. This treatment may be useful in preventing posterior capsule opacification. Financial Disclosure No author has a financial or proprietary interest in any material or method mentioned. Additional disclosures are found in the footnotes. PMID:20494774

Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: laboratory photolysis, biodegradation, and sorption experiments.

PubMed

Yamamoto, Hiroshi; Nakamura, Yudai; Moriguchi, Shigemi; Nakamura, Yuki; Honda, Yuta; Tamura, Ikumi; Hirata, Yoshiko; Hayashi, Akihide; Sekizawa, Jun

2009-02-01

We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption-namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol-and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals-propranolol, indomethacin, and ifenprodil-were relatively easily photodegraded (i.e., half-life<24h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life>24h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K(d) values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K(d) values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (logK(oc)) showed a poor linear correlation with the octanol-water distribution coefficient (logD(ow)) at neutral pH. These results suggest other sorption mechanisms-such as electrochemical affinity, in addition to hydrophobic interaction-play an important role in sorption to sediment/soil at neutral pH.

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.

Photolytic and photocatalytic degradation of quinclorac in ultrapure and paddy field water: identification of transformation products and pathways.

PubMed

Pareja, Lucía; Pérez-Parada, Andrés; Agüera, Ana; Cesio, Verónica; Heinzen, Horacio; Fernández-Alba, Amadeo R

2012-05-01

Quinclorac (QNC) is an effective but rather persistent herbicide commonly used in rice production. This herbicide presents a mean persistence in the environment so its residues are considered of environmental relevance. However, few studies have been conducted to investigate its environmental behavior and degradation. In the present work, direct photolysis and TiO(2) photocatalysis of the target compound in ultrapure and paddy field water were investigated. After 10h photolysis in ultrapure water, the concentration of QNC declined 26% and 54% at 250 and 700 W m(-2), respectively. However, the amount of quinclorac in paddy field water remained almost constant under the same irradiation conditions. QNC dissipated completely after 40 min of TiO(2) photocatalysis in ultrapure water, whereas 130 min were necessary to degrade 98% of the initial concentration in paddy field water. Possible QNC photolytic and photocatalytic degradation pathways are proposed after structure elucidation of the main transformation products, through liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry and exact mass measurements. Pyridine ring hydroxylation at C-9 followed by ring opening and/or oxidative dechlorination were the key steps of QNC degradation. Copyright © 2012 Elsevier Ltd. 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

FlashPhotol: Using a Flash Photolysis Apparatus Simulator to Introduce Students to the Kinetics of Transient Species and Fast Reactions

ERIC Educational Resources Information Center

Bigger, Stephen W.

2016-01-01

FlashPhotol is an educational software package that introduces students to the kinetics of transient species and fast reactions. This is achieved by means of a computer-simulated flash photolysis apparatus that comprises all major functional elements and that students can use to perform various experiments. The experimental interface presents a…

Carbon Stable Isotope Fractionation of Sulfamethoxazole during Biodegradation by Microbacterium sp. Strain BR1 and upon Direct Photolysis.

PubMed

Birkigt, Jan; Gilevska, Tetyana; Ricken, Benjamin; Richnow, Hans-Hermann; Vione, Davide; Corvini, Philippe F-X; Nijenhuis, Ivonne; Cichocka, Danuta

2015-05-19

Carbon isotope fractionation of sulfamethoxazole (SMX) during biodegradation by Microbacterium sp. strain BR1 (ipso-hydroxylation) and upon direct photolysis was investigated. Carbon isotope signatures (δ(13)C) of SMX were measured by LC-IRMS (liquid chromatography coupled to isotope ratio mass spectrometry). A new LC-IRMS method for the SMX metabolite, 3-amino-5-methylisoxazole (3A5MI), was established. Carbon isotope enrichment factors for SMX (ε(C)) were -0.6 ± 0.1‰ for biodegradation and -2.0 ± 0.1‰ and -3.0 ± 0.2‰ for direct photolysis, at pH 7.4 and pH 5, respectively. The corresponding apparent kinetic isotope effects (AKIE) for ipso-hydroxylation were 1.006 ± 0.001; these fall in the same range as AKIE in previously studied hydroxylation reactions. The differences in SMX and 3A5MI fractionation upon biotic and abiotic degradation suggest that compound specific stable isotope analysis (CSIA) is a suitable method to distinguish SMX reaction pathways. In addition, the study revealed that the extent of isotope fractionation during SMX photolytic cleavage is pH-dependent.

Photochemical water oxidation and origin of nonaqueous uranyl peroxide complexes.

PubMed

McGrail, Brendan T; Pianowski, Laura S; Burns, Peter C

2014-04-02

Sunlight photolysis of uranyl nitrate and uranyl acetate solutions in pyridine produces uranyl peroxide complexes. To answer longstanding questions about the origin of these complexes, we conducted a series of mechanistic studies and demonstrate that these complexes arise from photochemical oxidation of water. The peroxo ligands are easily removed by protonolysis, allowing regeneration of the initial uranyl complexes for potential use in catalysis.

Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry.

PubMed

Celeiro, Maria; Facorro, Rocio; Dagnac, Thierry; Vilar, Vítor J P; Llompart, Maria

2017-08-01

The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl, metalaxyl, myclobutanil and tebuconazole) was evaluated in different types of water. Two different systems, direct UV photolysis and UVC/H 2 O 2 advanced oxidation process (AOP), were applied for the photodegradation tests. For the monitoring of the target compound degradation, a method based on direct injection liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. Several fungicide photodegradation by-products were tentatively identified by high-resolution mass spectrometry (HRMS) as well. For the photolysis studies, the efficiency of different types of radiation, UVC (λ = 254 nm) and UVA (λ = 365 nm), was compared. UVC photolysis provided the highest removal with a complete degradation for fenhexamide and kresoxim-methyl, and percentages between 48 and 78% for the other compounds, excluding iprovalicarb and myclobutanil with removals <35%, after 30 min of irradiation. Besides, the photodegradation tests were performed with different initial concentrations of fungicides, and the efficiency of two photoreactor systems was compared. In all cases, the kinetics followed pseudo-first order, and the half-life times could also be calculated. The addition of H 2 O 2 under UVC light allowed an improvement of the reaction kinetics, especially for the most recalcitrant fungicides, obtaining in all cases removals higher than 82% in less than 6 min. Finally, in order to evaluate the suitability of the proposed systems, both UVC photolysis and UVC/H 2 O 2 system were tested in different real water matrices (wastewater, tap water, swimming pool water and river water), showing that the UVC/H 2 O 2 system had the highest removal efficiency in less than 6 min, for all water samples.

DEUTERIUM FRACTIONATION DURING AMINO ACID FORMATION BY PHOTOLYSIS OF INTERSTELLAR ICE ANALOGS CONTAINING DEUTERATED METHANOL

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

Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira

2016-08-10

Deuterium (D) atoms in interstellar deuterated methanol might be distributed into complex organic molecules through molecular evolution by photochemical reactions in interstellar grains. In this study, we use a state-of-the-art high-resolution mass spectrometer coupled with a high-performance liquid chromatography system to quantitatively analyze amino acids and their deuterated isotopologues formed by the photolysis of interstellar ice analogs containing singly deuterated methanol CH{sub 2}DOH at 10 K. Five amino acids (glycine, α -alanine, β -alanine, sarcosine, and serine) and their deuterated isotopologues whose D atoms are bound to carbon atoms are detected in organic residues formed by photolysis followed by warmingmore » up to room temperature. The abundances of singly deuterated amino acids are in the range of 0.3–1.1 relative to each nondeuterated counterpart, and the relative abundances of doubly and triply deuterated species decrease with an increasing number of D atoms in a molecule. The abundances of amino acids increase by a factor of more than five upon the hydrolysis of the organic residues, leading to decreases in the relative abundances of deuterated species for α -alanine and β -alanine. On the other hand, the relative abundances of the deuterated isotopologues of the other three amino acids did not decrease upon hydrolysis, indicating different formation mechanisms of these two groups upon hydrolysis. The present study facilitates both qualitative and quantitative evaluations of D fractionation during molecular evolution in the interstellar medium.« less

Helicopter crashes into water: warning time, final position, and other factors affecting survival.

PubMed

Brooks, Christopher J; MacDonald, Conor V; Baker, Susan P; Shanahan, Dennis F; Haaland, Wren L

2014-04-01

According to 40 yr of data, the fatality rate for a helicopter crash into water is approximately 25%. Does warning time and the final position of the helicopter in the water influence the survival rate? The National Transportation Safety Board (NTSB) database was queried to identify helicopter crashes into water between 1981 and 2011 in the Gulf of Mexico and Hawaii. Fatality rate, amount of warning time prior to the crash, and final position of the helicopter were identified. There were 133 helicopters that crashed into water with 456 crew and passengers. Of these, 119 occupants (26%) did not survive; of those who did survive, 38% were injured. Twelve died after making a successful escape from the helicopter. Crashes with < 15 s warning had a fatality rate of 22%, compared to 12% for 16-60 s warning and 5% for > 1 min. However, more than half of fatalities (57%) came from crashes for which the warning time could not be determined. Lack of warning time and how to survive in the water after the crash should be a topic for study in all marine survival/aircraft ditching courses. Investigators should be trained to provide estimates of warning time when investigating helicopter crashes into water.

Theoretical Study of the Photolysis Mechanisms of Methylpentaphenyldimetallanes (Ph₃MM'Ph₂Me; M, M' = Si and Ge).

PubMed

Su, Shih-Hao; Su, Ming-Der

2018-06-04

The mechanisms of the photolysis reactions are studied theoretically at the M06-2X/6-311G(d) level of theory, using the four types of group 14 molecules that have the general structure, Ph₃M⁻M'Ph₂Me (M and M' = Si and Ge), as model systems. This study provides the first theoretical evidence for the mechanisms of these photorearrangements of compounds that contain a M⁻M' single bond. The model investigations indicate that the preferred reaction route for the photolysis reactions is, as follows: reactant → Franck-Condon (FC) region → minimum (triplet) → transition state (triplet) → triplet/singlet intersystem crossing → photoproducts (both di-radicals and singlets). The theoretical findings demonstrate that the formation of radicals results from reactions of the triplet states of these reactants. This could be because both the atomic radius and the chemical properties of silicon and germanium are quite similar to each other and compared to other group 14 elements, their photolytic mechanisms are nearly the same. The results for the photolytic mechanisms that are studied in this work are consistent with the available experimental observations and allow for a number of predictions for other group 14 dimetallane analogues to be made.

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.

76 FR 57646 - Final Withdrawal of Certain Federal Aquatic Life Water Quality Criteria Applicable to Wisconsin

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-16

... limits in National Pollutant Discharge Elimination System (NPDES) permits, and may affect Clean Water Act... the final Water Quality Guidance for the Great Lakes System (Guidance), required by CWA Section 118(c... waters of the Great Lakes System in Wisconsin designated as Warm Water Sportfish and Warm Water Forage...

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.

Assessing the environmental fate of S-metolachlor, its commercial product Mercantor Gold® and their photoproducts using a water-sediment test and in silico methods.

PubMed

Gutowski, Lukasz; Baginska, Ewelina; Olsson, Oliver; Leder, Christoph; Kümmerer, Klaus

2015-11-01

Pesticides enter surface and groundwater by several routes in which partition to sediment contributes to their fate by abiotic (e.g. photolysis, hydrolysis) and biotic processes. Yet, little is known about S-metolachlor (SM) transformation in water-sediment systems. Therefore, a newly developed screening water-sediment test (WST) was applied to compare biodegradation and sorption processes between pure SM and Mercantor Gold® (MG), a commercial formulation of SM. Photolysis in water was performed by Xe lamp irradiation. Subsequently, the biodegradability of SM and MG photolysis mixtures was examined in WST. The primary elimination of SM from water phase was monitored and structures of its TPs resulting from biotransformation (bio-TPs) were elucidated by LC-MS/MS. SM was extracted from sediment in order to estimate the role of sorption in WST for its elimination. A set of in silico prediction software tools was applied for toxicity assessment of SM and its bio-TPs. Obtained results suggest that the MG adjuvants do not significantly affect biodegradation, but do influence diffusion of SM into sediment. 50% of SM could not be re-extracted from sediment with 0.01 M CaCl2 aqueous solution recommended in OECD test guideline for adsorption. Neither the parent compound nor the photo-TPs were biodegraded. However, new bio-TPs have been generated from SM and MG photo-TPs due to bacterial activity in the water-sediment interphase. Moreover, according to in silico assessment of the bio-TPs the biotransformation might lead to an increased toxicity to the water organisms compared with the SM. This might raise concerns of bio-TPs presence in the environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Direct photolysis rates and transformation pathways of the lampricides TFM and niclosamide in simulated sunlight

USGS Publications Warehouse

McConville, Megan B.; Hubert, Terrance D.; Remucal, Christina K.

2016-01-01

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2–5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Direct Photolysis Rates and Transformation Pathways of the Lampricides TFM and Niclosamide in Simulated Sunlight.

PubMed

McConville, Megan B; Hubert, Terrance D; Remucal, Christina K

2016-09-20

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2',5-dichloro-4'-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2-5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Photochemical transformation of phenylurea herbicides in surface waters: a model assessment of persistence, and implications for the possible generation of hazardous intermediates.

PubMed

Fabbri, Debora; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-01-01

This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Study of the photochemical transformation of 2-ethylhexyl 4-(dimethylamino)benzoate (OD-PABA) under conditions relevant to surface waters.

PubMed

Calza, P; Vione, D; Galli, F; Fabbri, D; Dal Bello, F; Medana, C

2016-01-01

We studied the aquatic environmental fate of 2-ethylhexyl 4-(dimethylamino)benzoate (OD-PABA), a widespread sunscreen, to assess its environmental persistence and photoinduced transformation. Direct photolysis is shown to play a key role in phototransformation, and this fast process is expected to be the main attenuation route of OD-PABA in sunlit surface waters. The generation of transformation products (TPs) was followed via HPLC/HRMS. Five (or four) TPs were detected in the samples exposed to UVB (or UVA) radiation, respectively. The main detected TPs of OD-PABA, at least as far as HPLC-HRMS peak areas are concerned, would involve a dealkylation or hydroxylation/oxidation process in both direct photolysis and indirect phototransformation. The latter was simulated by using TiO2-based heterogeneous photocatalysis, involving the formation of nine additional TPs. Most of them resulted from the further degradation of the primary TPs that can also be formed by direct photolysis. Therefore, these secondary TPs might also occur as later transformation intermediates in natural aquatic systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modeling phototransformation reactions in surface water bodies: 2,4-dichloro-6-nitrophenol as a case study.

PubMed

Maddigapu, Pratap Reddy; Minella, Marco; Vione, Davide; Maurino, Valter; Minero, Claudio

2011-01-01

The anionic form of 2,4-dichloro-6-nitrophenol (DCNP), which prevails in surface waters over the undissociated one, has a direct photolysis quantum yield of (4.53 ± 0.78) × 10(-6) under UVA irradiation and second-order reaction rate constants of (2.8 ± 0.3) × 10(9) M(-1) s(-1) with •OH, (3.7 ± 1.4) × 10(9) M(-1) s(-1) with (1)O(2), and (1.36 ± 0.09) × 10(8) M(-1) s(-1) with the excited triplet state of anthraquinone-2-sulfonate, adopted as a proxy for the photoactive dissolved organic compounds in surface waters. DCNP also shows negligible reactivity with the carbonate radical. Insertion of the data into a model of surface water photochemistry indicates that the direct photolysis and the reactions with •OH and (1)O(2) would be the main phototransformation processes of DCNP, with •OH prevailing in organic-poor and (1)O(2) in organic-rich waters. The model results compare well with the field data of DCNP in the Rhône river delta (Southern France), where (1)O(2) would be the main reactive species for the phototransformation of the substrate.

Photolytic dehalogenation of disinfection byproducts in water by natural sunlight irradiation.

PubMed

Abusallout, Ibrahim; Hua, Guanghui

2016-09-01

The aqueous photolysis of halogenated disinfection byproducts (DBPs) by natural sunlight irradiation was studied to determine their photolytic dehalogenation kinetics. Total organic halogen analysis was used to quantify the dehalogenation extents of DBPs during outdoor photolysis experiments. Dichloroacetamide, chloral hydrate, chloroform, dichloroacetonitrile, monochloro-, monobromo-, dichloro-, dibromo-, and trichloroacetic acids were generally resistant to photolytic dehalogenation and showed less than 10% reduction after 6 h sunlight irradiation. Monoiodoacetic acid, tribromoacetic acid, bromoform, dibromoacetonitrile, and trichloronitromethane showed moderate to high dehalogenation degrees with half-lives of 4.0-19.3 h. Diiodoacetic acid, triiodoacetic acid, and iodoform degraded rapidly under the sunlight irradiation and exhibited half-lives of 5.3-10.2 min. In general, the photosensitive cleavage of carbon-halogen bonds of DBPs increased with increasing number of halogens (tri- > di- > mono-halogenated) and size of the substituted halogens (I > Br > Cl). Nitrate, nitrite, and pH had little impact on the photodehalogenation of DBPs under typical levels in surface waters. The presence of natural organic matter (NOM) inhibited the photodehalogenation of DBPs by light screening. The NOM inhibiting effects were more pronounced for the fast degrading iodinated DBPs. The results of this study improve our understanding about the photolytic dehalogenation of wastewater-derived DBPs in surface waters during water reuse. Published by Elsevier Ltd.

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.

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.

Fact Sheet: Notice of Ambient Water Quality Criteria Document for Tributyltin (TBT) - Final

EPA Pesticide Factsheets

Information pertaining to 2004 Final Acute and Chronic Ambient Aquatic Life Water Quality Criteria for Tributyltin (TBT) for freshwater and saltwater. This fact sheet includes the safe levels of TBT that should protect the majority of species.

The environmental fate of the antiviral drug oseltamivir carboxylate in different waters.

PubMed

Bartels, Peter; von Tümpling, Wolf

2008-11-01

Since the efficacy of oseltamivir carboxylate (OC) as the active metabolite of Tamiflu has been demonstrated against influenza viruses and even against the avian influenza virus (H5N1), millions of Tamiflu treatment courses are stockpiled worldwide. This was done not at least to follow the recommendations of the World Health Organization (WHO) to cope with a viral influenza pandemic. Concentrations up to 26-32 microg l(-1) OC in river catchment areas in the United States and in the United Kingdom had been predicted recently for a pandemic case, assuming an apparent persistence of the Tamiflu metabolite. Such concentrations may involve the risk of generation of antiviral resistance. But there is still a lack of data concerning the stability of OC in a surface water environment. Under this aspect these predictions have to be validated with concrete facts about the environmental fate of OC. In this article we summarized the results of three different daylight exposure experiments with OC in different waters under sterile and non-sterile conditions simulating shallow water processes at the latitude of approximately 52 degrees N. Using a river water solution containing 50 microg l(-1) OC under non-sterile conditions a half-life time of 17.8 days was observed. Direct photolysis plays no or only a negligible role for the decomposition of OC. Degradation of OC seems to occur as a combination of microbial metabolism and indirect photolysis.

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.

Final Rule: Definition of “Waters of the United States” – Addition of Applicability Date to 2015 Clean Water Rule

EPA Pesticide Factsheets

Link to the final rule of the applicability date of the clean water rule, The 2015 Rule will not be applicable until two years following publication of the applicability date rule in the Federal Register.

Climate Change Vulnerability Assessments: Four Case Studies of Water Utility Practices (2011 Final)

EPA Science Inventory

EPA has released the final report titled, Climate Change Vulnerability Assessments: Four Case Studies of Water Utility Practices. This report was prepared by the National Center for Environmental Assessment's Global Climate Research Staff in the Office of Research and D...

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

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.

Study of photocatalytic degradation of tributyltin, dibutylin and monobutyltin in water and marine sediments.

PubMed

Brosillon, Stephan; Bancon-Montigny, Chrystelle; Mendret, Julie

2014-08-01

This study reports on the first assessment of the treatment of sediments contaminated by organotin compounds using heterogeneous photocatalysis. Photocatalysis of organotins in water was carried out under realistic concentration conditions (μgL(-1)). Degradation compounds were analyzed by GC-ICP-MS; a quasi-complete degradation of tributyltin (TBT) in water (99.8%) was achieved after 30min of photocatalytic treatment. The degradation by photolysis was about (10%) in the same conditions. For the first time decontamination of highly polluted marine sediments (certified reference material and harbor sediments) by photocatalysis proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix. In sediment, TBT degradation yield ranged from 32% to 37% after only 2h of irradiation (TiO2-UV) and the by-products: dibutyltin (DBT) and monobutyltin (MBT) were degraded very rapidly in comparison with TBT. It was shown that during photocatalysis of organotins in sediments, the hydroxyl radical attack and photolysis are the two ways for the degradation of adsorbed TBT. Copyright © 2014 Elsevier Ltd. All rights reserved.

RESPONSE PROTOCOL TOOLBOX: PLANNING FOR AND RESPONDING TO DRINKING WATER CONTAMINATION THREATS AND INCIDENTS. MODULE 1: WATER UTILITIES PLANNING GUIDE - INTERIM FINAL - DECEMBER 2003

EPA Science Inventory

The interim final Response Protocol Toolbox: Planning for and Responding to Contamination Threats to Drinking Water Systems is designed to help the water sector effectively and appropriately respond to intentional contamination threats and incidents. It was produced by EPA, buil...

Manmade organic compounds in the surface waters of the United States: a review of current understanding

USGS Publications Warehouse

Smith, James A.; Witkowski, Patrick J.; Fusillo, Thomas V.

1987-01-01

This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves between water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be absorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rate commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence that the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison to concentrations determined during ongoing research. Finally, where sufficient data exist, regional and temporal contamination trends in the United States are discussed.

Manmade organic compounds in the surface waters of the United States; a review of current understanding

USGS Publications Warehouse

Smith, James A.; Witkowski, P.J.; Fusillo, Thomas V.

1988-01-01

This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves among water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be adsorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rates commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison with concentrations determined during ongoing research. Finally, where data are sufficient, regional and temporal contamination trends in the United States are discussed.

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.

Degradation of emerging contaminants from water under natural sunlight: The effect of season, pH, humic acids and nitrate and identification of photodegradation by-products.

PubMed

Koumaki, Elena; Mamais, Daniel; Noutsopoulos, Constantinos; Nika, Maria-Christina; Bletsou, Anna A; Thomaidis, Nikolaos S; Eftaxias, Alexander; Stratogianni, Georgia

2015-11-01

Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocrine disrupting chemicals (EDCs) were investigated in order to evaluate their photochemical fate in aquatic environment and to assess the effect of season and specific characteristics of water (pH, humic acids and nitrate concentration) on the removal of target EDCs and NSAIDs through photodegradation. An additional objective was the identification of the photodegradation by-products of specific NSAIDs and their dependence on irradiation time. Selected compounds' transformation was investigated under natural sunlight radiation while control experiments were conducted in the dark. As expected, most of compounds' degradation rate decreased with decreasing light intensity between two different experimental periods. Most of the tested compounds exhibited different rates of degradation during direct and indirect photolysis. The degradation rate of the selected compounds increased in the presence of NO3(-) and the photodegradation rate was higher for some compounds in alkaline than in acidic solution. The effect of humic acids' presence in the water depends on the absorbance spectrum of the compound and the produced photosensitizers. More specifically, humic acids act as inner filter toward most of the selected NSAIDs and as photosensitizers toward most of the EDCs. The results of the irradiation experiments in the presence of both humic acids and NO3(-), indicate that the direct photolysis is much more efficient than indirect photochemical processes. Finally, several degradation by-products of ketoprofen and diclofenac were identified in the samples, exposed to sunlight. The dependence of these by-products on radiation time is also demonstrated. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3

DOE PAGES

Prather, M. J.

2015-05-27

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observed statistics for the vertical correlation of cloud layers, Cloud-J 7.3 provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations represented by four quadrature atmospheres produces mean J values in an atmospheric column with root-mean-square errors of 4% or less compared with 10–20% errors using simpler approximations.more » Cloud-J is practical for chemistry-climate models, requiring only an average of 2.8 Fast-J calls per atmosphere, vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections is also incorporated into Cloud-J.« less

A study of the degradation of organophosphorus pesticides in river waters and the identification of their degradation products by chromatography coupled with mass spectrometry.

PubMed

Zhao, Xueheng; Hwang, Huey-Min

2009-05-01

The degradation of selected organophosphorus pesticides (OPs), i.e., malathion and parathion, in river water, has been studied with solar simulator irradiation. The degradation of OPs and formation of degradation products were determined by chromatography coupled with mass spectrometry analysis. The effect of a photosensitizer, i.e., riboflavin, on the photolysis of OPs in a river-water environment was examined. There was no significant increase in the degradation rate in the presence of the photosensitizer. Degradation products of the OPs were identified with gas chromatography coupled with mass spectrometry (GC-MS) after derivatization by pentafluorobenzyl bromide (PFBB) and with high-performance liquid chromatography-mass spectrometry (HPLC-MS) with electrospray (ESI) or atomospheric pressure chemical ionization (APCI). Malaoxon, paraoxon, 4-nitrophenol, aminoparathion, O,O-dimethylthiophosphoric acid, and O,O-dimethyldithiophosphoric acid, have been separated and identified as the degradation products of malathion and parathion after photolysis in river water. Based on the identified transformation products, a rational degradation pathway in river water for both OPs is proposed. The identities of these products can be used to evaluate the toxic effects of the OPs and their transformation products on natural environments.

Synthesis and Photolysis of Model Compounds for Mechanistic Studies of 1,3,5-Trinitro-1,3,5-Triazacyclohexane (RDX) Decomposition.

DTIC Science & Technology

1978-06-01

However, once irradiation was stopped the radical disappeared within a half hour . When the temperature was Increased to 40 °C the radical existed...and Russat proposed that the mechanism is bimolecular with the products OK - . ‘ being the nitrone and hydroxy l amine. Experimenta l support for this...process was provided by K. U. Ingold 15 . Kaminsky and Lamchen 16 and ethers have shown that the photolysis of cyclic nitrones gives oxi- ziridines

76 FR 3126 - Final Determination of the Assistant Administrator for Water Pursuant to Section 404(c) of the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-19

... area will have an unacceptable adverse effect on municipal water supplies, shellfish beds and fishery... Assistant Administrator for Water Pursuant to Section 404(c) of the Clean Water Act Concerning the Spruce No...: This is a notice of EPA's Final Determination pursuant to section 404(c) of the Clean Water Act to...

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

Is [Co4(H2O)2(α-PW9O34)2](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments.

PubMed

Natali, Mirco; Berardi, Serena; Sartorel, Andrea; Bonchio, Marcella; Campagna, Sebastiano; Scandola, Franco

2012-09-11

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.

Primary processes in photolysis of octopus rhodopsin.

PubMed

Ohtani, H; Kobayashi, T; Tsuda, M; Ebrey, T G

1988-01-01

The photolysis of octopus rhodopsin was studied by picosecond time-resolved spectroscopy at physiological temperature (8 degrees C) and by steady-state spectroscopy at very low temperature (10 K). Both hypsorhodopsin and bathorhodopsin were formed from a bathorhodopsin-like red-shifted intermediate "primerhodopsin," which was the primary photoproduct with our time resolution (36 ps). Though it was proposed that hypsorhodopsin is formed solely by a multiphoton process, the present results obtained by using blue light pulses (461 nm) of low intensity showed that hypsorhodopsin is formed by a single photon mechanism via thermal decay from primerhodopsin. When the excitation intensity is increased, a channel for the photochemical formation of hypsorhodopsin from primerhodopsin is opened. There are two thermal pathways leading from primerhodopsin. One process is the formation of hypsorhodopsin, which is later thermally converted to bathorhodopsin, and the other is the direct formation of bathorhodopsin from primerhodopsin. The formation efficiencies at room temperature of hypsorhodopsin and bathorhodopsin at very low excitation intensity were estimated to be larger than 0.6 and smaller than 0.4, respectively. The formation of hypsorhodopsin was also found in the early stages of the irradiation of octopus rhodopsin with weak continuous light at 10 K. However bathorhodopsin is formed three times more efficiently than hypsorhodopsin at 10 K.At physiological temperatures the formation of hypsorhodopsin in D(2)O takes place more slowly than in H(2)O. This indicates that the lifetime of primerhodopsin is decreased by H(2)O/D(2)O exchange. The rate constant for the primerhodopsin --> bathorhodopsin conversion is more sensitive than that for the primerhodopsin --> hypsorhodopsin conversion. The transformation of hypsorhodopsin to bathorhodopsin shows no deuterium effect at low temperature.

Application of effect-directed analysis to identify mutagenic nitrogenous disinfection by-products of advanced oxidation drinking water treatment.

PubMed

Vughs, D; Baken, K A; Kolkman, A; Martijn, A J; de Voogt, P

2018-02-01

Advanced oxidation processes are important barriers for organic micropollutants in (drinking) water treatment. It is however known that medium pressure UV/H 2 O 2 treatment may lead to mutagenicity in the Ames test, which is no longer present after granulated activated carbon (GAC) filtration. Many nitrogen-containing disinfection by-products (N-DBPs) result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM) during medium pressure UV treatment of water. Identification of the N-DBPs and the application of effect-directed analysis to combine chemical screening results with biological activity would provide more insight into the relation of specific N-DBPs with the observed mutagenicity and was the subject of this study. To this end, fractions of medium pressure UV-treated and untreated water extracts were prepared using preparative HPLC and tested using the Ames fluctuation test. In addition, high-resolution mass spectrometry was performed on all fractions to assess the presence of N-DBPs. Based on toxicity data and read across analysis, we could identify five N-DBPs that are potentially genotoxic and were present in relatively high concentrations in the fractions in which mutagenicity was observed. The results of this study offer opportunities to further evaluate the identity and potential health concern of N-DBPs formed during advanced oxidation UV drinking water treatment.

Inactivation and injury of total coliform bacteria after primary disinfection of drinking water by TiO2 photocatalysis.

PubMed

Rizzo, Luigi

2009-06-15

In this study the potential application of TiO(2) photocatalysis as primary disinfection system of drinking water was investigated in terms of coliform bacteria inactivation and injury. As model water the effluent of biological denitrification unit for nitrate removal from groundwater, which is characterized by high organic matter and bacteria release, was used. The injury of photocatalysis on coliform bacteria was characterized by means of selective (mEndo) and less selective (mT7) culture media. Different catalyst loadings as well as photolysis and adsorption effects were investigated. Photocatalysis was effective in coliform bacteria inactivation (91-99% after 60 min irradiation time, depending on both catalyst loading and initial density of coliform bacteria detected by mEndo), although no total removal was observed after 60 min irradiation time. The contribution of adsorption mechanism was significant (60-98% after 60 min, depending on catalyst loading) compared to previous investigations probably due to the nature of source water rich in particulate organic matter and biofilm. Photocatalysis process did not result in any irreversible injury (98.8% being the higher injury) under investigated conditions, thus a bacteria regrowth may take place under optimum environment conditions if any final disinfection process (e.g., chlorine or chlorine dioxide) is not used.

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.

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

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

Nanomaterial Case Studies: Nanoscale Titanium Dioxide in Water Treatment and in Topical Sunscreen (Final)

EPA Science Inventory

EPA announced the availability of the final report, Nanomaterial Case Studies: Nanoscale Titanium Dioxide in Water Treatment and in Topical Sunscreen. This report is a starting point to determine what is known and what needs to be known about selected nanomaterials as par...

Effects of blue or violet light on the inactivation of Staphylococcus aureus by riboflavin-5'-phosphate photolysis.

PubMed

Wong, Tak-Wah; Cheng, Chien-Wei; Hsieh, Zong-Jhe; Liang, Ji-Yuan

2017-08-01

The light sensitive compound riboflavin-5'-phosphate (or flavin mononucleotide, FMN) generates reactive oxygen species (ROS) upon photo-irradiation. FMN is required by all flavoproteins because it is a cofactor of biological blue-light receptors. The photochemical effects of FMN after irradiation by blue or violet light on the inactivation of Staphylococcus aureus strains, including a methicillin-resistant strain (MRSA), were investigated in this study. Upon blue- or violet-light photo-treatment, FMN was shown to inactivate S. aureus due to the generated ROS. Effective bacterial inactivation can be achieved by FMN photolysis without an exogenous electron provider. Inactivation rates of 94.9 and 95.2% in S. aureus and MRSA, respectively, can be reached by blue light irradiation (2.0mW/cm 2 ) with 120μM FMN for 120min. A lower FMN concentration and a shorter time are required to reach similar effects by violet light irradiation. Inactivation rates of 96.3 and 97.0% in S. aureus and MRSA, respectively, can be reached by violet light irradiation (1.0mW/cm 2 ) with 30μM FMN for 30min. The sensitivity of the inherent photosensitizers is lower under blue-light irradiation. A long exposure photolytic treatment of FMN by blue light is required to inactivate S. aureus. Violet light was found to be more efficient in S. aureus inactivation at the same radiant intensity. FMN photolysis with blue or violet light irradiation enhanced the inactivation rates of S. aureus and MRSA. FMN photochemical treatment could be a supplemental technique in hygienic decontamination processes. Copyright © 2017 Elsevier B.V. All rights reserved.

Revisions to the Clean Water Act Regulatory Definition of Discharge of Dredged Material; Final Rule

EPA Pesticide Factsheets

The U.S. Army Corps of Engineers (Corps) and the Environmental Protection Agency (EPA) promulgated a final rule Amending a Clean Water Act (CWA) section 404 regulation that defines the term discharge of dredged material.

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.

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.

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.

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

PubMed

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

2016-04-15

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

Photolysis rates in correlated overlapping cloud fields: Cloud-J 7.3c

DOE PAGES

Prather, M. J.

2015-08-14

A new approach for modeling photolysis rates ( J values) in atmospheres with fractional cloud cover has been developed and is implemented as Cloud-J – a multi-scattering eight-stream radiative transfer model for solar radiation based on Fast-J. Using observations of the vertical correlation of cloud layers, Cloud-J 7.3c provides a practical and accurate method for modeling atmospheric chemistry. The combination of the new maximum-correlated cloud groups with the integration over all cloud combinations by four quadrature atmospheres produces mean J values in an atmospheric column with root mean square (rms) errors of 4 % or less compared with 10–20 %more » errors using simpler approximations. Cloud-J is practical for chemistry–climate models, requiring only an average of 2.8 Fast-J calls per atmosphere vs. hundreds of calls with the correlated cloud groups, or 1 call with the simplest cloud approximations. Another improvement in modeling J values, the treatment of volatile organic compounds with pressure-dependent cross sections, is also incorporated into Cloud-J.« less

EXPOSURES AND INTERNAL DOSES OF TRIHALOMETHANES IN HUMANS: MULTI-ROUTE CONTRIBUTIONS FROM DRINKING WATER (FINAL)

EPA Science Inventory

The National Center for Environmental Assessment (NCEA) has released a final report that presents and applies a method to estimate distributions of internal concentrations of trihalomethanes (THMs) in humans resulting from a residential drinking water exposure. The report presen...

Variation in chlorotoluron photodegradation rates as a result of seasonal changes in the composition of natural waters.

PubMed

Oliver, Robin G; Wallace, Derek F; Earll, Mark

2013-01-01

It is important to understand the degradation of organic molecules in surface waters to ensure that risk assessments, intended to prevent adverse effects on human health and the environment, are robust. One important degradation mechanism in surface waters is photodegradation. This process is generally studied in laboratory test systems, and the significance of the results is then extrapolated to the field. The aim of this work was to assess how fluctuations in the composition of surface water influence the photodegradation rate of chlorotoluron. Photodegradation DT(50) values in the lake (mean = 26.0 days) and pond (mean = 26.0 days) were significantly slower than in the river (mean = 6.8 days) and stream (mean = 7.3 days) samples. The DT(50) values in the pond and lake samples were similar to the direct photolysis value (mean = 28.6 days). Photodegradation was significantly faster in the stream and river samples, suggesting that indirect photolysis was significant in those waters. Principal component analysis indicated a strong inverse correlation between nitrate concentration and degradation rate. Nitrate concentration had a strong influence on the rate of photodegradation, with increasing nitrate concentrations sharply reducing the DT(50) . However, this effect was restricted to a narrow concentration range and levelled off quite quickly, such that further increases in the nitrate concentration had no significant effect on the rate of degradation. Extrapolating photodegradation rates of chlorotoluron from the laboratory to the field should be relatively straightforward, provided the nitrate concentrations in the waters are known. Copyright © 2012 Society of Chemical Industry.

APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

PubMed

Bodrato, Marco; Vione, Davide

2014-04-01

The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

IR-Monitored Photolysis of CO-Inhibited Nitrogenase: A Major EPR-Silent Species with Coupled Terminal CO Ligands

PubMed Central

Yan, Lifen; Dapper, Christie H.; Scott, Aubrey D.; Newton, William E.

2015-01-01

We have used Fourier transform infrared spectroscopy (FT-IR) to observe the photolysis and recombination of a novel EPR-silent CO-inhibited form of α-H195Q nitrogenase from Azotobacter vinelandii. Photolysis at 4 K yields a strong negative IR difference band at 1938 cm−1, along with a weaker negative feature at 1911 cm−1. These bands and the associated chemical species have both been assigned the label ‘Hi-3’. A positive band at 1921 cm−1 is assigned to the ‘Lo-3’ photoproduct. By using an isotopic mixture of 12C16O and 13C18O, we show that the Hi-3 bands arise from coupling of two similar CO oscillators with one uncoupled frequency at ~1917 cm−1. Although in previous studies Lo-3 was not observed to recombine, by extending the observation range to 200–240 K we found that recombination to Hi-3 does indeed occur, with an activation energy of ~6.5 kJ mol−1. The frequencies of the Hi-3 bands suggest terminal CO ligation. We tested this hypothesis with DFT calculations on models with terminal CO ligands on Fe2 and Fe6 of the FeMo-cofactor. An S = 0 model with both CO ligands in exo positions predicts symmetric and asymmetric stretches at 1938 and 1909 cm−1 respectively, with relative band intensities of ~3.5:1, in good agreement with experiment. From the observed IR intensities, we find that Hi-3 is present at a concentration about equal to that of the EPR-active Hi-1 species. The relevance of Hi-3 to the nitrogenase catalytic mechanism and its recently discovered Fischer-Tropsch chemistry is discussed. PMID:23136072

Formation kinetics of a novel product from photolysis of cytosine in phosphate-buffered solutions

NASA Astrophysics Data System (ADS)

Wenqing, Wang; Feng, Lin; Jilan, Wu

1999-01-01

For studying the role of phosphate in the origin of life and the effect of far-ultraviolet light induced photochemical damage to RNA, DNA and its components, it was found that the photolysis of nucleobases, nucleosides and nucleotides was strongly enhanced by phosphate under the irradiation of medium pressure mercury lamp (MPML). Ultraviolet irradiation (190-220 nm) of cytosine in 0.05 mol dm -3 phosphate buffered solution at pH 8-9 leads to the production of a novel compound C 4H 6N 3O 5P in the presence of oxygen. The main photoproduct has been isolated, purified and characterized by use of 1H- and 31P-NMR spectroscopy, elemental analysis, ultraviolet and infrared spectroscopy and electron impact mass spectrometry. Phosphate effect can be inhibited by amino acids. The formation mechanism of the photoproduct and the kinetics was studied.

Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

PubMed

Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

2017-10-01

Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 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.

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.

Free radical generation by non-equilibrium atmospheric pressure plasma in alcohol-water mixtures: an EPR-spin trapping study

NASA Astrophysics Data System (ADS)

Uchiyama, Hidefumi; Ishikawa, Kenji; Zhao, Qing-Li; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Krishna, Murali C.; Ishijima, Tatsuo; Matsuya, Yuji; Hori, Masaru; Noguchi, Kyo; Kondo, Takashi

2018-03-01

Free radical species in aqueous solution—various alcohol-water reaction mixtures—by exposure to non-equilibrium cold atmospheric pressure Ar plasma (CAP), were monitored using electron paramagnetic resonance spin-trapping techniques with 3, 5-dibromo-4-nitrosobenzene sulfonate as a water soluble nitroso spin trap. The major radical species were formed by H-abstraction from alcohol molecules due to ·OH radicals. In the ethanol-water mixture ·CH2CH2OH produced by H abstraction from CH3 group of the ethanol and ·CH3 radicals were detected. The latter was due to the decomposition of unstable CH3·CHOH to form the ·CH3 radicals and the stable formaldehyde by C-C bond fission. These intermediates are similar to those observed by reaction with ·OH radicals generation in the H2O2-UV photolysis of the reaction mixtures. The evidence of ·CH3 radical formation in the pyrolytic decomposition of the reaction mixtures by exposure to ultrasound or in methane irradiated with microwave plasma have been reported previously. However, the pyrolytic ·CH3 radicals were not found in both plasma and H2O2-UV photolysis condition. These results suggests that free radicals produced by Ar-CAP are most likely due to the reaction between abundant ·OH radicals and alcohol molecules.

Final programmatic environmental impact statement for the uranium mill tailings remedial action ground water project. Volume I

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

None

1996-10-01

This programmatic environmental impact statement (PElS) was prepared for the Uranium Mill Tailings Remedial Action (UMTRA) Ground Water Project to comply with the National Environmental Policy Act (NEPA). This PElS provides an analysis of the potential impacts of the alternatives and ground water compliance strategies as well as potential cumulative impacts. On November 8, 1978, Congress enacted the Uranium Mill Tailings Radiation Control Act (UMTRCA) of 1978, Public Law, codified at 42 USC §7901 et seq. Congress found that uranium mill tailings " ... may pose a potential and significant radiation health hazard to the public, and that every reasonablemore » effort should be made to provide for stabilization, disposal, and control in a safe, and environmentally sound manner of such tailings in order to prevent or minimize other environmental hazards from such tailings." Congress authorized the Secretary of Energy to designate inactive uranium processing sites for remedial action by the U.S. Department of Energy (DOE). Congress also directed the U.S. Environmental Protection Agency (EPA) to set the standards to be followed by the DOE for this process of stabilization, disposal, and control. On January 5, 1983, EPA published standards (40 CFR Part 192) for the disposal and cleanup of residual radioactive materials. On September 3, 1985, the U.S. Court of Appeals for the Tenth Circuit set aside and remanded to EPA the ground water provisions of the standards. The EPA proposed new standards to replace remanded sections and changed other sections of 40 CFR Part 192. These proposed standards were published in the Federal Register on September 24, 1987 (52 FR 36000). Section 108 of the UMTRCA requires that DOE comply with EPA's proposed standards in the absence of final standards. The Ground Water Project was planned under the proposed standards. On January 11, 1995, EPA published the final rule, with which the DOE must now comply. The PElS and the Ground Water Project

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.

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.

Hydraulic Fracturing for Oil and Gas: Impacts from the Hydraulic Fracturing Water Cycle on Drinking Water Resources in the United States (Final Report)

EPA Science Inventory

This final report provides a review and synthesis of available scientific information concerning the relationship between hydraulic fracturing activities and drinking water resources in the United States.

The report is organized around activities in the hydraulic...

Ozone and photocatalytic processes to remove the antibiotic sulfamethoxazole from water.

PubMed

Beltrán, Fernando J; Aguinaco, Almudena; García-Araya, Juan F; Oropesa, Ana

2008-08-01

In this study, water containing the pharmaceutical compound sulfamethoxazole (SMT) was subjected to the various treatments of different oxidation processes involving ozonation, and photolysis and catalysis under different experimental conditions. Removal rates of SMT and total organic carbon (TOC), from experiments of simple UVA radiation, ozonation (O(3)), catalytic ozonation (O(3)/TiO(2)), ozone photolysis (O(3)/UVA), photocatalytic oxidation (O(2)/TiO(2)/UVA) and photocatalytic ozonation (O(3)/UVA/TiO(2)), have been compared. Photocatalytic ozonation leads to the highest SMT removal rate (pH 7 in buffered systems, complete removal is achieved in less than 5min) and total organic carbon (in unbuffered systems, with initial pH=4, 93% TOC removal is reached). Also, lowest ozone consumption per TOC removed and toxicity was achieved with the O(3)/UVA/TiO(2) process. Direct ozone and free radical reactions were found to be the principal mechanisms for SMT and TOC removal, respectively. In photocatalytic ozonation, with buffered (pH 7) aqueous solutions phosphates (buffering salts) and accumulation of bicarbonate scavengers inhibit the reactions completely on the TiO(2) surface. As a consequence, TOC removal diminishes. In all cases, hydrogen peroxide plays a key role in TOC mineralization. According to the results obtained in this work the use of photocatalytic ozonation is recommended to achieve a high mineralization degree of water containing SMT type compounds.

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

PubMed

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

2014-10-16

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

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Cost effective solar hot water system for Econo-Travel Motor Hotel, Chesapeake, Virginia. Final report

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

Not Available

1978-12-01

The final report of a cost effective solar hot water heating system installed on the Econo-Travel Motor Hotel at 4725 W. Military Highway, Chesapeake, Virginia, is presented. The description of the system along with the final breakdown performance data and payback time are given. The payback time for the installed system will be approximately four (4) years instead of the 6.65 years estimated for the proposal. The additional savings is due to the reduction in the peak demand charge since the electric hot water heaters are not required to operate at the same time each morning as the dryers usedmore » for the laundry. As called for in the proposal to DOE, the success of the system will be determined by the reduction in the utility cost and reduced use of our fossil fuels. The results shown in the hotel's monthly electricity bills indicate that this goal has been accomplished.« less

Photodegradation behaviour of sethoxydim and its comercial formulation Poast® under environmentally-relevant conditions in aqueous media. Study of photoproducts and their toxicity.

PubMed

Sevilla-Morán, Beatriz; Calvo, Luisa; López-Goti, Carmen; Alonso-Prados, José L; Sandín-España, Pilar

2017-02-01

Photolysis is an important route for the abiotic degradation of many pesticides. However, the knowledge of the photolytic behaviour of these compounds and their commercial formulations under environmentally-relevant conditions are limited. The present study investigated the importance of photochemical processes on the persistence and fate of the herbicide sethoxydim and its commercial formulation Poast ® in aqueous media. Moreover, the effect of important natural water substances (nitrate, calcium, and ferric ions) on the photolysis of the herbicide was also studied. The results showed that additives existing in the commercial formulation Poast ® accelerated the rate of photolysis of sethoxydim by a factor of 3. On the contrary, the presence of nitrate and calcium ions had no effect on the photodegradation rate while ferric ions resulted in an important decrease in the half-life of sethoxydim possibly due to the formation of a complex. Different transformation products were identified in the course of sethoxydim irradiation and the effect of experimental conditions on their concentrations was investigated. Finally, Microtox ® test revealed that aqueous solutions of sethoxydim photoproducts increased the toxicity to the bacteria Vibrio fischeri. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pulsed laser photolysis study of the reaction between O(3P) and HO2

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.; Nicovich, J. M.

1983-01-01

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

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.

Solar photolysis of soluble microbial products as precursors of disinfection by-products in surface water.

PubMed

Wu, Jie; Ye, Jian; Peng, Huanlong; Wu, Meirou; Shi, Weiwei; Liang, Yongmei; Liu, Wei

2018-06-01

In the Pearl River Delta area, the upstream municipal wastewater is commonly discharged into rivers which are a pivotal source of downstream drinking water. Solar irradiation transforms some of the dissolved organic matter discharged from the wastewater, also affecting the formation of disinfection by-products in subsequent drinking water treatment plants. The effect of simulated solar radiation on soluble microbial products extracted from activated sludge was documented in laboratory experiments. Irradiation was found to degrade macromolecules in the effluent, yielding smaller, more reactive intermediate species which reacted with chlorine or chloramine to form higher levels of noxious disinfection by-products. The soluble microbial products were found to be more active in formation of disinfection by-products regard than naturally-occurring organic matter. The results show that solar irradiation induced the formation of more trihalomethane (THMs), chloral hydrate (CH) and trichloronitromethane (TCNM), causing greater health risks for downstream drinking water. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metabolism of niclosamide in sediment and water systems

USGS Publications Warehouse

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

2004-01-01

A series of experiments analyzed the kinetics and mechanisms of [ 14C]niclosamide degradation. The aerobic aquatic metabolism of [ 14C]niclosamide was studied in nonsterile river water/sediment mixtures. Test systems, maintained under aerobic conditions, were treated with niclosamide and incubated in the dark at 25.0 ?? 1.0 ??C for 30 days. Half-lives of 4.9 and 5.4 days were calculated for the chlorosalicylic acid- and chloronitroaniline-labeled test systems, respectively. From 0 to 21 days after treatment (DAT), the only metabolism product observed in either test system was aminoniclosamide. At the final sampling interval, five peaks were resolved from the chlorosalicylic acid label, and three peaks were resolved from the chloronitroaniline label test substance. By 30 DAT, sediment-bound residues represented ???70% of the observed radioactivity. For the anaerobic aquatic metabolism of [14C]niclosamide, test systems were incubated under anaerobic conditions for 365 days. Half-lives of 0.65 day for the chlorosalicylic acid label and 2.79 days for the chloronitroaniline label were calculated. From 0 to 3 DAT, niclosamide was first transformed into aminoniclosamide. Aminoniclosamide is readily formed, as it was observed in the chlorosalicylic acid label 0 DAT sampling. Several minor metabolites were observed in the water and sediment extracts. None of these metabolites were formed to a significant amount until the parent niclosamide dissipated below the detection limit. Two of the byproducts from these metabolism studies are polar unknowns eluting at 3 and 5 min by HPLC, similar to the unknowns observed in aqueous photolysis studies.

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

1993-01-01

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

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.

Water-soluble resist for environmentally friendly lithography

NASA Astrophysics Data System (ADS)

Lin, Qinghuang; Simpson, Logan L.; Steinhaeusler, Thomas; Wilder, Michelle; Willson, C. Grant; Havard, Jennifer M.; Frechet, Jean M. J.

1996-05-01

This paper describes an 'environmentally friendly,' water castable, water developable photoresist system. The chemically amplified negative-tone resist system consists of three water-soluble components: a polymer, poly(methyl acrylamidoglycolate methyl ether), [poly(MAGME)]; a photoacid generator, dimethyl dihydroxyphenylsulfonium triflate and a crosslinker, butanediol. Poly(MAGME) was synthesized by solution free radical polymerization. In the three-component resist system, the acid generated by photolysis of the photoacid generator catalyzes the crosslinking of poly(MAGME) in the exposed regions during post-exposure baking, thus rendering the exposed regions insoluble in water. Negative tone relief images are obtained by developing with pure water. The resist is able to resolve 1 micrometer line/space features (1:1 aspect ratio) with an exposure dose of 100 mJ/cm2 at 248 nm. The resist can be used to generate etched copper relief images on printed circuit boards using aqueous sodium persulfate as the etchant. The crosslinking mechanism has been investigated by model compound studies using 13C NMR. These studies have revealed that the acid catalyzed reaction of the poly(MAGME) with butanediol proceeds via both transesterification and transacetalization (transaminalization) reactions at low temperatures, and also via transamidation at high temperatures.

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.

75 FR 43160 - Clean Water Act Section 303(d): Final Agency Action on One Arkansas Total Maximum Daily Load (TMDL)

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-23

... ENVIRONMENTAL PROTECTION AGENCY [FRL-9179-3 ] Clean Water Act Section 303(d): Final Agency Action on One Arkansas Total Maximum Daily Load (TMDL) AGENCY: Environmental Protection Agency (EPA). ACTION: Notice of availability. SUMMARY: This notice announces the final agency action on one TMDL established by...

Final report of the SIM.QM-S8 supplementary comparison, trace metals in drinking water

NASA Astrophysics Data System (ADS)

Yang, Lu; Nadeau, Kenny; Gedara Pihillagawa, Indu; Meija, Juris; Mester, Zoltan; Napoli, Romina; Pérez Zambra, Ramiro; Ferreira, Elizabeth; Alejandro Ahumada Forigua, Diego; Abella Gamba, Johanna Paola

2018-01-01

After completing a supplementary comparison SIM.QM-S7, the National Metrology Institute of Colombia (NMIC) requested to National Research Council of Canada (NRC) a subsequent bilateral comparison, because INMC considered that its results in SIM.QM-S7 unrepresentative of its standards. In this context, NRC agreed to coordinate this bilateral comparison with the aim of demonstrating the measurement capabilities of trace elements in fresh water. Participants included NMIC and LATU. No measurement method was prescribed by the coordinating laboratory. Therefore, NMIs used measurement methods of their choice. However, the majority of NMIs/DIs used ICP-MS. This SIM.QM-S8 Supplementary Comparison provides NMIs with the needed evidence for CMC claims for trace elements in fresh waters and similar matrices. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Water Recovery from Advanced Water Purification Facility Reverse Osmosis Concentrate by Photobiological Treatment Followed by Secondary Reverse Osmosis.

PubMed

Ikehata, Keisuke; Zhao, Yuanyuan; Kulkarni, Harshad; Li, Yuan; Snyder, Shane A; Ishida, Kenneth P; Anderson, Michael A

2018-06-19

Reverse osmosis (RO)-based desalination and advanced water purification facilities have inherent challenges associated with concentrate management and disposal. Although enhanced permeate recovery and concentrate minimization are desired, membrane scaling due to inorganic constituents such as silica, calcium, phosphate, and iron hinders the process. To solve this problem, a new diatom-based photobiological process has been developed to remove these scaling constituents by biological uptake and precipitation. In this study, RO concentrate samples were collected from a full-scale advanced water reclamation facility in California and were treated in 3.8- and 57-L photobioreactors inoculated with a brackish water diatom Pseudostaurosira trainorii PEWL001 using light-emitting diode bulbs or natural sunlight as a light source. The photobiological treatment removed 95% of reactive silica and 64% of calcium and enabled additional water recovery using a secondary RO at a recovery rate up to 66%. This represents 95% overall recovery including 85% recovery in the primary RO unit. In addition to the scaling constituents, the photobiological treatment removed twelve pharmaceuticals and personal care products, as well as N-nitrosodimethylamine, from RO concentrate samples primarily via photolysis. This novel approach has a strong potential for application to brackish water desalination and advanced water purification in arid and semi-arid areas.

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.

Carbon dioxide photolysis from 150 to 210 nm: singlet and triplet channel dynamics, UV-spectrum, and isotope effects.

PubMed

Schmidt, Johan A; Johnson, Matthew S; Schinke, Reinhard

2013-10-29

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ~167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ~0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues ((12)C(16)O2, (12)C(17)O(16)O, (12)C(18)O(16)O, (13)C(16)O2, and (13)C(18)O(16)O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of (17)O containing CO2 more efficient.

Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects

PubMed Central

Schmidt, Johan A.; Johnson, Matthew S.; Schinke, Reinhard

2013-01-01

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ∼167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ∼0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues (12C16O2, 12C17O16O, 12C18O16O, 13C16O2, and 13C18O16O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of 17O containing CO2 more efficient. PMID:23776249

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

Water pulsejet research. Final report

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

Payne, P.R.; Brown, R.G.; Brown, J.P.

1979-04-01

The steam water pulsejet (SWPJ) - a modern derivative of the Piot-McHugh putt-putt toy boat - is discussed. Studies have revealed that, like its air-breathing relatives, one type of SWPJ is a type of wave engine. This report first reviews the background literature and then summarizes recent improvements in our understanding of the engine's operation. An appendix attempts to show the various physical processes of the wave engine version in a quantifiable way. At low temperatures, the ideal cycle efficiency of this version is almost identical with the Carnot limit, diverging above a ..delta..T approx. = 150/sup 0/F. Maximum idealmore » cycle efficiency occurs in the 500/sup 0/-600/sup 0/F range, and is 30%-40%. In addition to the two wave engines (simple wave engine, and a wave engine with a water trap), the boundary layer boiler was developed which may but need not involve wave effects and the Piot-cycle. In the latter engine, some water is flashed rapidly to steam in a separate (but connected) compartment and reaches high pressure before the water column (because of its inertia) has moved appreciably. Ideal efficiencies for this cycle can be of the order of 10%-20%. Although a great deal of knowledge was gained, the present program was unsuccessful in applying the newly discovered cycles to build reliable and efficient solar powered pumps.« less

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.

[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.

Polycyclic Aromatic Hydrocarbon Ionization Energy Lowering in Water Ices

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.; Allamandola, Louis J.

2004-01-01

In studying various interstellar and solar system ice analogs, we have recently found that upon vacuum ultraviolet photolysis, polycyclic aromatic hydrocarbons (PAHs) frozen in water ice at low temperatures are easily ionized and indefinitely stabilized as trapped ions (Gudipati; Gudipati & Allamandola). Here we report the first experimental study that shows that PAH ionization energy is significantly lowered in PAH/H2O ices, in agreement with recent theoretical work (Woon & Park). The ionization energy (IE) of the PAH studied here, quaterrylene (C40H20, IE = 6.11 eV), is lowered by up to 2.11 eV in water ice. PAH ionization energy reduction in low-temperature water ice substantially expands the astronomical regions in which trapped ions and electrons may be important. This reduction in ionization energy should also hold for other types of trapped species in waterrich interstellar, circumstellar, and solar system ices. Subject headings: ISM: clouds - methods: laboratory - molecular processes - radiation mechanisms: nonthermal -ultraviolet: ISM - ultraviolet: solar system

75 FR 17917 - Clean Water Act Section 303(d): Final Agency Action on Seven Total Maximum Daily Loads (TMDLs) in...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-08

... ENVIRONMENTAL PROTECTION AGENCY [FRL-9135-1] Clean Water Act Section 303(d): Final Agency Action... the Clean Water Act (CWA). Documents from the administrative record file for the seven TMDLs... Oxygen. 010401 East Atchafalaya Mercury. Basin and Morganza Floodway South to Interstate 10 Canal. 010501...

KEY COMPARISON: Final Report on CCT-K7: Key comparison of water triple point cells

NASA Astrophysics Data System (ADS)

Stock, M.; Solve, S.; del Campo, D.; Chimenti, V.; Méndez-Lango, E.; Liedberg, H.; Steur, P. P. M.; Marcarino, P.; Dematteis, R.; Filipe, E.; Lobo, I.; Kang, K. H.; Gam, K. S.; Kim, Y.-G.; Renaot, E.; Bonnier, G.; Valin, M.; White, R.; Dransfield, T. D.; Duan, Y.; Xiaoke, Y.; Strouse, G.; Ballico, M.; Sukkar, D.; Arai, M.; Mans, A.; de Groot, M.; Kerkhof, O.; Rusby, R.; Gray, J.; Head, D.; Hill, K.; Tegeler, E.; Noatsch, U.; Duris, S.; Kho, H. Y.; Ugur, S.; Pokhodun, A.; Gerasimov, S. F.

2006-01-01

The triple point of water serves to define the kelvin, the unit of thermodynamic temperature, in the International System of Units (SI). Furthermore, it is the most important fixed point of the International Temperature Scale of 1990 (ITS-90). Any uncertainty in the realization of the triple point of water contributes directly to the measurement uncertainty over the wide temperature range from 13.8033 K to 1234.93 K. The Consultative Committee for Thermometry (CCT) decided at its 21st meeting in 2001 to carry out a comparison of water triple point cells and charged the BIPM with its organization. Water triple point cells from 20 national metrology institutes were carried to the BIPM and were compared with highest accuracy with two reference cells. The small day-to-day changes of the reference cells were determined by a least-squares technique. Prior to the measurements at the BIPM, the transfer cells were compared with the corresponding national references and therefore also allow comparison of the national references of the water triple point. This report presents the results of this comparison and gives detailed information about the measurements made at the BIPM and in the participating laboratories. It was found that the transfer cells show a standard deviation of 50 µK the difference between the extremes is 160 µK. The same spread is observed between the national references. The most important result of this work is that a correlation between the isotopic composition of the cell water and the triple point temperature was observed. To reduce the spread between different realizations, it is therefore proposed that the definition of the kelvin should refer to water of a specified isotopic composition. The CCT recommended to the International Committee of Weights and Measures (CIPM) to clarify the definition of the kelvin in the SI brochure by explicitly referring to water with the isotopic composition of Vienna Standard Mean Ocean Water (VSMOW). The CIPM

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

PubMed Central

Nkosi, Steven S; Mwakikunga, Bonex W; Sideras-Haddad, Elias; Forbes, Andrew

2012-01-01

Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III) acetylacetonate and Pt(II) acetylacetonate. Fe(II) and Pt(I) acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001) diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence. PMID:24198494

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.

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.

Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches.

PubMed

Hori, Hisao; Hayakawa, Etsuko; Einaga, Hisahiro; Kutsuna, Shuzo; Koike, Kazuhide; Ibusuki, Takashi; Kiatagawa, Hiroshi; Arakawa, Ryuichi

2004-11-15

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

RESPONSE PROTOCOL TOOLBOX: PLANNING FOR AND RESPONDING TO DRINKING WATER CONTAMINATION THREATS AND INCIDENTS. OVERVIEW AND APPLICATION. INTERIM FINAL - DECEMBER 2003

EPA Science Inventory

The interim final Response Protocol Toolbox: Planning for and Responding to Contamination Threats to Drinking Water Systems is designed to help the water sector effectively and appropriately respond to intentional contamination threats and incidents. It was produced by EPA, buil...

Cost effective solar hot water system for Econo-Travel Motor Hotel located at Richmond, Virginia. Final report

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

Not Available

1979-09-01

The final report is presented of a cost effective solar hot water heating system installed on the Econo-Travel Motor Hotel at 5408 Williamsburg Road, Richmond, Virginia. The description of the system is given along with the final cost breakdown, expected performance data and expected payback time for the installed system is estimated to be approximately five (5) years instead of the 6.65 years estimated for the proposal. The additional savings is due to the reduction in the peak demand charge since the electric hot water heaters are not required to operate at the same time each morning as the dryersmore » used for the laundry. The success of the system will be determined by the reduction in the utility cost and reduced use of our fossil fuels. The results shown in the hotel's monthly electricity bills indicate that this goal has been accomplished.« less

Phototransformation of the sunlight filter benzophenone-3 (2-hydroxy-4-methoxybenzophenone) under conditions relevant to surface waters.

PubMed

Vione, Davide; Caringella, Rosalinda; De Laurentiis, Elisa; Pazzi, Marco; Minero, Claudio

2013-10-01

The UV filter benzophenone-3 (BP3) has UV photolysis quantum yield ΦBP3=(3.1±0.3)·10(-5) and the following second-order reaction rate constants: with (•)OH, k(BP3,(•)OH)=(2.0±0.4)·10(10) M(-1) s(-1); with the triplet states of chromophoric dissolved organic matter ((3)CDOM*), K(BP3,(3)CDOM*)=(1.1±0.1)·10(9) M(-1) s(-1); with (1)O2, k(BP3,(1)O2)=(2.0±0.1)·10(5) M(-1) s(-1), and with CO3(-•), k(BP3,CO3(-•))<5·10(7) M(-1) s(-1). These data allow the modelling of BP3 photochemical transformation, which helps filling the knowledge gap about the environmental persistence of this compound. Under typical surface-water conditions, direct photolysis and reactions with (•)OH and (3)CDOM* would be the main processes of BP3 phototransformation. Reaction with (•)OH would prevail at low DOC, direct photolysis at intermediate DOC (around 5 mg C L(-1)), and reaction with (3)CDOM* at high DOC. If the reaction rate constant with CO3(-•) is near the upper limit of experimental measures (5·10(7) M(-1) s(-1)), the CO3(-•) degradation process could be somewhat important for DOC<1 mg C L(-1). The predicted half-life time of BP3 in surface waters under summertime conditions would be of some weeks, and it would increase with increasing depth and DOC. BP3 transformation intermediates were detected upon reaction with (•)OH. Two methylated derivatives were tentatively identified, and they were probably produced by reaction between BP3 and fragments arising from photodegradation. The other intermediates were benzoic acid (maximum concentration ~10% of initial BP3) and benzaldehyde (1%). Copyright © 2013 Elsevier B.V. All rights reserved.

Final report of the SIM.QM-S7 supplementary comparison, trace metals in drinking water

NASA Astrophysics Data System (ADS)

Yang, Lu; Nadeau, Kenny; Gedara Pihillagawa, Indu; Meija, Juris; Grinberg, Patricia; Mester, Zoltan; Valle Moya, Edith; Solís González, Faviola Alejandra; del Rocio Arvizu Torres, María; Yañez Muñoz, Oscar; Velina Lara-Manzano, Judith; Mazzitello, Gisela; Prina, Pedro; Acosta, Osvaldo; Napoli, Romina; Pérez Zambra, Ramiro; Ferreira, Elizabeth; Dobrovolskiy, Vladimir; Aprelev, Aleksei; Stakheev, Aleksei; Frolov, Dmitriy; Gusev, Leonid; Ivanova, Veronika; Näykki, Teemu; Sara-Aho, Timo; Venegas Padilla, Jimmy; Acuña Cubillo, Carlos; Bremmer, Dwyte; Freemantle, Ruel; Taebunpakul, Sutthinun; Tangpaisarnkul, Nongluck; Rodruangthum, Patumporn; Kaewkhomdee, Nattikarn; Thiengmanee, Usana; Tangjit, Tararat; Buzoianu, Mirella; Alejandro Ahumada Forigua, Diego; Abella Gamba, Johanna Paola; Alfredo Chavarro Medina, Luis; Sobina, Egor; Tabatchikova, Tatyana; Alexopoulos, Charalambos; Kakoulides, Elias; Delgado, Mabel; Flores, Liliana; Knox, Saira; Siewlal, Kester; Maharaj, Avinash

2018-01-01

SIM.QM-S7 was performed to assess the analytical capabilities of National Metrology Institutes (NMIs) and Designated Institutes (DIs) of SIM members (or other regions) for the accurate determination of trace metals in drinking water. The study was proposed by the coordinating laboratories National Research Council Canada (NRC) and Centro Nacional de Metrologia (CENAM) as an activity of Inorganic Analysis Working Group (IAWG) of Consultative Committee for Amount of Substance - Metrology in Chemistry and Biology (CCQM). Participants included 16 NMIs/DIs from 15 countries. No measurement method was prescribed by the coordinating laboratories. Therefore, NMIs used measurement methods of their choice. However, the majority of NMIs/DIs used ICP-MS. This SIM.QM-S7 Supplementary Comparison provides NMIs/DIs with the needed evidence for CMC claims for trace elements in fresh waters and similar matrices. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

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.

Ketamine and the metabolite norketamine: persistence and phototransformation toxicity in hospital wastewater and surface water.

PubMed

Lin, Angela Yu-Chen; Lee, Wan-Ning; Wang, Xiao-Huan

2014-04-15

Ketamine has been increasingly used both recreationally and medicinally around the world. Although the metabolic pathways to form its metabolite norketamine have been carefully investigated in humans and animals, knowledge of their environmental occurrence and fate is limited. In this study, we investigated the occurrence of ketamine and norketamine in 20 natural bodies of water, effluents from 13 hospitals, two wastewater treatment plants and one water supply plant. Ketamine was found at concentrations as high as 10 μg/L. Ketamine and norketamine were consistently found in similar concentrations (ketamine/norketamine ratio: 0.3-4.6) in the collected water samples, and this ratio similar to that found in urine samples. Dark incubation experiments have shown that ketamine is not susceptible to microbial degradation or hydrolysis. Phototransformation was demonstrated to significantly reduce the concentration of ketamine and norketamine in river waters (t(1/2) = 12.6 ± 0.4 and 10.1 ± 0.4 h, respectively) and resulted in byproducts that are similar to human metabolites. Both direct and indirect photolysis led to the N-demethylation of ketamine to form norketamine and other byproducts, including hydroxy-norketamine (HNK), dehydronorketamine (DNK), hydroxy-ketamine (HK) and isomer forms of ketamine and norketamine. Irradiated solutions exhibited higher toxicity (via the Microtox test). Although a final risk assessment could not be made due to a lack of studies on the chronic effects on aquatic organisms, the high and persistent environmental occurrences of ketamine and norketamine as well as the increasingly acute toxicity of the photo byproducts demonstrate the importance of including metabolites in evaluation of the overall risk of ketamine. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Cost effective solar hot water system for Econo-Travel Motor Hotel located at Woodbrdge, VA. Final report

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

Not Available

1978-11-01

The final report of a cost effective solar hot water heating system installed on the Econo-Travel Motor Hotel at 13317 Gordon Boulevard, Woodbridge, Virginia is given. The description of the system along with the final breakdown, performance data and payback time are given. The payback time for the installed system will be approximately four (4) years instead of the 7.2 years estimated for the proposal. The additional savings is due to the reduction in the peak demand charge since the electric hot water heaters are not required to operate at the same time each morning as the dryers used formore » the laundry. As called for in the proposal to DOE, the success of the system will be determined by the reduction in the utility cost and reduced use of our fossil fuels. The results shown in the hotel's monthly electricity bills indicate that this goal has been accomplished.« less

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.

Seasonal/Diurnal Mapping of Ozone and Water in the Martian Atmosphere

NASA Technical Reports Server (NTRS)

Novak, R. E.; Mumma, M. J.; DiSanti, M. A.; DelloRusso, N.; Magee-Sauer, K.; Bonev, B.

2003-01-01

Ozone and water are key species for understanding the stability and evolution of Mars atmosphere; they are closely linked (along with CO, H, OH, and O) through photochemistry. Photolysis of water produces the OH radical (thought to catalyze reformation of CO2 from CO and O2) and atomic hydrogen (which reacts with O3 forming OH and O2). Atomic hydrogen also reacts with O2 (forming HO2), thereby reducing the amount of O2 available to reform O3 from collisions between O and O2. Hence ozone and water should be anti-correlated on Mars. Photolysis of O3 produces O2(a(sup 1) delta g) with 90% efficiency, and the resulting emission band system near 1.27 mm traces the presence and abundance of ozone. This approach was initially used to study ozone on Earth and then applied to Mars. In 1997, we measured several lines of the O2(a(sup 1) delta g) emission using CSHELL at the NASA IRTF; the O2(a(sup 1) delta g) state is also quenched by collisions with CO2. This quenching dominates at lower altitudes so that the detected emissions are used to detect ozone column densities above 20 km. The slit was positioned N-S along Mars' central meridian resulting in a one-dimensional map of ozone. Nearly simultaneous maps may be made of water using CSHELL by detecting the v1 fundamental band of HDO near 3.67 microns and using the D/H ratio for Mars. This technique was used by DiSanti and Mumma. With CSHELL, measurements for both O2(a(sup 1) delta g) emissions and HDO absorptions can be made during the day or night. Since January, 1997, we have repeated these measurements at different times during the Martian year. For all of these dates, we have positioned the slit N-S along the central meridian; for some of these dates, we have also stepped the slit across the planet at 1 arc-sec intervals generating a 2-dimensional map. We have also positioned the slit E-W on Mars thus providing diurnal variations of ozone and water along the slit.

Hydroxo radicals, C-H activation, and Pt-C bond formation from 77 K photolysis of a platinum(IV) hydroxo complex.

PubMed

Wickramasinghe, Lasantha A; Sharp, Paul R

2014-11-17

Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

RESPONSE PROTOCOL TOOLBOX: PLANNING FOR AND RESPONDING TO DRINKING WATER CONTAMINATION THREATS AND INCIDENTS. MODULE 4: ANALYTICAL GUIDE. INTERIM FINAL - DECEMBER 2003

EPA Science Inventory

The interim final Response Protocol Toolbox: Planning for and Responding to Contamination Threats to Drinking Water Systems is designed to help the water sector effectively and appropriately respond to intentional contamination threats and incidents. It was produced by EPA, buil...

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

Connectivity of Streams and Wetlands to Downstream Waters: A Review and Synthesis of the Scientific Evidence (Final Report)

EPA Science Inventory

The U.S. Environmental Protection Agency's (USEPA) Office of Research and Development has finalized the report Connectivity of Streams and Wetlands to Downstream Waters: A Review and Synthesis of the Scientific Evidence. The report reviews more than 1,200 peer-reviewe...

Cost effective solar hot water system for Econo-Travel Motor Hotel located at Bluefield, West Virginia. Final report

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

Not Available

1979-07-01

The final report of a cost effective solar hot water heating system installed on the Econo-Travel Motor Hotel at 3400 Cumberland Road, Bluefield, West Virginia. The description of the system along with the final breakdown performance data and payback time are given. The payback time for the installed system will be approximately five (5) years instead of the 7.73 years estimated for the proposal. The additional savings is due to the reduction in the peak demand charge since the electric hot water heaters are not required to operate at the same time each morning as the dryers used for themore » laundry. The success of the system will be determined by the reduction in the utility cost and reduced use of our fossil fuels. The results shown in the hotel's monthly electricity bills indicate that this goal has been accomplished.« less

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.

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.

Hg-sensitized photolysis of diethylamine in the absence and presence of O/sub 2/ or N/sub 2/O

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

DeStefano, G.; Heicklen, J.

1986-09-11

The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O/sub 2/ or N/sub 2/O at room temperature. In the absence of foreign gases, the products were H/sub 2/, CH/sub 3/CH=NC/sub 2/H/sub 5/ and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and similarly ordered 0.02. Thus CH/sub 3/CHNHC/sub 2/H/sub 5/ radicals are produced exclusively and they are removed by self reaction: 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. DEA + CH/sub 3/CH=NC/sub 2/H/sub 5/ (4a) and 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. diamine III (4b), with k/sub 4a//k/sub 4b/ = 47.0 +/- 5.6. In the presence ofmore » O/sub 2/ the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH/sub 3/CH=NC/sub 2/H/sub 5/ as the exclusive product: (CH/sub 3/CHNHC/sub 2/H/sub 5/ + O/sub 2/ ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + HO/sub 2/ (5). The Hg-sensitized photolysis of N/sub 2/O gives O(/sup 3/P) atoms, which in the presence of DEA react to give the imine and (C/sub 2/H/sub 5/)/sub 2/NOH (DEHA) as products in concerted parallel steps: O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + H/sub 2/O (9a) and O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. (C/sub 2/H/sub 5/)/sub 2/NOH (9b), with k/sub 9a//k/sub 9b/ similarly ordered 9.5 +/- 1.7.« less

Spectroscopic signatures of ozone at the air–water interface and photochemistry implications

PubMed Central

Anglada, Josep M.; Martins-Costa, Marilia; Ruiz-López, Manuel F.; Francisco, Joseph S.

2014-01-01

First-principles simulations suggest that additional OH formation in the troposphere can result from ozone interactions with the surface of cloud droplets. Ozone exhibits an affinity for the air–water interface, which modifies its UV and visible light spectroscopic signatures and photolytic rate constant in the troposphere. Ozone cross sections on the red side of the Hartley band (290- to 350-nm region) and in the Chappuis band (450–700 nm) are increased due to electronic ozone–water interactions. This effect, combined with the potential contribution of the O3 + hν → O(3P) + O2(X3Σg−) photolytic channel at the interface, leads to an enhancement of the OH radical formation rate by four orders of magnitude. This finding suggests that clouds can influence the overall oxidizing capacity of the troposphere on a global scale by stimulating the production of OH radicals through ozone photolysis by UV and visible light at the air–water interface. PMID:25071195

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.

Holographic Photolysis for Multiple Cell Stimulation in Mouse Hippocampal Slices

PubMed Central

Papagiakoumou, Eirini; Ventalon, Cathie; Angulo, María Cecilia; Emiliani, Valentina

2010-01-01

Background Advanced light microscopy offers sensitive and non-invasive means to image neural activity and to control signaling with photolysable molecules and, recently, light-gated channels. These approaches require precise and yet flexible light excitation patterns. For synchronous stimulation of subsets of cells, they also require large excitation areas with millisecond and micrometric resolution. We have recently developed a new method for such optical control using a phase holographic modulation of optical wave-fronts, which minimizes power loss, enables rapid switching between excitation patterns, and allows a true 3D sculpting of the excitation volumes. In previous studies we have used holographic photololysis to control glutamate uncaging on single neuronal cells. Here, we extend the use of holographic photolysis for the excitation of multiple neurons and of glial cells. Methods/Principal Findings The system combines a liquid crystal device for holographic patterned photostimulation, high-resolution optical imaging, the HiLo microscopy, to define the stimulated regions and a conventional Ca2+ imaging system to detect neural activity. By means of electrophysiological recordings and calcium imaging in acute hippocampal slices, we show that the use of excitation patterns precisely tailored to the shape of multiple neuronal somata represents a very efficient way for the simultaneous excitation of a group of neurons. In addition, we demonstrate that fast shaped illumination patterns also induce reliable responses in single glial cells. Conclusions/Significance We show that the main advantage of holographic illumination is that it allows for an efficient excitation of multiple cells with a spatiotemporal resolution unachievable with other existing approaches. Although this paper focuses on the photoactivation of caged molecules, our approach will surely prove very efficient for other probes, such as light-gated channels, genetically encoded photoactivatable

Crystal structure of a photolysis product of vitamin B6: A pyridodihydrofuran-condensed skeleton compound of pyridoxal 5‧-phosphate

NASA Astrophysics Data System (ADS)

Aoki, Katsuyuki; Nakamura, Hideyuki; Hattori, Toshiaki; Hu, Ning-Hai; Onishi, Masayoshi

2017-11-01

An aqueous solution dissolving pyridoxal 5‧-phosphate (PLP) was exposed to sun-light at room temperature to yield a photolysis product, 4b,9b-dihydro-4b,9b-dihydroxy-1,6-dimethyl-4,9-bis(phosphonooxymethyl){pyrido[3‧,4‧:2,3]furo[4,5-b]}pyrido[4,3-d]furan (1), whose structure was crystallographically determined. The product 1 was found to be a novel C(sp3)-C(sp3) side-sharing pyridodihydrofuran-condensed skeleton compound with the two pyridodihydrofuran planes taking a 'V-shape'-like molecular configuration. Hydrogen bonding patterns of molecules of 1 in the crystal lattice are analyzed by the graph set approach. The most probable mechanism for the formation of 1 is described.

(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.

Final Determination - signed November 23, 1990

EPA Pesticide Factsheets

Final determination of the U.S. EPA’s Assistant Administrator for Water pursuant to section 404(c) of the Clean Water Act concerning the Two Forks water supply impoundments in Jefferson and Douglas counties, Colorado.

Final Determination - signed March 1, 1990

EPA Pesticide Factsheets

Final Determination of the U.S. Environmental Protection Agency's Assistant Administrator for Water pursuant to Section 404(c) of the Clean Water Act concerning the proposed Big River water supply impoundment in Kent county, RI.

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.

Solar heating and domestic hot water system installed at Kansas City, Fire Station, Kansas City, Missouri. Final report

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

None

1980-07-01

This document is the final report of the solar energy heating and hot water system installed at the Kansas City Fire Station, Number 24, 2309 Hardesty Street, Kansas City, Missouri. The solar system was designed to provide 47 percent of the space heating, 8800 square feet area and 75 percent of the domestic hot water (DHW) load. The solar system consists of 2808 square feet of Solaron, model 2001, air, flat plate collector subsystem, a concrete box storage subsystem which contains 1428 cubic feet of 1/2 inch diameter pebbles weighing 71 1/2 tons, a DHW preheat tank, blowers, pumps, heatmore » exchangers, air ducting, controls and associated plumbing. Two 120-gallon electric DHW heaters supply domestic hot water which is preheated by the solar system. Auxiliary space heating is provided by three electric heat pumps with electric resistance heaters and four 30-kilowatt electric unit heaters. There are six modes of system operation. This project is part of the Department of Energy PON-1 Solar Demonstration Program with DOE cost sharing $154,282 of the $174,372 solar system cost. The Final Design Review was held March 1977, the system became operational March 1979 and acceptance test was completed in September 1979.« less

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.

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

Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride

NASA Astrophysics Data System (ADS)

Thomson, Robert K.; Cantat, Thibault; Scott, Brian L.; Morris, David E.; Batista, Enrique R.; Kiplinger, Jaqueline L.

2010-09-01

Uranium nitride [U≡N]x is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U≡N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U≡N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C6F5)3. These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.

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

PubMed

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

2016-03-15

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

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

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2014 CFR

2014-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2012 CFR

2012-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2013 CFR

2013-07-01

... test system has been designed that is buffered to maintain pH and is pre-aged in sunlight to produce, subsequently, a predictable bleaching behavior. (v) The purpose of Phase 1 is to prepare, pre-age, and dilute... reason, kpE, which contains kIE, is likewise valid only for the experimental data and latitude. (8) The...

The catalytic role of water in the photochemistry of ammonia ice: from diluted to concentrated phase

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Krim, Lahouari

2017-10-01

Using infrared spectroscopy as an in situ probe for reactions occurring in the solid phase, we investigated the influence of water molecules on the photochemistry of ammonia ices. Experiments were carried out in diluted and concentrated phases and between 3 and 130 K. We showed that the photolysis of NH3-H2O (2 per cent of H2O) ices using continuous radiation from 115 to 400 nm produces NH2OH as the main photoproduct, but also that such a photoinduced reaction strongly depends on both the initial ice temperature and the environment where the primary reactants NH3 and H2O are trapped. Our experimental results highlight the catalytic role played by H2O molecules in enhancing the formation yield of NH2 during the photolysis process through the NH3 + OH → NH2 + H2O hydrogen abstraction reaction, which is only favored at low temperatures in the range of 3-60 K. During heating of such irradiated ammonia-water ices, the amount of NH2OH keeps rising while that of NH2, is greatly reduced only from 70 K onwards. These behaviours are attributed to the competition that occurs between NH2 formation from the NH3 + OH reaction and its consumption from the NH2 + OH radical recombination. These results might explain the variable abundances of NH2 and NH3 provided by previous astronomical observations, where the NH2/NH3 ratio ranges from 0.02 to 0.5 depending on the regions of the interstellar medium that were analysed.

A radiative transfer module for calculating photolysis rates and solar heating in climate models: Solar-J v7.5

NASA Astrophysics Data System (ADS)

Hsu, Juno; Prather, Michael J.; Cameron-Smith, Philip; Veidenbaum, Alex; Nicolau, Alex

2017-07-01

Solar-J is a comprehensive radiative transfer model for the solar spectrum that addresses the needs of both solar heating and photochemistry in Earth system models. Solar-J is a spectral extension of Cloud-J, a standard in many chemical models that calculates photolysis rates in the 0.18-0.8 µm region. The Cloud-J core consists of an eight-stream scattering, plane-parallel radiative transfer solver with corrections for sphericity. Cloud-J uses cloud quadrature to accurately average over correlated cloud layers. It uses the scattering phase function of aerosols and clouds expanded to eighth order and thus avoids isotropic-equivalent approximations prevalent in most solar heating codes. The spectral extension from 0.8 to 12 µm enables calculation of both scattered and absorbed sunlight and thus aerosol direct radiative effects and heating rates throughout the Earth's atmosphere.The Solar-J extension adopts the correlated-k gas absorption bins, primarily water vapor, from the shortwave Rapid Radiative Transfer Model for general circulation model (GCM) applications (RRTMG-SW). Solar-J successfully matches RRTMG-SW's tropospheric heating profile in a clear-sky, aerosol-free, tropical atmosphere. We compare both codes in cloudy atmospheres with a liquid-water stratus cloud and an ice-crystal cirrus cloud. For the stratus cloud, both models use the same physical properties, and we find a systematic low bias of about 3 % in planetary albedo across all solar zenith angles caused by RRTMG-SW's two-stream scattering. Discrepancies with the cirrus cloud using any of RRTMG-SW's three different parameterizations are as large as about 20-40 % depending on the solar zenith angles and occur throughout the atmosphere.Effectively, Solar-J has combined the best components of RRTMG-SW and Cloud-J to build a high-fidelity module for the scattering and absorption of sunlight in the Earth's atmosphere, for which the three major components - wavelength integration, scattering, and

Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

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

Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

2012-05-17

Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less

Influence of DOM components, salinity, pH, nitrate, and bicarbonate on the indirect photodegradation of acetaminophen in simulated coastal waters.

PubMed

Bai, Ying; Cui, Zhengguo; Su, Rongguo; Qu, Keming

2018-04-18

The indirect photodegradation behaviors of acetaminophen (APAP) were investigated in the presence of four kinds of dissolved organic matter (DOM) and were also assessed in the presence of seawater components and conditions such as salinity, pH, nitrate and bicarbonate. The results showed three important findings: firstly, in the indirect photolysis of APAP, the contributions of 3 DOM*, ·OH and 1 O 2 were >85.0%, 2.3-9.9% and 0.8-2.6% at pH 8.0. Secondly, DOM was divided into four terrestrial humic-like components by Excitation-emission matrix spectroscopy (EEMs) combined with parallel factor analysis (PARAFAC). This study showed a good linearity between DOM fluorescence components and the indirect photodegradation of APAP (R 2  = 0.92) and the differences in photodegradation rates of APAP among various DOM solutions were due to the diverse compositions of DOM. Finally, salinity was an important factor influencing the removal of APAP, and the APAP photodegradation rate constants increased from (3.33 ± 0.07) × 10 -5 s -1 to (1.25 ± 0.05) × 10 -4 s -1 with increasing salinity. The increased pseudo-first-order rate constants for photolysis of APAP with increasing salinity, pH and nitrate were attributed to the enhanced generation of reactive intermediates (RI) and easier reactions between RI and APAP. The increased APAP removal rate constant with increasing bicarbonate was likely ascribed to the yield of ∙CO 3 - . This is the first report of the roles of DOM components and salinity on the indirect photolysis of APAP. These findings would be essential to predict the photochemical fate of APAP and would also allow for a better understanding of the environmental fate of other phenolic contaminants. Copyright © 2018 Elsevier Ltd. All rights reserved.

High-resolution simulations of the final assembly of Earth-like planets. 2. Water delivery and planetary habitability.

PubMed

Raymond, Sean N; Quinn, Thomas; Lunine, Jonathan I

2007-02-01

The water content and habitability of terrestrial planets are determined during their final assembly, from perhaps 100 1,000-km "planetary embryos " and a swarm of billions of 1-10-km "planetesimals. " During this process, we assume that water-rich material is accreted by terrestrial planets via impacts of water-rich bodies that originate in the outer asteroid region. We present analysis of water delivery and planetary habitability in five high-resolution simulations containing about 10 times more particles than in previous simulations. These simulations formed 15 terrestrial planets from 0.4 to 2.6 Earth masses, including five planets in the habitable zone. Every planet from each simulation accreted at least the Earth's current water budget; most accreted several times that amount (assuming no impact depletion). Each planet accreted at least five water-rich embryos and planetesimals from the past 2.5 astronomical units; most accreted 10-20 water-rich bodies. We present a new model for water delivery to terrestrial planets in dynamically calm systems, with low-eccentricity or low-mass giant planets-such systems may be very common in the Galaxy. We suggest that water is accreted in comparable amounts from a few planetary embryos in a " hit or miss " way and from millions of planetesimals in a statistically robust process. Variations in water content are likely to be caused by fluctuations in the number of water-rich embryos accreted, as well as from systematic effects, such as planetary mass and location, and giant planet properties.

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.

Femtosecond Photolysis of CO-Ligated Protoheme and Hemoproteins: Appearance of Deoxy Species with a 350-Fsec Time Constant

NASA Astrophysics Data System (ADS)

Martin, J. L.; Migus, A.; Poyart, C.; Lecarpentier, Y.; Astier, R.; Antonetti, A.

1983-01-01

Photolysis of HbCO, MbCO, and CO-protoheme has been investigated by measuring transient differential spectra and kinetics of induced absorption after excitation with a 250-fsec laser pulse at 307 nm. Probing was performed by a part of a continuum pulse between 395 and 445 nm. Photodissociation of the three liganded species occurred within the pulse duration. By contrast, the formation of deoxy species appeared with a mean (± SD) response time of 350± 50 fsec. This time constant was identical for the three species and independent of the presence or absence of the protein structure. Our results suggest the formation of a transient high-spin in plane iron (II) species which relaxes in 350 fsec to a high-spin stable state with concerted kinetics of CO departure and iron displacement. The spin transition is suspected to occur via liganded excited states which relax in part to nonreactive states with a 3,2-psec time constant.

The benzylperoxyl radical as a source of hydroxyl and phenyl radicals.

PubMed

Sander, Wolfram; Roy, Saonli; Bravo-Rodriguez, Kenny; Grote, Dirk; Sanchez-Garcia, Elsa

2014-09-26

The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O2 is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O-O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H2O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Homogeneous sonophotolysis of food processing industry wastewater: Study of synergistic effects, mineralization and toxicity removal.

PubMed

Durán, A; Monteagudo, J M; Sanmartín, I; Gómez, P

2013-03-01

The mineralization of industrial wastewater coming from food industry using an emerging homogeneous sonophotolytic oxidation process was evaluated as an alternative to or a rapid pretreatment step for conventional anaerobic digestion with the aim of considerably reducing the total treatment time. At the selected operation conditions ([H(2)O(2)]=11,750ppm, pH=8, amplitude=50%, pulse length (cycles)=1), 60% of TOC is removed after 60min and 98% after 180min when treating an industrial effluent with 2114ppm of total organic carbon (TOC). This process removed completely the toxicity generated during storing or due to intermediate compounds. An important synergistic effect between sonolysis and photolysis (H(2)O(2)/UV) was observed. Thus the sonophotolysis (ultrasound/H(2)O(2)/UV) technique significantly increases TOC removal when compared with each individual process. Finally, a preliminary economical analysis confirms that the sono-photolysis with H(2)O(2) and pretreated water is a profitable system when compared with the same process without using ultrasound waves and with no pretreatment. Copyright © 2012 Elsevier B.V. All rights reserved.

Final Determination - signed August 31, 2008

EPA Pesticide Factsheets

Final Determination of the U.S. EPA’s Assistant Administrator for Water pursuant to Section 404(c) of the Clean Water Act concerning the proposed Yazoo Backwater area pumps project, Issaquena county, Mississippi.

RESPONSE PROTOCOL TOOLBOX: PLANNING FOR AND RESPONDING TO DRINKING WATER CONTAMINATION THREATS AND INCIDENTS, MODULE 3: SITE CHARACTERIZATION AND SAMPLING GUIDE. INTERIM FINAL - DECEMBER 2003

EPA Science Inventory

The interim final Response Protocol Toolbox: Planning for and Responding to Contamination Threats to Drinking Water Systems is designed to help the water sector effectively and appropriately respond to intentional contamination threats and incidents. It was produced by EPA, buil...

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.

Field Water Balance of Landfill Final Covers

EPA Science Inventory

Landfill covers are critical to waste containment, yet field performance of specific cover designs has not been well documented and seldom been compared in side-by-side testing. A study was conducted to assess the ability of landfill final covers to control percolation into unde...

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.

Final Determination - signed March 21, 1988

EPA Pesticide Factsheets

Information about final determination of the U.S. EPA's Assistant Administrator for water, concerning wetlands owned by the Russo Development Corporation in Carlstadt, New Jersey pursuant to section 404(c) of the Clean Water Act.

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

PubMed

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

2015-03-15

In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3). Copyright © 2015 Elsevier Ltd. All rights reserved.

Ground water hydrology report: Revision 1, Attachment 3. Final

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

NONE

1996-12-01

This report presents ground water hydrogeologic activities for the Maybell, Colorado, Uranium Mill Tailings Remedial Action Project site. The Department of Energy has characterized the hydrogeology, water quality, and water resources at the site and determined that the proposed remedial action would comply with the requirements of the EPA ground water protection standards.

Use of saline water in energy development. Final report

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

Israelsen, C.E.; Adams, V.D.; Batty, J.C.

1980-06-01

Information was assembled relative to future energy-related projects in the upper basin, and estimates were made of their anticipated water needs. Using computer models, various options were tested for using saline water for coal-fired power plant cooling. Both cooling towers and brine evaporation ponds were included. Information is presented of several proven water treatment technologies, and comparisons are made of their cost effectiveness when placed in various combinations in the power plant makeup and blowdown water systems. A relative value scale was developed which compares graphically the relative values of waters of different salinities based on three different water treatmentmore » options and predetermined upper limits of cooling tower circulating salinities. Coal from several different mines was slurried in waters of different salinities. Samples were analyzed in the laboratory to determine which constituents had been leached from or absorbed by the coal, and what possible deleterious effects this might have on the burning properties of the coal, or on the water for culinary use or irrigation.« less

Hydrogen Migration and Vinylidene Pathway for Formation of Methane in the 193 nm Photodissociation of Propene: CH3CH=CH2 and CD3CD=CD2

NASA Technical Reports Server (NTRS)

Zhao, Yi-Lei; Laufer, Allan H.; Halpern, Joshua B.; Fahr, Askar

2007-01-01

Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.

Photodegradation routes of the herbicide bromoxynil in solution and sorbed on silica nanoparticles.

PubMed

Escalada, Juan P; Arce, Valeria B; Carlos, Luciano; Porcal, Gabriela V; Biasutti, M Alicia; Criado, Susana; García, Norman A; Mártire, Daniel O

2014-04-01

Some organic contaminants dissolved in natural waters tend to adsorb on suspended particles and sediments. In order to mimic the photodegradation routes in natural waters of bromoxynil (BXN) adsorbed on silica, we here prepare and characterize silica nanoparticles modified with BXN (NP-BXN). We measure the direct photolysis quantum yield of aqueous BXN at 307 nm (0.064 ± 0.001) and detect the formation of bromide ions as a reaction product. Under similar conditions the photolysis quantum yield of BXN bonded to NP-BXN is much lower (0.0021 ± 0.0004) and does not lead to formation of bromide ions. The rate constant of the reaction of NP-BXN with the excited triplet states of riboflavin, a molecule employed as a proxy of chromophore dissolved organic matter (DOM) was measured in laser flash-photolysis experiments. The rate constants for the overall (kt) and chemical interaction (kr) of singlet oxygen with NP-BXN were also measured. Kinetic computer simulations show that the relevance of the direct and indirect (through reactions with reactive species generated in photoinduced processes) photodegradation routes of BXN is very much affected by sorption on silica. Immobilization of the herbicide on the particles, on one hand, affects the photolysis mechanism and lowers its photolysis quantum yield. On the other hand, the results obtained in aqueous suspensions indicate that immobilization also lowers the rate of collisional encounter, which affects the quenching rate constants of excited triplet states and singlet oxygen with the herbicide.

Photocatalytic generation of hydrogen from water

NASA Technical Reports Server (NTRS)

Bottoms, W. R.; Miles, R. B.

1976-01-01

A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains

NASA Technical Reports Server (NTRS)

Ferris, J. P.

1986-01-01

With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.

A radiative transfer module for calculating photolysis rates and solar heating in climate models: Solar-J v7.5

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

Hsu, Juno; Prather, Michael J.; Cameron-Smith, Philip

Solar-J is a comprehensive radiative transfer model for the solar spectrum that addresses the needs of both solar heating and photochemistry in Earth system models. Solar-J is a spectral extension of Cloud-J, a standard in many chemical models that calculates photolysis rates in the 0.18–0.8 µm region. The Cloud-J core consists of an eight-stream scattering, plane-parallel radiative transfer solver with corrections for sphericity. Cloud-J uses cloud quadrature to accurately average over correlated cloud layers. It uses the scattering phase function of aerosols and clouds expanded to eighth order and thus avoids isotropic-equivalent approximations prevalent in most solar heating codes. Themore » spectral extension from 0.8 to 12 µm enables calculation of both scattered and absorbed sunlight and thus aerosol direct radiative effects and heating rates throughout the Earth's atmosphere. Furthermore, the Solar-J extension adopts the correlated-k gas absorption bins, primarily water vapor, from the shortwave Rapid Radiative Transfer Model for general circulation model (GCM) applications (RRTMG-SW). Solar-J successfully matches RRTMG-SW's tropospheric heating profile in a clear-sky, aerosol-free, tropical atmosphere. Here, we compare both codes in cloudy atmospheres with a liquid-water stratus cloud and an ice-crystal cirrus cloud. For the stratus cloud, both models use the same physical properties, and we find a systematic low bias of about 3 % in planetary albedo across all solar zenith angles caused by RRTMG-SW's two-stream scattering. Discrepancies with the cirrus cloud using any of RRTMG-SW's three different parameterizations are as large as about 20–40 % depending on the solar zenith angles and occur throughout the atmosphere. Effectively, Solar-J has combined the best components of RRTMG-SW and Cloud-J to build a high-fidelity module for the scattering and absorption of sunlight in the Earth's atmosphere, for which the three major components – wavelength

A radiative transfer module for calculating photolysis rates and solar heating in climate models: Solar-J v7.5

DOE PAGES

Hsu, Juno; Prather, Michael J.; Cameron-Smith, Philip; ...

2017-01-01

Solar-J is a comprehensive radiative transfer model for the solar spectrum that addresses the needs of both solar heating and photochemistry in Earth system models. Solar-J is a spectral extension of Cloud-J, a standard in many chemical models that calculates photolysis rates in the 0.18–0.8 µm region. The Cloud-J core consists of an eight-stream scattering, plane-parallel radiative transfer solver with corrections for sphericity. Cloud-J uses cloud quadrature to accurately average over correlated cloud layers. It uses the scattering phase function of aerosols and clouds expanded to eighth order and thus avoids isotropic-equivalent approximations prevalent in most solar heating codes. Themore » spectral extension from 0.8 to 12 µm enables calculation of both scattered and absorbed sunlight and thus aerosol direct radiative effects and heating rates throughout the Earth's atmosphere. Furthermore, the Solar-J extension adopts the correlated-k gas absorption bins, primarily water vapor, from the shortwave Rapid Radiative Transfer Model for general circulation model (GCM) applications (RRTMG-SW). Solar-J successfully matches RRTMG-SW's tropospheric heating profile in a clear-sky, aerosol-free, tropical atmosphere. Here, we compare both codes in cloudy atmospheres with a liquid-water stratus cloud and an ice-crystal cirrus cloud. For the stratus cloud, both models use the same physical properties, and we find a systematic low bias of about 3 % in planetary albedo across all solar zenith angles caused by RRTMG-SW's two-stream scattering. Discrepancies with the cirrus cloud using any of RRTMG-SW's three different parameterizations are as large as about 20–40 % depending on the solar zenith angles and occur throughout the atmosphere. Effectively, Solar-J has combined the best components of RRTMG-SW and Cloud-J to build a high-fidelity module for the scattering and absorption of sunlight in the Earth's atmosphere, for which the three major components – wavelength

Separations on water-ice. Final report

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

Dasgupta, P.K.

1998-07-01

This report focuses on processes to separate water frozen into ice. Research topics include the following: normal phase columnar chromatography; electrophoresis in a planar format; and zone melting type separations on a solid column of ice. Attempts were made to dope the emulsion with {beta}-cyclodextrin in order to separate commercially important chiral drugs such as Inderal.

Photolysis of CH{sub 3}CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH{sub 3} and HCO radicals and H atoms

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

Morajkar, Pranay; Schoemaecker, Coralie; Fittschen, Christa, E-mail: christa.fittschen@univ-lille1.fr

2014-06-07

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH{sub 3}CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO{sub 2} radicals by reaction with O{sub 2}. The CH{sub 3} radical yield has been determined using the same technique following their conversion into CH{sub 3}O{sub 2}. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO{sub 2} profiles, obtained under various O{sub 2} concentrations, to a complex model, while the CH{submore » 3} yield has been determined relative to the CH{sub 3} yield from 248 nm photolysis of CH{sub 3}I. Time resolved HO{sub 2} profiles under very low O{sub 2} concentrations suggest that another unknown HO{sub 2} forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O{sub 2}. HO{sub 2} profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH{sub 3}CHO + hν{sub 248nm} → CH{sub 3}CHO{sup *}, CH{sub 3}CHO{sup *} → CH{sub 3} + HCO ϕ{sub 1a} = 0.125 ± 0.03, CH{sub 3}CHO{sup *} → CH{sub 3} + H + CO ϕ{sub 1e} = 0.205 ± 0.04, CH{sub 3}CHO{sup *}→{sup o{sub 2}}CH{sub 3}CO + HO{sub 2} ϕ{sub 1f} = 0.07 ± 0.01. The CH{sub 3}O{sub 2} quantum yield has been determined in separate experiments as ϕ{sub CH{sub 3}} = 0.33 ± 0.03 and is in excellent agreement with the CH{sub 3} yields derived from the HO{sub 2} measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH{sub 3}CHO. From arithmetic considerations taking into account the HO{sub 2} and CH{sub 3} measurements we deduce a remaining quantum yield for the molecular pathway: CH{sub 3}CHO{sup *} → CH{sub 4} + CO ϕ{sub 1b} = 0.6. All experiments

Trace Element Removal in Distributed Drinking Water Treatment Systems by Cathodic H2O2 Production and UV Photolysis

PubMed Central

2017-01-01

As water scarcity intensifies, point-of-use and point-of-entry treatment may provide a means of exploiting locally available water resources that are currently considered to be unsafe for human consumption. Among the different classes of drinking water contaminants, toxic trace elements (e.g., arsenic and lead) pose substantial operational challenges for distributed drinking water treatment systems. Removal of toxic trace elements via adsorption onto iron oxides is an inexpensive and robust treatment method; however, the presence of metal-complexing ligands associated with natural organic matter (NOM) often prevents the formation of iron precipitates at the relatively low concentrations of dissolved iron typically present in natural water sources, thereby requiring the addition of iron which complicates the treatment process and results in a need to dispose of relatively large amounts of accumulated solids. A point-of-use treatment device consisting of a cathodic cell that produced hydrogen peroxide (H2O2) followed by an ultraviolet (UV) irradiation chamber was used to decrease colloid stabilization and metal-complexing capacity of NOM present in groundwater. Exposure to UV light altered NOM, converting ∼6 μM of iron oxides into settable forms that removed between 0.5 and 1 μM of arsenic (As), lead (Pb), and copper (Cu) from solution via adsorption. After treatment, changes in NOM consistent with the loss of iron-complexing carboxylate ligands were observed, including decreases in UV absorbance and shifts in the molecular composition of NOM to higher H/C and lower O/C ratios. Chronoamperometric experiments conducted in synthetic groundwater revealed that the presence of Ca2+ and Mg2+ inhibited intramolecular charge-transfer within photoexcited NOM, leading to substantially increased removal of iron and trace elements. PMID:29240414

Trace Element Removal in Distributed Drinking Water Treatment Systems by Cathodic H2O2 Production and UV Photolysis.

PubMed

Barazesh, James M; Prasse, Carsten; Wenk, Jannis; Berg, Stephanie; Remucal, Christina K; Sedlak, David L

2018-01-02

As water scarcity intensifies, point-of-use and point-of-entry treatment may provide a means of exploiting locally available water resources that are currently considered to be unsafe for human consumption. Among the different classes of drinking water contaminants, toxic trace elements (e.g., arsenic and lead) pose substantial operational challenges for distributed drinking water treatment systems. Removal of toxic trace elements via adsorption onto iron oxides is an inexpensive and robust treatment method; however, the presence of metal-complexing ligands associated with natural organic matter (NOM) often prevents the formation of iron precipitates at the relatively low concentrations of dissolved iron typically present in natural water sources, thereby requiring the addition of iron which complicates the treatment process and results in a need to dispose of relatively large amounts of accumulated solids. A point-of-use treatment device consisting of a cathodic cell that produced hydrogen peroxide (H 2 O 2 ) followed by an ultraviolet (UV) irradiation chamber was used to decrease colloid stabilization and metal-complexing capacity of NOM present in groundwater. Exposure to UV light altered NOM, converting ∼6 μM of iron oxides into settable forms that removed between 0.5 and 1 μM of arsenic (As), lead (Pb), and copper (Cu) from solution via adsorption. After treatment, changes in NOM consistent with the loss of iron-complexing carboxylate ligands were observed, including decreases in UV absorbance and shifts in the molecular composition of NOM to higher H/C and lower O/C ratios. Chronoamperometric experiments conducted in synthetic groundwater revealed that the presence of Ca 2+ and Mg 2+ inhibited intramolecular charge-transfer within photoexcited NOM, leading to substantially increased removal of iron and trace elements.

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James H.; Considine, David B.; Platnick, Steven; Norris, Peter M.; Duncan, Bryan N.; Pierce, Robert B.; Chen, Gao; Yantosca, Robert M.

2009-01-01

Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest

Ecotoxicological effect of ketamine: Evidence of acute, chronic and photolysis toxicity to Daphnia magna.

PubMed

Li, Shih-Wei; Wang, Yu-Hsiang; Lin, Angela Yu-Chen

2017-09-01

Ketamine has been increasingly used in medicine and has the potential for abuse or illicit use around the world. Ketamine cannot be removed by conventional wastewater treatment plants. Although ketamine and its metabolite norketamine have been detected to a significant degree in effluents and aquatic environments, their ecotoxicity effects in aquatic organisms remain undefined. In this study, we investigated the acute toxicity of ketamine and its metabolite, along with the chronic reproductive toxicity of ketamine (5-100μg/L) to Daphnia magna. Multiple environmental scenarios were also evaluated, including drug mixtures and sunlight irradiation toxicity. Ketamine and norketamine caused acute toxicity to D. magna, with half lethal concentration (LC 50 ) values of 30.93 and 25.35mg/L, respectively, after 48h of exposure. Irradiated solutions of ketamine (20mg/L) significantly increased the mortality of D. magna; pre-irradiation durations up to 2h rapidly increased the death rate to 100%. A new photolysis byproduct (M.W. 241) of norketamine that accumulates during irradiation was identified for the first time. The relevant environmental concentration of ketamine produced significant reproductive toxicity effects in D. magna, as revealed by the reduction of the number of total live offspring by 33.6-49.8% (p < 0.05). The toxicity results indicate that the environmental hazardous risks of the relevant ketamine concentration cannot be ignored and warrant further examination. Copyright © 2017 Elsevier Inc. All rights reserved.

Photoinduced degradation of carbaryl in a wetland surface water.

PubMed

Miller, Penney L; Chin, Yu-Ping

2002-11-06

The photoinduced degradation of carbaryl (1-naphthyl-N-methyl carbamate) was studied in a wetland's surface water to examine the photochemical processes influencing its transformation. For this particular wetland water, at high pH, it was difficult to delineate the photolytic contribution to the overall degradation of carbaryl. At lower pH values, the extent of the degradation attributable to indirect pathways, that is, in the presence of naturally occurring photosensitizers, increased significantly. Moreover, the photoenhanced degradation at the lower pH values was found to be seasonally and spatially dependent. Analysis of water samples revealed two primary constituents responsible for the observed indirect photolytic processes: nitrate and dissolved natural organic matter (NOM). Nitrate in the wetland appears at high concentrations (> or =1 mM) seasonally after the application of fertilizers in the watershed and promotes contaminant destruction through the photochemical production of the hydroxyl radical (HO*). The extent of the observed indirect photolysis pathway appears to be dependent upon the concentration of nitrates and the presence of HO* scavengers such as dissolved NOM and carbonate alkalinity. Paradoxically, during low-nitrate events (<50 microM), NOM becomes the principal photosensitizer through either the production of HO*, direct energy transfer from the excited triplet state, and/or production of an unidentified transient species.

Elimination of disinfection byproduct formation potential in reclaimed water during solar light irradiation.

PubMed

Qian-Yuan, Wu; Chao, Li; Ye, Du; Wen-Long, Wang; Huang, Huang; Hong-Ying, Hu

2016-05-15

Ecological storage of reclaimed water in ponds and lakes is widely applied in water reuse. During reclaimed water storage, solar light can degrade pollutants and improve water quality. This study investigated the effects of solar light irradiation on the disinfection byproduct formation potential in reclaimed water, including haloacetonitriles (HANs), trichloronitromethane (TCNM), trihalomethanes (THMs), haloketones (HKs) and chloral hydrate (CH). Natural solar light significantly decreased the formation potential of HANs, TCNM, and HKs in reclaimed water, but had a limited effect on the formation potential of THMs and CH. Ultraviolet (UV) light in solar radiation played a dominant role in the decrease of the formation potential of HANs, TCNM and HKs. Among the disinfection byproducts, the removal kinetic constant of dichloroacetonitrile (DCAN) with irradiation dose was much larger than those for dichloropropanone (1,1-DCP), trichloropropanone (1,1,1-TCP) and TCNM. During solar irradiation, fluorescence spectra intensities of reclaimed water also decreased significantly. The removal of tyrosine (Tyr)-like and tryptophan (Trp)-like protein fluorescence spectra intensity volumes was correlated to the decrease in DCAN formation potential. Solar irradiation was demonstrated to degrade Trp, Tyr and their DCAN formation potential. The photolysis products of Trp after solar irradiation were detected as kynurenine and tryptamine, which had chloroform, CH and DCAN formation potential lower than those of Trp. Copyright © 2016. Published by Elsevier Ltd.

Hydride Conformers of the Nitrogenase FeMo-cofactor Two-Electron Reduced State E2(2H), Assigned Using Cryogenic Intra Electron Paramagnetic Resonance Cavity Photolysis.

PubMed

Lukoyanov, Dmitriy A; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2018-03-24

Early studies in which nitrogenase was freeze-trapped during enzymatic turnover revealed the presence of high-spin ( S = 3 / 2 ) electron paramagnetic resonance (EPR) signals from the active-site FeMo-cofactor (FeMo-co) in electron-reduced intermediates of the MoFe protein. Historically denoted as 1b and 1c, each of the signals is describable as a fictitious spin system, S' = 1 / 2 , with anisotropic g' tensor, 1b with g' = [4.21, 3.76, ?] and 1c with g' = [4.69, ∼3.20, ?]. A clear discrepancy between the magnetic properties of 1b and 1c and the kinetic analysis of their appearance during pre-steady-state turnover left their identities in doubt, however. We subsequently associated 1b with the state having accumulated 2[e - /H + ], denoted as E 2 (2H), and suggested that the reducing equivalents are stored on the catalytic FeMo-co cluster as an iron hydride, likely an [Fe-H-Fe] hydride bridge. Intra-EPR cavity photolysis (450 nm; temperature-independent from 4 to 12 K) of the E 2 (2H)/1b state now corroborates the identification of this state as storing two reducing equivalents as a hydride. Photolysis converts E 2 (2H)/1b to a state with the same EPR spectrum, and thus the same cofactor structure as pre-steady-state turnover 1c, but with a different active-site environment. Upon annealing of the photogenerated state at temperature T = 145 K, it relaxes back to E 2 (2H)/1b. This implies that the 1c signal comes from an E 2 (2H) hydride isomer of E 2 (2H)/1b that stores its two reducing equivalents either as a hydride bridge between a different pair of iron atoms or an Fe-H terminal hydride.

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.

Theoretical study on the photolysis mechanism of 2,3-diazabicyclo[2.2.2]oct-2-ene.

PubMed

Chen, Hui; Li, Shuhua

2005-09-28

A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state.

The effect of water on the solid state characteristics of pharmaceutical excipients: Molecular mechanisms, measurement techniques, and quality aspects of final dosage form

PubMed Central

Szakonyi, Gergely; Zelkó, Romána

2012-01-01

In this paper we give an overview about the interaction of water molecules with pharmaceutical excipients. Most of these excipients are amorphous or partially amorphous polymers and their characteristics are very sensitive to the water content. In the course of the manufacturing processes water sorption is possible, therefore in some cases it is important to strictly control the residual moisture content of a dosage form. There are several mechanisms of water sorption, like water is able to bind to polar groups of hygroscopic excipients and could also exist in the capillary system of amorphous excipients. Several techniques are available to characterise the states of water inside the materials and the effects of residual water on polymers. For this purpose water sorption measurements, differential scanning calorimetry and the Fourier-transform infrared spectroscopy are reviewed. The importance of water content and storage conditions of pharmaceuticals on the properties of the final dosage forms are also demonstrated with practical examples. PMID:23071956

Carbon and water footprint of pork supply chain in Catalonia: From feed to final products.

PubMed

Noya, Isabel; Aldea, Xavier; Gasol, Carles M; González-García, Sara; Amores, Maria José; Colón, Joan; Ponsá, Sergio; Roman, Isabel; Rubio, Miguel A; Casas, Eudald; Moreira, María Teresa; Boschmonart-Rives, Jesús

2016-04-15

A systematic tool to assess the Carbon Footprint (CF) and Water Footprint (WF) of pork production companies was developed and applied to representative Catalan companies. To do so, a cradle-to-gate environmental assessment was carried out by means of the LCA methodology, taking into account all the stages involved in the pork chain, from feed production to the processing of final products, ready for distribution. In this approach, the environmental results are reported based on eight different functional units (FUs) according to the main pork products obtained. With the aim of ensuring the reliability of the results and facilitating the comparison with other available reports, the Product Category Rules (PCR) for Catalan pork sector were also defined as a basis for calculations. The characterization results show fodder production as the main contributor to the global environmental burdens, with contributions higher than 76% regardless the environmental indicator or the life cycle stage considered, which is in agreement with other published data. In contrast, the results in terms of CF and WF lay above the range of values reported elsewhere. However, major discrepancies are mainly due to the differences in the co-products allocation criteria. In this sense, economic/physical allocation and/or system expansion have been mostly considered in literature. In contrast, no allocation was considered appropriate in this study, according to the characteristics of the industries and products under assessment; thus, the major impacts fall on the main product, which derives on comparatively higher environmental burdens. Finally, due to the relevance of fodder production in the overall impact assessment results, strategies to reduce greenhouse gases (GHG) emissions as well as water use associated to this stage were proposed in the pork supply chain. Copyright © 2016 Elsevier Ltd. All rights reserved.

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 the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

DOE PAGES

Yan, Danhua; Tao, Jing; Kisslinger, Kim; ...

2015-10-13

Here we develop a novel technique for preparing high quality Ti-doped hematite thin films for photoelectrochemical (PEC) water splitting, through sputtering deposition of metallic iron films from an iron target embedded with titanium (dopants) pellets, followed by a thermal oxidation step that turns the metal films into doped hematite. It is found that the hematite domain size can be tuned from ~10 nm to over 100 nm by adjusting the sputtering atmosphere from more oxidative to mostly inert. The better crystallinity at a larger domain size ensures excellent PEC water splitting performance, leading to record high photocurrent from pure planarmore » hematite thin films on FTO substrates. Titanium doping further enhances the PEC performance of hematite photoanodes. The photocurrent is improved by 50%, with a titanium dopant concentration as low as 0.5 atom%. As a result, it is also found that the role of the titanium dopant in improving the PEC performance is not apparently related to the films’ electrical conductivity which had been widely believed, but is more likely due to the passivation of surface defects by the titanium dopants.« less

HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION ...

EPA Pesticide Factsheets

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

Assessing the Salting-Out Behavior of 2,4-Dinitrobenzaldehyde and 2,6-Dinitrobenzaldehyde from Solubility Values in Pure Water and Seawater at Temperatures between (280 and 313) K

DTIC Science & Technology

2011-05-12

Dinitrobenzaldehyde from Solubility Values in Pure Water and Seawater at Temperatures between (280 and 313) K Dianne J. Luning Prak* and Daniel W. O’Sullivan...1998, 37, 25–31. (7) O’Sullivan, D. W.; Denzel, J. R.; Luning Prak, D. J. Photolysis of 2,4-Dinitrotoluene and 2,6-Dinitrotoluene in Seawater. Aquat...Solubility of Aromatic Compounds.Chemosphere 1984, 13, 881–888. (13) Luning Prak, D. J.; O’Sullivan, D. W. Solubility of 2,4-Dini- trotoluene and 2,4,6

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

PubMed

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

2015-01-01

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

A 2D Microphysical Analysis of Aerosol Nucleation in the Polar Winter Stratosphere: Implications for H2SO4 Photolysis and Nucleation Mechanisms

NASA Technical Reports Server (NTRS)

Mills, Michael J.; Toon, Owen B.; Mills, Michael J.; Solomon, Susan

1997-01-01

Each spring a layer of small particles forms between 20 and 30 km in the polar regions. Results are presented from a 2D microphysical model of sulfate aerosol, which provide the first self-consistent explanation of the observed "CN layer." Photochemical conversion of sulfuric acid to SO2 in the upper stratosphere and mesosphere is necessary for this layer to form. Recent laboratory measurements of H2SO4 and SO3 photolysis rates are consistent with such conversion, though an additional source of SO2 may be required. Nucleation throughout the polar winter extends the top of the aerosol layer to higher altitudes, despite strong downward transport of ambient air. This finding may be important to heterogeneous chemistry at the top of the aerosol layer in polar winter and spring.

Development of a membrane-based process for the treatment of oily waste waters. Final report, March 4, 1992--March 5, 1994

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

McCray, S.B.

1994-05-25

This is a final report from Bend Research, Inc., (BRI) to the U.S. Department of Energy (DOE) for work performed under Contract No. DE-AC22-92MT92005, titled {open_quotes}Development of a Membrane-Based Process for the Treatment of Oily Waste Waters.{close_quotes} This report covers the period from March 4, 1992, to March 5, 1994. The overall goal of this program was to develop an economical oily-water treatment system based on reverse osmosis (RO). The RO system would be used to (1) reduce oil production costs by reducing the volume of waste water that must be disposed of, (2) form the basis of a genericmore » waste-water treatment system that can easily be integrated into oil-field operations, especially at production facilities that are small or in remote locations; and (3) produce water clean enough to meet existing and anticipated environmental regulations. The specific focus of this program was the development of a hollow-fiber membrane module capable of treating oily waste waters.« less

Final report on APMP.T-K7 key comparison of water triple point cells

NASA Astrophysics Data System (ADS)

Tsai, S. F.; White, R.; Tamba, J.; Yamazawa, K.; Ho, M. K.; Tsui, C. M.; Zaid, G.; Achmadi, A.; Gam, K. S.; Othman, H.; Ali, N. M.; Yuan, K. H.; Shaochun, Y.; Liedberg, H.; Yaokulbodee, C.

2016-01-01

APMP.T-K7, was held from February 2008 to September 2009 to compare the national realizations of the water triple point among eleven NMIs. To reach the objective, each participating laboratory sent a transfer cell to CMS and stated a value for the temperature difference of the transfer cell, relative to the corresponding national standard, representing 273.16 K. CMS (Taiwan) organized the comparison, with the support from co-pilot institutes MSL (New Zealand) and NMIJ (Japan). The other eight participating laboratories included NMIA, SCL, KIM-LIPI, KRISS, NMIM/SIRIM, NMC, NMISA, and NIMT. This report presents the results of the TPW comparison, gives detailed information about the measurements made at the CMS and at the participating laboratories, and aims to link the results of APMP.T-K7 to CCT-K7. The results of this key comparison are also represented in the form of degrees of equivalence for the purposes of the MRA. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCT, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

An Integrated Water Treatment Technology Solution for Sustainable Water Resource Management in the Marcellus Shale

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

Matthew Bruff; Ned Godshall; Karen Evans

2011-04-30

This Final Scientific/ Technical Report submitted with respect to Project DE-FE0000833 titled 'An Integrated Water Treatment Technology Solution for Sustainable Water Resource Management in the Marcellus Shale' in support of final reporting requirements. This final report contains a compilation of previous reports with the most current data in order to produce one final complete document. The goal of this research was to provide an integrated approach aimed at addressing the increasing water resource challenges between natural gas production and other water stakeholders in shale gas basins. The objective was to demonstrate that the AltelaRain{reg_sign} technology could be successfully deployed inmore » the Marcellus Shale Basin to treat frac flow-back water. That objective has been successfully met.« less

Aquatic photochemistry of sulfamethazine: multivariate effects of main water constituents and mechanisms.

PubMed

Li, Yingjie; Liu, Xiangliang; Zhang, Biaojun; Zhao, Qun; Ning, Ping; Tian, Senlin

2018-03-01

The ubiquity of sulfonamides (SAs) in natural waters requires insight into their environmental fate for ecological risk assessment. Extensive studies focused on the effect of univariate water constituents on the photochemical fate of SAs, yet the multivariate effects of water constituents in environmentally relevant concentrations on SA photodegradation are poorly understood. Here, response surface methodology was employed to explore the integrative effects of main water constituents (dissolved organic matter (DOM), NO 3 - , HCO 3 - , Cu 2+ ) on the photodegradation of a representative SA (sulfamethazine). Results showed that besides single factors, interaction of factors also significantly impacted the photodegradation. Radical scavenging experiments indicated that triplet-excited DOM ( 3 DOM*) was responsible for the enhancing effect of DOM on the photodegradation. Additionally, DOM may also quench the 3 DOM*-mediated oxidation intermediate of sulfamethazine causing the inhibiting effect of DOM-DOM interaction. We also found that HCO 3 - was oxidized by triplet-excited sulfamethazine producing CO 3 ˙ - , and the high reactivity of CO 3 ˙ - with sulfamethazine (second-order rate constant 2.2 × 10 8 M -1 s -1 ) determined by laser flash photolysis revealed the enhancing photodegradation mechanism of HCO 3 - . This study is among the first attempts to probe the photodegradation of SAs considering the integrative effects of water constituents, which is important in accurate ecological risk assessment of organic pollutants in the aquatic environment.

Photolysis of water for H2 production with the use of biological and artificial catalysts

NASA Astrophysics Data System (ADS)

Hall, D. O.; Adams, M. W. W.; Morris, P.; Rao, K. K.

1980-02-01

An aqueous mixture of chloroplasts, hydrogenase and electron transfer catalyst on illumination liberates H2, the source of the H atoms being water. The rate and duration of H2 production from such a system depends on the stability of chloroplast and hydrogenase activities in light and oxygen. Both chloroplasts and hydrogenases can be stabilized to a certain degree by immobilization in gels or by incubation in bovine serum albumin. Natural electron carriers of hydrogenases are ferredoxin, cytochrome c3 and NAD. Viologen dyes and synthetic iron-sulphur particles (Jeevanu) can substitute for the biological carriers. Methyl viologen, photoreduced in the presence of chloroplasts, can liberate H2 in combination with Pt (Adam's catalyst). An aqueous solution of proflavine can be photoreduced in the presence of organic electron donors such as EDTA, cysteine, dithiothreitol, etc.; the reduced proflavine can subsequently liberate H2 with MV-Pt, MV-hydrogenase, ferredoxin-hydrogenase or cytochrome-hydrogenase systems.

The disinfection of drinking water. Final report

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

Not Available

The current status of theoretically possible methods for disinfecting drinking water is reviewed. The specific biocidal activity of each of the disinfectants is considered, as well as information (or lack of it) on the practical application and reliability of the methods.

10 CFR 430.49 - Finality of decision.

Code of Federal Regulations, 2014 CFR

2014-01-01

... Finality of decision. (a) A decision to prescribe a rule that a State energy conservation standard, water conservation standard (in the case of faucets, showerheads, water closets, and urinals) or other requirement... DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY CONSERVATION PROGRAM FOR CONSUMER PRODUCTS Petitions To...

10 CFR 430.49 - Finality of decision.

Code of Federal Regulations, 2013 CFR

2013-01-01

... DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY CONSERVATION PROGRAM FOR CONSUMER PRODUCTS Petitions To... Finality of decision. (a) A decision to prescribe a rule that a State energy conservation standard, water conservation standard (in the case of faucets, showerheads, water closets, and urinals) or other requirement...

10 CFR 430.49 - Finality of decision.

Code of Federal Regulations, 2012 CFR

2012-01-01

... DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY CONSERVATION PROGRAM FOR CONSUMER PRODUCTS Petitions To... Finality of decision. (a) A decision to prescribe a rule that a State energy conservation standard, water conservation standard (in the case of faucets, showerheads, water closets, and urinals) or other requirement...

10 CFR 430.49 - Finality of decision.

Code of Federal Regulations, 2010 CFR

2010-01-01

... DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY CONSERVATION PROGRAM FOR CONSUMER PRODUCTS Petitions To... Finality of decision. (a) A decision to prescribe a rule that a State energy conservation standard, water conservation standard (in the case of faucets, showerheads, water closets, and urinals) or other requirement...

10 CFR 430.49 - Finality of decision.

Code of Federal Regulations, 2011 CFR

2011-01-01

... DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY CONSERVATION PROGRAM FOR CONSUMER PRODUCTS Petitions To... Finality of decision. (a) A decision to prescribe a rule that a State energy conservation standard, water conservation standard (in the case of faucets, showerheads, water closets, and urinals) or other requirement...

Wasted water pressure and potential energy generation. A feasibility study of the hydroelectric potential in part of the domestic water system of Boulder, Colorado. Draft final

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

Stern, P.S.; Kiel, J.; Fey, L.

1980-11-01

Colorado Project/Tip's study of the feasibility of using the City of Boulder's domestic water system for the generation of electricity was funded by an Appropriate Technology Grant from the Department of Energy, Region VIII. It has looked at how the extreme pressure being generated in this gravity water system can be used for a beneficial use rather than the current practice of simply venting or releasing it to the atmosphere. Turbines or pumps are studied as the means of converting the wasted pressure into energy. A review of the water system showed that five potential sites exist for installations ofmore » turbines or pumps: Silver Lake, Kossler, Sunshine, Orodell and 6th and Canyon. Data on water flows, elevation differences, pressures and operating procedures were integrated into an optimized flow control strategy for operating the water system while gaining maximum potential for the generation of electricity. Water from the mountain watersheds would continue to flow into the Betasso Water Treatment Plant as now. However, flows from the Silver Lake Line would be made constant as possible on a daily basis with the Kossler Line supplying additional needs. Flows of treated water from the Betasso Plant would be split 85/15 into the Sunshine/Orodell Lines rather than the current 60/40 split. Using the optimized flow control strategy, the power available for each site can be calculated from the pressures experienced, or elevation differences. Turbines can then be selected which would be appropriate for each site. Finally, the cost of the installed turbine plus auxiliary equipment to connect it to a load can be calculated and related to the minimum price which would be necessary to allow the project to break even.« less

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

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

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.

Reducing the chlorine dioxide demand in final disinfection of drinking water treatment plants using activated carbon.

PubMed

Sorlini, Sabrina; Biasibetti, Michela; Collivignarelli, Maria Cristina; Crotti, Barbara Marianna

2015-01-01

Chlorine dioxide is one of the most widely employed chemicals in the disinfection process of a drinking water treatment plant (DWTP). The aim of this work was to evaluate the influence of the adsorption process with granular activated carbon (GAC) on the chlorine dioxide consumption in final oxidation/disinfection. A first series of tests was performed at the laboratory scale employing water samples collected at the outlet of the DWTP sand filter of Cremona (Italy). The adsorption process in batch conditions with seven different types of GAC was studied. A second series of tests was performed on water samples collected at the outlet of four GAC columns installed at the outlet of the DWTP sand filter. The results showed that the best chlorine dioxide demand (ClO2-D) reduction yields are equal to 60-80% and are achieved in the first 30 min after ClO2 addition, during the first 16 days of the column operation using a mineral, coal-based, mesoporous GAC. Therefore, this carbon removes organic compounds that are more rapidly reactive with ClO2. Moreover, a good correlation was found between the ClO2-D and UV absorbance at wavelength 254 nm using mineral carbons; therefore, the use of a mineral mesoporous GAC is an effective solution to control the high ClO2-D in the disinfection stage of a DWTP.

Photochemical defluorination of aqueous perfluorooctanoic acid (PFOA) by Fe(0)/GAC micro-electrolysis and VUV-Fenton photolysis.

PubMed

Zhang, Li-Hong; Cheng, Jian-Hua; You, Xia; Liang, Xiao-Yan; Hu, Yong-You

2016-07-01

Perfluorooctanoic acid (PFOA) is extremely persistent and bioaccumulative in the environment; thus, it is very urgent to investigate an effective and moderate technology to treat the pollution of PFOA. In this study, a process combined iron and granular activated carbon (Fe(0)/GAC) micro-electrolysis with VUV-Fenton system is employed for the remediation of PFOA. Approximately 50 % PFOA (10 mg L(-1)) could be efficiently defluorinated under the following conditions: pH 3.0, dosage of Fe 7.5 g L(-1), dosage of GAC 12.5 g L(-1), and concentration of H2O2 22.8 mmol L(-1). Meanwhile, during the process, evident defluorination was observed and the concentration of fluoride ion was eventually 3.23 mg L(-1). The intermediates including five shorter-chain perfluorinated carboxylic acids (PFCAs), i.e., C7, C6, C5, C4, and C3, were also analyzed by high-performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) and defluorination mechanisms of PFOA was proposed, which involved photochemical of OH·, direct photolysis (185-nm VUV), and photocatalytic degradation of PFOA in the presence of Fe(3+) (254-nm UV).

Columbia Plateau Basin and Fifteenmile Subbasin Water Rights Acquisitons; Oregon Water Trust Combined Work Plan, 2002-2003 Final Report.

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

Paulus, Fritz

2003-12-01

This is the Final Report submitted regarding Oregon Water Trust's Combined Work Plan for fiscal year 2003, with the contract period April 2002 to May 2003. Of this 12 month period, six month were spent concluding our work for the 2002 irrigation season and six months were spent preparing for the 2003 irrigation season. After this grant was completed, projects were finished with funding from the Columbia Basin Water Transactions Program. Many of the 2003 irrigation season successes began in the fall of 2002, when projects were researched and partnerships were developed. Trout Creek Ranch was one of the largemore » successes. During the 2003 irrigation season, 2.6 cfs was leased which led to a permanent instream transfer, protecting critical spawning habitat for summer steelhead in the Deschutes basin. Another success was the Walla Walla Lease Bank project. This project is an agreement between the OWT, the Walla Walla Irrigation District and 11 individual landowners. Through this single year lease, 7.9 cfs of water was legally protected in the Walla Walla River. The Vidando lease on Middle Fork John Day River was renewed for 2 more years, protecting 11.29 cfs. An innovative single year split-season lease was conducted with Voight on Standard Creek in the John Day basin to protect 4.93 cfs. Many other deals were conducted and the total was an impressive 50.43 cfs instream during 2003 and 9.39 cfs pending approval for the 2004 season. Included is a summary of the activities within the Fifteenmile subbasin and the Columbia Plateau basin by quarter and two tables. The summary of activities is broken down by objectives and quarters. The first summarizes the total cfs by type of lease or transfer. The second table lists all the projects by subbasin and provides project type, lease number, cfs, cost of acquisition, partners in the project and funding source.« less

75 FR 54871 - National Drinking Water Advisory Council's Climate Ready Water Utilities Working Group Meeting...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-09

... ENVIRONMENTAL PROTECTION AGENCY [FRL-9198-8] National Drinking Water Advisory Council's Climate... final in-person meeting of the Climate Ready Water Utilities (CRWU) Working Group of the National Drinking Water Advisory Council (NDWAC). The purpose of this meeting is to review and discuss final changes...

Water quality criteria for hexachloroethane: Final report

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

Davidson, K.A.; Hovatter, P.S.; Ross, R.H.

1988-03-01

The available data regarding the environmental fate, aquatic toxicity, and mammalian toxicity of hexachloroethane, which is used in military screening smokes, were reviewed. The USEPA guidelines were used to generate water quality criteria for the protection of aquatic life and its uses and of human health. 16 tabs.

Assessing the phototransformation of diclofenac, clofibric acid and naproxen in surface waters: Model predictions and comparison with field data.

PubMed

Avetta, Paola; Fabbri, Debora; Minella, Marco; Brigante, Marcello; Maurino, Valter; Minero, Claudio; Pazzi, Marco; Vione, Davide

2016-11-15

Phototransformation is important for the fate in surface waters of the pharmaceuticals diclofenac (DIC) and naproxen (NAP) and for clofibric acid (CLO), a metabolite of the drug clofibrate. The goal of this paper is to provide an overview of the prevailing photochemical processes, which these compounds undergo in the different conditions found in freshwater environments. The modelled photochemical half-life times of NAP and DIC range from a few days to some months, depending on water conditions (chemistry and depth) and on the season. The model indicates that direct photolysis is the dominant degradation pathway of DIC and NAP in sunlit surface waters, and potentially toxic cyclic amides were detected as intermediates of DIC direct phototransformation. With modelled half-life times in the month-year range, CLO is predicted to be more photostable than DIC or NAP and to be degraded mainly by reaction with the • OH radical and with the triplet states of chromophoric dissolved organic matter ( 3 CDOM*). The CLO intermediates arising from these processes and detected in this study (hydroquinone and 4-chlorophenol) are, respectively, a chronic toxicant to aquatic organisms and a possible carcinogen for humans. Hydroquinone is formed with only ∼5% yield upon CLO triplet-sensitised transformation, but it is highly toxic for algae and crustaceans. In contrast, the formation yield of 4-chlorophenol reaches ∼50% upon triplet sensitisation and ∼10% by · OH reaction. The comparison of model predictions with field data from a previous study yielded a very good agreement in the case of DIC and, when using 4-carboxybenzophenone as proxy for triplet sensitisation by CDOM, a good agreement was found for CLO as well. In the case of NAP, the comparison with field data suggests that its direct photolysis quantum yield approaches or even falls below the lower range of literature values. Copyright © 2016 Elsevier Ltd. All rights reserved.

Conservative and reactive solute transport in constructed wetlands

USGS Publications Warehouse

Keefe, Steffanie H.; Barber, Larry B.; Runkel, Robert L.; Ryan, Joseph N.; McKnight, Diane M.; Wass, Roland D.

2004-01-01

The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater‐dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first‐order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%).

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.

STABILITY OF CO{sub 2} ATMOSPHERES ON DESICCATED M DWARF EXOPLANETS

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

Gao, Peter; Hu, Renyu; Li, Cheng

2015-06-20

We investigate the chemical stability of CO{sub 2}-dominated atmospheres of desiccated M dwarf terrestrial exoplanets using a one-dimensional photochemical model. Around Sun-like stars, CO{sub 2} photolysis by Far-UV (FUV) radiation is balanced by recombination reactions that depend on water abundance. Planets orbiting M dwarf stars experience more FUV radiation, and could be depleted in water due to M dwarfs’ prolonged, high-luminosity pre-main sequences. We show that, for water-depleted M dwarf terrestrial planets, a catalytic cycle relying on H{sub 2}O{sub 2} photolysis can maintain a CO{sub 2} atmosphere. However, this cycle breaks down for atmospheric hydrogen mixing ratios <1 ppm, resultingmore » in ∼40% of the atmospheric CO{sub 2} being converted to CO and O{sub 2} on a timescale of 1 Myr. The increased O{sub 2} abundance leads to high O{sub 3} concentrations, the photolysis of which forms another CO{sub 2}-regenerating catalytic cycle. For atmospheres with <0.1 ppm hydrogen, CO{sub 2} is produced directly from the recombination of CO and O. These catalytic cycles place an upper limit of ∼50% on the amount of CO{sub 2} that can be destroyed via photolysis, which is enough to generate Earth-like abundances of (abiotic) O{sub 2} and O{sub 3}. The conditions that lead to such high oxygen levels could be widespread on planets in the habitable zones of M dwarfs. Discrimination between biological and abiotic O{sub 2} and O{sub 3} in this case can perhaps be accomplished by noting the lack of water features in the reflectance and emission spectra of these planets, which necessitates observations at wavelengths longer than 0.95 μm.« less

Water level determination for transportation projects : mean high water manual, final report, November 2009.

DOT National Transportation Integrated Search

2009-11-01

To ensure proficient network management and safe usage of navigable waterways especially in waters that are : subject to tides, it is essential that the height of the water at various tidal phases be known. This knowledge is also : essential for prop...

Ozonation and H2O2/UV treatment of clofibric acid in water: a kinetic investigation.

PubMed

Andreozzi, Roberto; Caprio, Vincenzo; Marotta, Raffaele; Radovnikovic, Anita

2003-10-31

The presence of pharmaceuticals or their active metabolites in surface and ground waters has been recently reported as mainly due to an incomplete removal of these pollutants in sewage treatment plants (STP). Advanced oxidation processes may represent a suitable tool to reduce environmental release of these species by enhancing the global efficiency of reduction of pharmaceuticals in the municipal sewage plant effluents. The present work aims at assessing the kinetics of abatement from aqueous solutions of clofibric acid (a metabolite of the blood lipid regulator clofibrate) which has been found in surface, ground and drinking waters. Ozonation and hydrogen peroxide photolysis are capable of fast removal of this species in aqueous solution, with an almost complete conversion of the organic chlorine content into chloride ions for the investigated reaction conditions. A validation of assessed kinetics at clofibric acid concentrations as low as those found in STP effluents is presented for both systems.

Water quality of selected streams in the coal area of southeastern Montana. Water-resources investigations (final)

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

Knapton, J.R.; McKinley, P.W.

1977-08-01

This report summarizes and evaluates water-quality data collected at 35 stream sites in the coal region of southeastern Montana. Sarpy Creek, Armells Creek, and Rosebud Creek sometimes have dissolved-solids concentrations that cause water to be marginal for agricultural purposes. At times of rainfall and snowmelt, the runoff water mixes with the base-flow component to improve the overall quality. Water in the Tongue River generally showed a downstream degradation in which some changes were related to the lithology of the aquifers contributing water to streamflow. Water from Pumpkin Creek and Mizpah Creek is used mostly for cattle watering. To some extentmore » water is used for irrigation although the salinity hazard was often high. The chemical quality of the Powder River changed little during flow downstream. High sediment loads of the river acted as transporting agents for many of the plant nutrients and trace-element constituents.« less

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

New insights into the environmental photochemistry of 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan): reconsidering the importance of indirect photoreactions.

PubMed

Bianco, Angelica; Fabbri, Debora; Minella, Marco; Brigante, Marcello; Mailhot, Gilles; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-04-01

Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) is a widely used antimicrobial agent that undergoes fairly slow biodegradation. It is often found in surface waters in both the acidic (HTric) and basic (Tric(-)) forms (pKa ∼8), and it can undergo direct photodegradation to produce several intermediates including a dioxin congener (2,8-dichlorodibenzodioxin, hereafter 28DCDD). The latter is formed from Tric(-) and causes non-negligible environmental concern. Differently from current literature reports, in this paper we show that the direct photolysis would not be the only important transformation pathway of triclosan in surface waters. This is particularly true for HTric, which could undergo very significant reactions with (•)OH and, if the laser-derived quenching rate constants of this work are comparable to the actual reaction rate constants, with the triplet states of chromophoric dissolved organic matter ((3)CDOM*). Model calculations suggest that reaction with (3)CDOM* could be the main HTric phototransformation pathway in deep waters with high dissolved organic carbon (DOC), while reaction with (•)OH could prevail in low-DOC waters. In the case of Tric(-) the direct photolysis is much more important than for HTric, but triplet-sensitised transformation could produce 28DCDD + 27DCDD with higher yield compared to the direct photolysis, and it could play some role as dioxin source in deep waters with elevated DOC. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fate and Transport of Mercury in Environmental Media and Human Exposure

PubMed Central

Kim, Moon-Kyung

2012-01-01

Mercury is emitted to the atmosphere from various natural and anthropogenic sources, and degrades with difficulty in the environment. Mercury exists as various species, mainly elemental (Hg0) and divalent (Hg2+) mercury depending on its oxidation states in air and water. Mercury emitted to the atmosphere can be deposited into aqueous environments by wet and dry depositions, and some can be re-emitted into the atmosphere. The deposited mercury species, mainly Hg2+, can react with various organic compounds in water and sediment by biotic reactions mediated by sulfur-reducing bacteria, and abiotic reactions mediated by sunlight photolysis, resulting in conversion into organic mercury such as methylmercury (MeHg). MeHg can be bioaccumulated through the food web in the ecosystem, finally exposing humans who consume fish. For a better understanding of how humans are exposed to mercury in the environment, this review paper summarizes the mechanisms of emission, fate and transport, speciation chemistry, bioaccumulation, levels of contamination in environmental media, and finally exposure assessment of humans. PMID:23230463

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.

Seasonal occurrence and degradation of 2-methylisoborneol in water supply reservoirs.

PubMed

Westerhoff, Paul; Rodriguez-Hernandez, M; Baker, Larry; Sommerfeld, Milton

2005-12-01

Methylisoborneol (MIB) and geosmin are cyanobacterial metabolites that occur at nanograms per liter levels in surface water supplies and are responsible for many taste and odor complaints about the aesthetics of drinking water. This study evaluated three water supply reservoirs with bottom-release (hypolimnion) outlet structures in Arizona. MIB concentrations were always higher than geosmin concentrations, but both followed similar seasonal trends. MIB concentrations increased from spring to late summer, and stratified vertically with depth in the water column; the highest concentrations were always in the upper 10 m of the water column. Thermal destratification in the autumn increased MIB concentrations released from the outlet of reservoirs and impacted downstream utilities for several months. By winter of each year MIB concentrations were non-detectable. Mass balance analyses on MIB indicated that in-reservoir reactions were more important in changing MIB concentrations than conservative hydraulic "flushing" of the reservoir. Maximum net loss rates for MIB in the field (R(F,max)) were on the order of 0.23-1.7 ng/L-day, and biodegradation appeared more important than volatilization, photolysis or adsorption. Using lake water in laboratory experiments, bacterial biodegradation rates (R(L)) ranged from 0.5-1 ng/L-day and were comparable to R(F,max) values. Based upon these rates, MIB concentrations in a reservoir would decrease by approximately 30 ng/L over a period of 1 month. This was the magnitude change in MIB concentrations commonly observed after autumn thermal destratification of the reservoirs.

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.

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'.

Performance of small water treatment plants: The case study of Mutshedzi Water Treatment Plant

NASA Astrophysics Data System (ADS)

Makungo, R.; Odiyo, J. O.; Tshidzumba, N.

The performance of small water treatment plants (SWTPs) was evaluated using Mutshedzi WTP as a case study. The majority of SWTPs in South Africa (SA) that supply water to rural villages face problems of cost recovery, water wastages, limited size and semi-skilled labour. The raw and final water quality analyses and their compliance were used to assess the performance of the Mutshedzi WTP. Electrical conductivity (EC), pН and turbidity were measured in the field using a portable multimeter and a turbidity meter respectively. Atomic Absorption Spectrometry and Ion Chromatography were used to analyse metals and non-metals respectively. The results were compared with the Department of Water Affairs (DWA) guidelines for domestic use. The turbidity levels partially exceeded the recommended guidelines for domestic water use of 1 NTU. The concentrations of chemical parameters in final water were within the DWA guidelines for domestic water use except for fluoride, which exceeded the maximum allowable guideline of 1.5 mg/L in August 2009. Mutshedzi WTP had computed compliance for raw and final water analyses ranging from 79% to 93% and 86% to 93% throughout the sampling period, respectively. The results from earlier studies showed that the microbiological quality of final water in Mutshedzi WTP complied with the recommended guidelines, eliminating the slight chance of adverse aesthetic effects and infectious disease transmission associated with the turbidity values between 1 and 5 NTU. The study concluded that Mutshedzi WTP, though moving towards compliance, is still not producing adequate quality of water. Other studies also indicated that the quantity of water produced from Mutshedzi WTP was inadequate. The findings of the study indicate that lack of monitoring of quantity of water supplied to each village, dosage of treatment chemicals, the treatment capacity of the WTP and monitoring the quality of water treated are some of the factors that limit the performance of

Degradation of 4-chloro 2-aminophenol using combined strategies based on ultrasound, photolysis and ozone.

PubMed

Barik, Arati J; Gogate, Parag R

2016-01-01

The present work investigates the degradation of 4-chloro 2-aminophenol (4C2AP), a highly toxic organic compound, using ultrasonic reactors and combination of ultrasound with photolysis and ozonation for the first time. Two types of ultrasonic reactors viz. ultrasonic horn and ultrasonic bath operating at frequency of 20 kHz and 36 kHz respectively have been used in the work. The effect of initial pH, temperature and power dissipation of the ultrasonic horn on the degradation rate has been investigated. The established optimum parameters of initial pH as 6 (natural pH of the aqueous solution) and temperature as 30 ± 2°C were then used in the degradation studies using the combined approaches. Kinetic study revealed that degradation of 4C2AP followed first order kinetics for all the treatment approaches investigated in the present work. It has been established that US+UV+O3 combined process was the most promising method giving maximum degradation of 4C2AP in both ultrasonic horn (complete removal) and bath (89.9%) with synergistic index as 1.98 and 1.29 respectively. The cavitational yield of ultrasonic bath was found to be eighteen times higher as compared to ultrasonic horn implying that configurations with higher overall areas of transducers would be better selection for large scale treatment. Overall, the work has clearly demonstrated that combined approaches could synergistically remove the toxic pollutant (4C2AP). Copyright © 2015 Elsevier B.V. All rights reserved.

New Insights into the Photochemical Degradation of the Insensitive Munition Formulation IMX-101 in Water.

PubMed

Halasz, Annamaria; Hawari, Jalal; Perreault, Nancy N

2018-01-16

This study describes photolysis of the insensitive munition formulation IMX-101 [2,4-dinitroanisole (DNAN), NQ (nitroguanidine), and 3-nitro-1,2,4-triazol-5-one (NTO)] in aqueous solutions using a solar simulating photoreactor. Due to a large variance in the water solubility of the three constituents DNAN (276 mg L -1 ), NQ (5,000 mg L -1 ), and NTO (16,642 mg L -1 ), two solutions of IMX-101 were prepared: one with low concentration (109.3 mg L -1 ) and another with high concentration (2831 mg L -1 ). The degradation rate constants of DNAN, NQ, and NTO (0.137, 0.075, and 0.202 d -1 , respectively) in the low concentration solution were lower than those of the individually photolyzed components (0.262, 1.181, and 0.349 d -1 , respectively). In the high concentration solution, the molar loss of NTO was 4.3 times higher than that of NQ after 7 days of irradiation, although NQ was two times more concentrated and that NQ alone degraded faster than NTO. In addition to the known degradation products, DNAN removal in IMX-101 was accompanied by multiple productions of methoxydinitrophenols, which were not observed during photolysis of DNAN alone. One route for the formation of methoxydinitrophenols was suggested to involve photonitration of the DNAN photoproduct methoxynitrophenol during simultaneous photodenitration of NQ and NTO in IMX-101. Indeed, when DNAN was photolyzed in the presence of 15 NO 2 -labeled explosive CL-20, we detected methoxydinitrophenols with an increase of 1 mass unit, indicating that denitration of DNAN and renitration of products simultaneously occurred. As was the case with DNAN, we found that guanidine, a primary degradation product of NQ, also underwent renitration in the presence of NTO and the photocatalyst TiO 2 . We concluded that the three constituents of IMX-101 can be photodegraded in surface water and that fate and primary degradation products of IMX-101 can be influenced by the interactions between the formulation ingredients and their

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.

Blue light induced free radicals from riboflavin in degradation of crystal violet by microbial viability evaluation.

PubMed

Liang, Ji-Yuan; Yuann, Jeu-Ming P; Hsie, Zong-Jhe; Huang, Shiuh-Tsuen; Chen, Chiing-Chang

2017-09-01

Crystal violet (CV) is applied in daily use mainly as a commercial dye and antimicrobial agent. Waste water containing CV may affect aquatic ecosystems. Riboflavin, also known as vitamin B 2 , is non-toxic and an essential vitamin required for the functions of the human body. Riboflavin is photosensitive to UV and visible light in terms of generating reactive oxygen species. This study investigated the potential application of blue light on riboflavin, so as to come up with an effective way of degrading CV during its treatment. Photosensitivity of CV leading to degradation in the presence of riboflavin was investigated by light intensity, exposure time, and irradiation dosage. The degradation of CV during riboflavin photolysis treatment was studied by a UV/vis spectrometry and chromatography. The effects of CV degradation on microbial viability are relevant when considering the influences on the ecosystem. This study proved that riboflavin photochemical treatment with blue light degrades CV dye by ROS formation. The riboflavin photolysis-treated CV solution appeared to be transparent during conformational transformations of the CV that was rearranged by free radical species generated from riboflavin photolysis. After riboflavin photolysis, colony-forming units (CFUs) were determined for each CV solution. CFU preservation was 85.2% for the CV dissolved riboflavin solution treated with blue light irradiation at 2.0mW/cm 2 for 120min. Degradation of CV by riboflavin photochemical procedures can greatly reduce antimicrobial ability and serve as an environmental friendly waste water treatment method. Our results presented here concerning riboflavin photolysis in degradation of CV provide a novel technique, and a simple and safe practice for environmental decontamination processes. Copyright © 2017 Elsevier B.V. All rights reserved.

75 FR 7522 - United States Section; Notice of Availability of the Final Environmental Impact Statement, Flood...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-19

... Final EIS: Biological resources, cultural resources, water resources, land use, socioeconomic resources... INTERNATIONAL BOUNDARY AND WATER COMMISSION, UNITED STATES AND MEXICO United States Section..., International Boundary and Water Commission (USIBWC). ACTION: Notice of Availability of Final Environmental...

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

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.

Nuuanu YMCA Honolulu, Hawaii solar-water-heating project. Final report

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

Not Available

1981-10-14

The Nuuanu YMCA is a combination athletic facility and men's dormitory. The building is of masonry construction, and includes a four-story dormitory on which the solar water heating system was mounted. The water storage tank was placed at a higher elevation than the collectors so that the majority of the system would operate in thermosyphon. A small system with a pump is included on another roof of the building and is circulated into the same storage tank. A pump was later added to the thermosyphon system. The system has 182 collector panels, each consisting of a polycarbonate box, low ironmore » tempered glazing, copper waterways and painted aluminum absorber. The water is stored in a 4000-gallon storage tank on the roof. The system provides domestic hot water and serves as a preheat system for the existing building water heaters. The system was installed and met performance criteria. An acceptance test plan is described and data are given. The thermosyphon system was found not to be efficient compared to the pumped system. System operation, maintenance and controls are described, and YMCA energy consumption data are given. Blueprints are included. (LEW)« less

Water quality mitigation banking : final report, December 2009.

DOT National Transportation Integrated Search

2009-12-01

Current practice in New Jersey for mitigating stormwater impacts caused by transportation infrastructure : projects is established by NJDEP Stormwater Regulations (N.J.A.C. 7:8). These rules outline specific : processes to offset impacts to water qua...

18 CFR 300.21 - Final confirmation and approval.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 18 Conservation of Power and Water Resources 1 2010-04-01 2010-04-01 false Final confirmation and approval. 300.21 Section 300.21 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY... reasonable number of years after first meeting the Administrator's other costs. (ii) The rates must be based...

18 CFR 300.21 - Final confirmation and approval.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 18 Conservation of Power and Water Resources 1 2012-04-01 2012-04-01 false Final confirmation and approval. 300.21 Section 300.21 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY... reasonable number of years after first meeting the Administrator's other costs. (ii) The rates must be based...

A flash photolysis-resonance fluorescence study of the formation of O(D-1) in the photolysis of water and reaction of O(D-1) with H2, Ar and He

NASA Technical Reports Server (NTRS)

Stief, L. J.; Payne, W. A.; Klemm, R. B.

1974-01-01

The relative importance of two primary processes in the photolyis of water: (1) H2O + h (nu) yields H + OH, and (2) H2O + h (nu) yields H2 + OD-1 were determined in a direct manner by time resolved detection (via resonance fluorescence) of H and O formed in processes 1 and 2 respectively. The initially formed OD-1 was deactivated to ground state OP-3 prior to detection via resonance fluorescence. The relative quantum yields for processes 1 and 2 are 0.89 and 0.11 for the wavelength interval 105 to 145nm and = to or greater than 0.99, and = to or less than 0.01 for the wavelength interval 145 to 185nm. Rate constants at 300 K for the reactions OD-1 + H2, + Ar, and + He are presented.

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

NASA Astrophysics Data System (ADS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Chang, Sherwood; Scharberg, Maureen A.

1995-11-01

The infrared (IR) spectra of ultraviolet (UV) and thermally processed, methanol-containing interstellar/ cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=-N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to polyoxymethylene {POM, ( CH2O )n}, and (3) ketones {R-C(=O)-R'} and amides {H2NC(=O)-R}. Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and 13C isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

A 5 year longitudinal study of water quality for final rinsing in the single chamber washer-disinfector with a reverse osmosis plant.

PubMed

Uetera, Yushi; Kishii, Kozue; Yasuhara, Hiroshi; Kumada, Naohito; Moriya, Kyoji; Saito, Ryoichi; Okazaki, Mitsuhiro; Misawa, Yoshiki; Kawamura, Kunio

2013-01-01

This report deals with the construction and management of the reverse osmosis (RO) water system for final rinsing of surgical instruments in the washer-disinfector. Numerous operational challenges were encountered in our RO water system and these were analyzed utilizing the Ishikawa Fishbone diagram. The aim was to find potential problems and promote preventive system management for RO water. It was found that the measures that existed were inappropriate for preventing contamination in the heat-labile RO water system. The storage tank was found to be significantly contaminated and had to be replaced with a new one equipped with a sampling port and water drainage system. Additional filters and an UV treatment lamp were installed. The whole system disinfection started 1.5 years later using a peracetic acid-based compound after confirming the material compatibility. Operator errors were found when a new water engineer took over the duty from his predecessor. It was also found that there were some deficiencies in the standard operating procedures (SOPs), and that on-the-job training was not enough. The water engineer failed to disinfect the sampling port and water drainage system. The RO membrane had been used for 4 years, even though the SOP standard specified changing it as every 3 years. Various bacteria, such as Rothia mucilaginosa, were cultured from the RO water sampled from the equipment. Because Rothia mucilaginosa is a resident in the oral cavity and upper respiratory tract, it is believed that the bacteria were introduced into the system by the maintenance personnel or working environment. Therefore, the presence of R. mucilaginosa implied the failure of sanitary maintenance procedures. This study suggests that water systems should be designed based on the plans for profound system maintenance. It also suggests that SOP and on-the job training are essential to avoid any operator errors. These results must be carefully considered when either constructing new

Interactive Photochemistry in Earth System Models to Assess Uncertainty in Ozone and Greenhouse Gases. Final report

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

Prather, Michael J.; Hsu, Juno; Nicolau, Alex

Atmospheric chemistry controls the abundances and hence climate forcing of important greenhouse gases including N 2O, CH 4, HFCs, CFCs, and O 3. Attributing climate change to human activities requires, at a minimum, accurate models of the chemistry and circulation of the atmosphere that relate emissions to abundances. This DOE-funded research provided realistic, yet computationally optimized and affordable, photochemical modules to the Community Earth System Model (CESM) that augment the CESM capability to explore the uncertainty in future stratospheric-tropospheric ozone, stratospheric circulation, and thus the lifetimes of chemically controlled greenhouse gases from climate simulations. To this end, we have successfullymore » implemented Fast-J (radiation algorithm determining key chemical photolysis rates) and Linoz v3.0 (linearized photochemistry for interactive O 3, N 2O, NO y and CH 4) packages in LLNL-CESM and for the first time demonstrated how change in O2 photolysis rate within its uncertainty range can significantly impact on the stratospheric climate and ozone abundances. From the UCI side, this proposal also helped LLNL develop a CAM-Superfast Chemistry model that was implemented for the IPCC AR5 and contributed chemical-climate simulations to CMIP5.« 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.

Ultraviolet radiation from the pulsed corona discharge in water

NASA Astrophysics Data System (ADS)

Lukes, Petr; Clupek, Martin; Babicky, Vaclav; Sunka, Pavel

2008-05-01

Quantitative analysis of ultraviolet radiation from the pulsed corona discharge in water with needle-plate electrode geometry (~1-3 J pulse-1) was performed using the potassium ferrioxalate actinometry. Photon flux J190-280 and radiant energy Q190-280 of the UV light emitted from the discharge at spectral region 190-280 nm was determined in dependence on the applied voltage (17-29 kV, positive polarity) and the solution conductivity (100-500 µS cm-1). The intensity of the UV radiation strongly increased with increasing water conductivity and applied voltage. Depending on the applied voltage the determined photon flux varied by more than two orders of magnitude within the range of solution conductivities 100-500 µS cm-1. It was found that photon flux from the discharge may be directly related to the discharge pulse mean power Pp as J190-280 = 44.33 P_p^{2.11} (quanta pulse-1). A significant role of UV radiation in the production of hydrogen peroxide and bacterial inactivation by the corona discharge in water has been identified. As the solution conductivity increased the yield of H2O2 produced by the discharge decreased due to increasing photolysis of H2O2 accounting for up to 14% of the total decomposition rate of H2O2. As regards bactericidal effects, it was estimated that the UV radiation contributes about 30% to the overall inactivation of Escherichia coli.

Blending Cr 2O 3 into a NiO-Ni electrocatalyst for sustained water splitting

DOE PAGES

Gong, Ming; Zhou, Wu; Kenney, Michael James; ...

2015-08-24

The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less

Impact of a new wavelength-dependent representation of methane photolysis branching ratios on the modeling of Titan’s atmospheric photochemistry

NASA Astrophysics Data System (ADS)

Gans, B.; Peng, Z.; Carrasco, N.; Gauyacq, D.; Lebonnois, S.; Pernot, P.

2013-03-01

A new wavelength-dependent model for CH4 photolysis branching ratios is proposed, based on the values measured recently by Gans et al. (Gans, B. et al. [2011]. Phys. Chem. Chem. Phys. 13, 8140-8152). We quantify the impact of this representation on the predictions of a photochemical model of Titan’s atmosphere, on their precision, and compare to earlier representations. Although the observed effects on the mole fraction of the species are small (never larger than 50%), it is possible to draw some recommendations for further studies: (i) the Ly-α branching ratios of Wang et al. (Wang, J.H. et al. [2000]. J. Chem. Phys. 113, 4146-4152) used in recent models overestimate the CH2:CH3 ratio, a factor to which a lot of species are sensitive; (ii) the description of out-of-Ly-α branching ratios by the “100% CH3” scenario has to be avoided, as it can bias significantly the mole fractions of some important species (C3H8); and (iii) complementary experimental data in the 130-140 nm range would be useful to constrain the models in the Ly-α deprived 500-700 km altitude range.

18 CFR 270.502 - Commission review of final determinations.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 18 Conservation of Power and Water Resources 1 2010-04-01 2010-04-01 false Commission review of final determinations. 270.502 Section 270.502 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY PROCEDURES GOVERNING DETERMINATIONS FOR TAX CREDIT PURPOSES...

Kinetic Requirements for the Measurement of Mesospheric Water Vapor at 6.8 (microns) under Non-LTE Conditions

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Russell, James M., III

1999-01-01

We present accuracy requirements for specific kinetic parameters used to calculate the populations and vibrational temperatures of the H2O(010) and H2O(020) states in the terrestrial mesosphere. The requirements are based on rigorous simulations of the retrieval of mesospheric water vapor profiles from measurements of water vapor infrared emission made by limb scanning instruments on orbiting satellites. Major improvements in the rate constants that describe vibration-to- vibration exchange between the H2O(010) and 02(1) states are required in addition to improved specification of the rate of quenching Of O2(1) by atomic oxygen (0). It is also necessary to more accurately determine the yield of vibrationally excited O2(l) resulting from ozone photolysis. A contemporary measurement of the rate of quenching of H2O(010) by N2 and O2 is also desirable. These rates are either highly uncertain or have never before been measured at atmospheric temperatures. The suggested improvements are necessary for the interpretation of water vapor emission measurements at 6.8 microns to be made from a new spaceflight experiment in less than 2 years. The approach to retrieving water vapor under non-LTE conditions is also presented.

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.

Role of effluent organic matter in the photochemical degradation of compounds of wastewater origin.

PubMed

Bodhipaksha, Laleen C; Sharpless, Charles M; Chin, Yu-Ping; MacKay, Allison A

2017-03-01

The photoreactivity of treated wastewater effluent organic matter differs from that of natural organic matter, and the indirect phototransformation rates of micropollutants originating in wastewater are expected to depend on the fractional contribution of wastewater to total stream flow. Photodegradation rates of four common compounds of wastewater origin (sulfamethoxazole, sulfadimethoxine, cimetidine and caffeine) were measured in river water, treated municipal wastewater effluent and mixtures of both to simulate various effluent-stream water mixing conditions that could occur in environmental systems. Compounds were chosen for their unique photodegradation pathways with the photochemically produced reactive intermediates, triplet-state excited organic matter ( 3 OM*), singlet oxygen ( 1 O 2 ), and hydroxyl radicals (OH). For all compounds, higher rates of photodegradation were observed in effluent relative to upstream river water. Sulfamethoxazole degraded primarily via direct photolysis, with some contribution from OH and possibly from carbonate radicals and other unidentified reactive intermediates in effluent-containing samples. Sulfadimethoxine also degraded mainly by direct photolysis, and natural organic matter appeared to inhibit this process to a greater extent than predicted by light screening. In the presence of effluent organic matter, sulfadimethoxine showed additional reactions with OH and 1 O 2 . In all water samples, cimetidine degraded by reaction with 1 O 2 (>95%) and caffeine by reaction with OH (>95%). In river water mixtures, photodegradation rate constants for all compounds increased with increasing fractions of effluent. A conservative mixing model was able to predict reaction rate constants in the case of hydroxyl radical reactions, but it overestimated rate constants in the case of 3 OM* and 1 O 2 pathways. Finally, compound degradation rate constants normalized to the rate of light absorption by water correlated with E 2 /E 3 ratios

Physicochemical regeneration of high silica zeolite Y used to clean-up water polluted with sulfonamide antibiotics.

PubMed

Braschi, I; Blasioli, S; Buscaroli, E; Montecchio, D; Martucci, A

2016-05-01

High silica zeolite Y has been positively evaluated to clean-up water polluted with sulfonamides, an antibiotic family which is known to be involved in the antibiotic resistance evolution. To define possible strategies for the exhausted zeolite regeneration, the efficacy of some chemico-physical treatments on the zeolite loaded with four different sulfonamides was evaluated. The evolution of photolysis, Fenton-like reaction, thermal treatments, and solvent extractions and the occurrence in the zeolite pores of organic residues eventually entrapped was elucidated by a combined thermogravimetric (TGA-DTA), diffractometric (XRPD), and spectroscopic (FT-IR) approach. The chemical processes were not able to remove the organic guest from zeolite pores and a limited transformation on embedded molecules was observed. On the contrary, both thermal treatment and solvent extraction succeeded in the regeneration of the zeolite loaded from deionized and natural fresh water. The recyclability of regenerated zeolite was evaluated over several adsorption/regeneration cycles, due to the treatment efficacy and its stability as well as the ability to regain the structural features of the unloaded material. Copyright © 2015. Published by Elsevier B.V.

Final report on APMP.T-K7.1 key comparison of water triple point cells, bilateral NMIJ-VMI

NASA Astrophysics Data System (ADS)

Yamazawa, Kazuaki; Nakano, Tohru; Thanh Binh, Pham

2018-01-01

APMP.T-K7.1, was held from July 2014 to May 2015 to compare the national realizations of the water triple point between NMIJ (Japan) and VMI (Vietnam). To reach the objective, VMI sent a transfer cell to NMIJ and stated a value for the temperature difference of the transfer cell, relative to the corresponding national standard, representing 273.16 K. This report presents the results of the TPW comparison, gives detailed information about the measurements made at the NMIJ and at the VMI, and aims to link the results of APMP.T-K7.1 to APMP.T-K7 and CCT-K7. The results of this key comparison are also represented in the form of degrees of equivalence for the purposes of the MRA. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCT, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Ultrasound (US), Ultraviolet light (UV) and combination (US+UV) assisted semiconductor catalysed degradation of organic pollutants in water: oscillation in the concentration of hydrogen peroxide formed in situ.

PubMed

Jyothi, K P; Yesodharan, Suguna; Yesodharan, E P

2014-09-01

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like ·OH, HO2·, O2(-), H2O2 etc. Among these, H2O2 is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H2O2 formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H2O2 formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H2O2 in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H2O2) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis>photocatalysis⩾sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis>photocatalysis>sonocatalysis>sonolysis>photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H2O2 have longer life time (memory effect). Copyright © 2014 Elsevier B.V. All rights reserved.

Self Assembly and Properties of C:WO3 Nano-Platelets and C:VO2/V2O5 Triangular Capsules Produced by Laser Solution Photolysis

PubMed Central

2010-01-01

Laser photolysis of WCl6 in ethanol and a specific mixture of V2O5 and VCl3 in ethanol lead to carbon modified vanadium and tungsten oxides with interesting properties. The presence of graphene’s aromatic rings (from the vibrational frequency of 1,600 cm−1) together with C–C bonding of carbon (from the Raman shift of 1,124 cm−1) present unique optical, vibrational, electronic and structural properties of the intended tungsten trioxide and vanadium dioxide materials. The morphology of these samples shows nano-platelets in WOx samples and, in VOx samples, encapsulated spherical quantum dots in conjunction with fullerenes of VOx. Conductivity studies revealed that the VO2/V2O5 nanostructures are more sensitive to Cl than to the presence of ethanol, whereas the C:WO3 nano-platelets are more sensitive to ethanol than atomic C. PMID:20671779

Geothermal Water Use: Life Cycle Water Consumption, Water Resource Assessment, and Water Policy Framework

DOE Data Explorer

Schroeder, Jenna N.

2014-06-10

This report examines life cycle water consumption for various geothermal technologies to better understand factors that affect water consumption across the life cycle (e.g., power plant cooling, belowground fluid losses) and to assess the potential water challenges that future geothermal power generation projects may face. Previous reports in this series quantified the life cycle freshwater requirements of geothermal power-generating systems, explored operational and environmental concerns related to the geochemical composition of geothermal fluids, and assessed future water demand by geothermal power plants according to growth projections for the industry. This report seeks to extend those analyses by including EGS flash, both as part of the life cycle analysis and water resource assessment. A regional water resource assessment based upon the life cycle results is also presented. Finally, the legal framework of water with respect to geothermal resources in the states with active geothermal development is also analyzed.

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.

Fluorescence quenching of protonated β-carbolines in water and microemulsions: evidence for heavy-atom and electron-transfer mechanisms.

PubMed

Mousa, Souad A; Douglas, Peter; Burrows, Hugh D; Fonseca, Sofia M

2013-09-01

The fluorescence quenching of protonated β-carbolines has been investigated in acidic aqueous solutions and in w/o microemulsions using I(-), Br(-), Cu(2+), SCN(-), and Pb(2+) as quenchers. It was found that fluorescence quenching by these compounds is much more efficient in water than in microemulsions since quenching in microemulsions depends on the simultaneous occupancy of the water droplets by both fluorophore and quencher. Linear Stern-Volmer plots were obtained in all cases, leading to quenching rate constants of ca. 10(8)-10(10) M(-1) s(-1) in water and ca. 10(7)-10(8) M(-1) s(-1) in microemulsions. In the case of quenching by SCN(-), ns flash photolysis studies indicate formation of (SCN)2(˙-) showing that at least part of the quenching process involves an electron transfer mechanism. This indicates that the singlet excited states of the protonated β-carbolines can act as relatively strong oxidants (E° > 1.6 V), capable of oxidizing many species, including the biologically relevant DNA base guanine. The observation of the (SCN)2(˙-) transient in microemulsions demonstrates that it is possible to have the protonated β-carboline and at least two thiocyanate ions in the same water pool.

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

NASA Technical Reports Server (NTRS)

Vander Wood, T. B.; Thiemens, M. H.

1980-01-01

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

PubMed

Wang, X; Shih, K; Li, X Y

2010-01-01

A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

Phototransformation rates and mechanisms for synthetic hormone growth promoters used in animal agriculture.

PubMed

Qu, Shen; Kolodziej, Edward P; Cwiertny, David M

2012-12-18

Trenbolone acetate, melengestrol acetate, and zeranol are synthetic hormones extensively used as growth promoters in animal agriculture, yet despite occurrence in water and soil little is known about their environmental fate. Here, we establish the time scales and mechanisms by which these synthetic growth promoters and their metabolites (SGPMs) undergo phototransformation in sunlit surface waters. The families of trenbolone acetate (including 17β-trenbolone, 17α-trenbolone, and trendione) and melengestrol acetate (including melengestrol) readily undergo direct photolysis, exhibiting half-lives between ∼0.25 and 1 h in both natural and simulated sunlight that were largely insensitive to solution variables (e.g., pH, temperature, and cosolutes). Direct photolysis yielded products that not only are more photostable but also maintain their steroidal ring structure and therefore may retain some biological activity. In contrast, zeranol, β-zearalanol, and zearalanone only exhibited reactivity in irradiated solutions of model humic and fulvic acids, and rates of indirect photolysis increased steadily from pH 7 to 9. Use of selective probe and quencher compounds suggest hydroxyl radical and triplet state dissolved organic matter are responsible for zeranol family decay at neutral pH, although singlet oxygen contributes modestly in more alkaline waters. This observed pH-dependence appears to result from photooxidants reacting primarily with the monodeprotonated form of zeranol (pK(a) values of 8.44 and 11.42). This investigation provides the first characterization of the fate of this emerging pollutant class in sunlit surface waters and prioritizes future efforts on the identity, fate, and biological impact of their more persistent phototransformation products.

N-Nitrosodimethylamine (NDMA) and its precursors in water and wastewater: A review on formation and removal.

PubMed

Sgroi, Massimiliano; Vagliasindi, Federico G A; Snyder, Shane A; Roccaro, Paolo

2018-01-01

This review summarizes major findings over the last decade related to N-Nitrosodimethylamine (NDMA) in water and wastewater. In particular, the review is focused on the removal of NDMA and of its precursors by conventional and advanced water and wastewater treatment processes. New information regarding formation mechanisms and precursors are discussed as well. NDMA precursors are generally of anthropogenic origin and their main source in water have been recognized to be wastewater discharges. Chloramination is the most common process that results in formation of NDMA during water and wastewater treatment. However, ozonation of wastewater or highly contaminated surface water can also generate significant levels of NDMA. Thus, NDMA formation control and remediation has become of increasing interest, particularly during treatment of wastewater-impacted water and during potable reuse application. NDMA formation has also been associated with the use of quaternary amine-based coagulants and anion exchange resins. UV photolysis with UV fluence far higher than typical disinfection doses is generally considered the most efficient technology for NDMA mitigation. However, recent studies on the optimization of biological processes offer a potentially lower-energy solution. Options for NDMA control include attenuation of precursor materials through physical removal, biological treatment, and/or deactivation by application of oxidants. Nevertheless, NDMA precursor identification and removal can be challenging and additional research and optimization is needed. As municipal wastewater becomes increasingly used as a source water for drinking, NDMA formation and mitigation strategies will become increasingly more important. The following review provides a summary of the most recent information available. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photodegradation of antibiotics under simulated solar radiation: implications for their environmental fate.

PubMed

Batchu, Sudha Rani; Panditi, Venkata R; O'Shea, Kevin E; Gardinali, Piero R

2014-02-01

Roxithromycin, erythromycin, ciprofloxacin and sulfamethoxazole are frequently detected antibiotics in environmental waters. Direct and indirect photolysis of these problematic antibiotics were investigated in pure and natural waters (fresh and salt water) under irradiation of different light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield and first order rate constants are reported and discussed. The antibiotics are degraded fastest under ultraviolet 254 nm, followed by 350 nm and simulated solar radiation. The composition of the matrix (pH, dissolved organic content, chloride ion concentration) played a significant role in the observed photodegradation. Under simulated solar radiation, ciprofloxacin and sulfamethoxazole degrade relatively quickly with half-lives of 0.5 and 1.5h, respectively. However, roxithromycin and erythromycin, macrolides are persistent (half-life: 2.4-10 days) under solar simulation. The transformation products (15) of the targeted antibiotics produced under irradiation experiments were identified using high resolution mass spectrometry and degradation pathways were proposed. © 2013.

Infectious Cryptosporidium parvum oocysts in final reclaimed effluent

USGS Publications Warehouse

Gennaccaro, A.L.; McLaughlin, M.R.; Quintero-Betancourt, W.; Huffman, D.E.; Rose, J.B.

2003-01-01

Water samples collected throughout several reclamation facilities were analyzed for the presence of infectious Cryptosporidium parvum by the focus detection method-most-probable-number cell culture technique. Results revealed the presence of infectious C. parvum oocysts in 40% of the final disinfected effluent samples. Sampled effluent contained on average seven infectious oocysts per 100 liters. Thus, reclaimed water is not pathogen free but contains infectious C. parvum.

First measurement of the νμ charged-current cross section on a water target without pions in the final state

NASA Astrophysics Data System (ADS)

Abe, K.; Amey, J.; Andreopoulos, C.; Antonova, M.; Aoki, S.; Ariga, A.; Ashida, Y.; Ban, S.; Barbi, M.; Barker, G. J.; Barr, G.; Barry, C.; Batkiewicz, M.; Berardi, V.; Berkman, S.; Bhadra, S.; Bienstock, S.; Blondel, A.; Bolognesi, S.; Bordoni, S.; Boyd, S. B.; Brailsford, D.; Bravar, A.; Bronner, C.; Buizza Avanzini, M.; Calland, R. G.; Campbell, T.; Cao, S.; Cartwright, S. L.; Catanesi, M. G.; Cervera, A.; Chappell, A.; Checchia, C.; Cherdack, D.; Chikuma, N.; Christodoulou, G.; Coleman, J.; Collazuol, G.; Coplowe, D.; Cudd, A.; Dabrowska, A.; De Rosa, G.; Dealtry, T.; Denner, P. F.; Dennis, S. R.; Densham, C.; Di Lodovico, F.; Dolan, S.; Drapier, O.; Duffy, K. E.; Dumarchez, J.; Dunne, P.; Emery-Schrenk, S.; Ereditato, A.; Feusels, T.; Finch, A. J.; Fiorentini, G. A.; Friend, M.; Fujii, Y.; Fukuda, D.; Fukuda, Y.; Garcia, A.; Giganti, C.; Gizzarelli, F.; Golan, T.; Gonin, M.; Hadley, D. R.; Haegel, L.; Haigh, J. T.; Hansen, D.; Harada, J.; Hartz, M.; Hasegawa, T.; Hastings, N. C.; Hayashino, T.; Hayato, Y.; Hillairet, A.; Hiraki, T.; Hiramoto, A.; Hirota, S.; Hogan, M.; Holeczek, J.; Hosomi, F.; Huang, K.; Ichikawa, A. K.; Ikeda, M.; Imber, J.; Insler, J.; Intonti, R. A.; Ishida, T.; Ishii, T.; Iwai, E.; Iwamoto, K.; Izmaylov, A.; Jamieson, B.; Jiang, M.; Johnson, S.; Jonsson, P.; Jung, C. K.; Kabirnezhad, M.; Kaboth, A. C.; Kajita, T.; Kakuno, H.; Kameda, J.; Karlen, D.; Katori, T.; Kearns, E.; Khabibullin, M.; Khotjantsev, A.; Kim, H.; Kim, J.; King, S.; Kisiel, J.; Knight, A.; Knox, A.; Kobayashi, T.; Koch, L.; Koga, T.; Koller, P. P.; Konaka, A.; Kormos, L. L.; Koshio, Y.; Kowalik, K.; Kudenko, Y.; Kurjata, R.; Kutter, T.; Lagoda, J.; Lamont, I.; Lamoureux, M.; Lasorak, P.; Laveder, M.; Lawe, M.; Licciardi, M.; Lindner, T.; Liptak, Z. J.; Litchfield, R. P.; Li, X.; Longhin, A.; Lopez, J. P.; Lou, T.; Ludovici, L.; Lu, X.; Magaletti, L.; Mahn, K.; Malek, M.; Manly, S.; Maret, L.; Marino, A. D.; Martin, J. F.; Martins, P.; Martynenko, S.; Maruyama, T.; Matveev, V.; Mavrokoridis, K.; Ma, W. Y.; Mazzucato, E.; McCarthy, M.; McCauley, N.; McFarland, K. S.; McGrew, C.; Mefodiev, A.; Metelko, C.; Mezzetto, M.; Minamino, A.; Mineev, O.; Mine, S.; Missert, A.; Miura, M.; Moriyama, S.; Morrison, J.; Mueller, Th. A.; Nakadaira, T.; Nakahata, M.; Nakamura, K. G.; Nakamura, K.; Nakamura, K. D.; Nakanishi, Y.; Nakayama, S.; Nakaya, T.; Nakayoshi, K.; Nantais, C.; Nielsen, C.; Nishikawa, K.; Nishimura, Y.; Novella, P.; Nowak, J.; O'Keeffe, H. M.; Okumura, K.; Okusawa, T.; Oryszczak, W.; Oser, S. M.; Ovsyannikova, T.; Owen, R. A.; Oyama, Y.; Palladino, V.; Palomino, J. L.; Paolone, V.; Patel, N. D.; Paudyal, P.; Pavin, M.; Payne, D.; Petrov, Y.; Pickering, L.; Pinzon Guerra, E. S.; Pistillo, C.; Popov, B.; Posiadala-Zezula, M.; Poutissou, J.-M.; Pritchard, A.; Przewlocki, P.; Quilain, B.; Radermacher, T.; Radicioni, E.; Ratoff, P. N.; Rayner, M. A.; Reinherz-Aronis, E.; Riccio, C.; Rondio, E.; Rossi, B.; Roth, S.; Ruggeri, A. C.; Rychter, A.; Sakashita, K.; Sánchez, F.; Scantamburlo, E.; Scholberg, K.; Schwehr, J.; Scott, M.; Seiya, Y.; Sekiguchi, T.; Sekiya, H.; Sgalaberna, D.; Shah, R.; Shaikhiev, A.; Shaker, F.; Shaw, D.; Shiozawa, M.; Shirahige, T.; Smy, M.; Sobczyk, J. T.; Sobel, H.; Steinmann, J.; Stewart, T.; Stowell, P.; Suda, Y.; Suvorov, S.; Suzuki, A.; Suzuki, S. Y.; Suzuki, Y.; Tacik, R.; Tada, M.; Takeda, A.; Takeuchi, Y.; Tamura, R.; Tanaka, H. K.; Tanaka, H. A.; Thakore, T.; Thompson, L. F.; Tobayama, S.; Toki, W.; Tomura, T.; Tsukamoto, T.; Tzanov, M.; Vagins, M.; Vallari, Z.; Vasseur, G.; Vilela, C.; Vladisavljevic, T.; Wachala, T.; Walter, C. W.; Wark, D.; Wascko, M. O.; Weber, A.; Wendell, R.; Wilking, M. J.; Wilkinson, C.; Wilson, J. R.; Wilson, R. J.; Wret, C.; Yamada, Y.; Yamamoto, K.; Yanagisawa, C.; Yano, T.; Yen, S.; Yershov, N.; Yokoyama, M.; Yuan, T.; Yu, M.; Zalewska, A.; Zalipska, J.; Zambelli, L.; Zaremba, K.; Ziembicki, M.; Zimmerman, E. D.; Zito, M.; T2K Collaboration

2018-01-01

This paper reports the first differential measurement of the charged-current interaction cross section of νμ on water with no pions in the final state. This flux-averaged measurement has been made using the T2K experiment's off-axis near detector, and is reported in doubly differential bins of muon momentum and angle. The flux-averaged total cross section in a restricted region of phase space was found to be σ =(0.95 ±0.08 (stat) ±0.06 (det syst)±0.04 (model syst)±0.08 (flux ))×10-38 cm2/n .

Drinking Water Criteria Document for Ethylene Dibromide (EDB) (Final Draft, 1985)

EPA Science Inventory

The Office of Drinking Water (ODW), U.S. Environmental Protection Agency has prepared a "Drinking Water Criteria Document on Ethylene Dibromide (EDB)". The Criteria Document is an extensive review of the following topics: Physical and chemical properties of ethylene dibromide, to...

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-).

PubMed

Yempally, Veeranna; Moncho, Salvador; Hasanayn, Faraj; Fan, Wai Yip; Brothers, Edward N; Bengali, Ashfaq A

2017-09-18

The photochemistry of two Mn(bpy)(CO) 3 X complexes (X = PhCC - , Br - ) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO) 2 ] affords the ionic complex [1-(MeCN) 2 ]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br - . Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

Chemiluminescent Determination of Oxamyl in Drinking Water and Tomato Using Online Postcolumn UV Irradiation in a Chromatographic System.

PubMed

Murillo Pulgarín, José A; García Bermejo, Luisa F; Durán, Armando Carrasquero

2018-03-07

High-performance liquid chromatography (HPLC) was used to separate oxamyl from other pesticides in drinking water and tomato paste. The eluate emerging from the column tail was mixed with an alkaline solution of Co 2+ in EDTA and irradiated with UV light to induce photolysis of the carbamate in order to obtain free radicals and other reactive species that oxidize luminol and produce chemiluminescence (CL) as a result. The intensity of the CL signal was monitored in the form of chromatographic peaks. Under the optimum operating conditions for the HPLC-UV-CL system, the analyte concentration was linearly related to peak area. The limit of detection as determined in accordance with the IUPAC criterion was 0.17 mg L -1 . Oxamyl was successfully extracted with recoveries of 88.7-103.1% from spiked tomato paste by using a simple QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) sample preparation approach. Similar recoveries were obtained from drinking water samples spiked with oxamyl concentrations above the LOD. The proposed method is a simple, fast, accurate choice for quantifying this pesticide.

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.

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3). [applications to spacecraft fuel cells

NASA Technical Reports Server (NTRS)

Sheridan, P. S.

1980-01-01

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

Final report on development and testing of the microwave oil-water monitor

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

Swanson, C.

1991-06-15

The oil-water monitor is a device invented by Dr. Claude Swanson of Applied Physics Technology to respond to the petroleum-loss problem in crude oil transfers. It is a device which measures water content in crude oil and other petroleum products, in a flowing pipe such as a pipeline or tanker manifold. It is capable of accurately measuring the water contamination levels in crude oil shipments, in real time as the crude oil flows through the loading manifold into the tanker, or at the receiving point as the oil is off-loaded. The oil-water monitor has application in the verification of oilmore » volumes and concentration of contaminants at petroleum transfer points. The industry-estimated level of water loss at transfer points due to inadequate monitoring technology amounts to several billion dollars per year, so there is a definite perceived need within the petroleum community for this type of accurate water monitoring technology. News articles indicating the importance of this problem are shown. The microwave oil-water monitor measures the water content in the oil, whether in the form of small droplets or large globules. Therefore it can be applied to the crude oil as it flows through crude oil pipes into the ship, or at transfer points in a crude oil distribution system. 4 refs., 18 figs.« less

Observed Seasonal to Decadal-Scale Responses in Mesospheric Water Vapor

NASA Technical Reports Server (NTRS)

Remsberg, Ellis

2010-01-01

The 14-yr (1991-2005) time series of mesospheric water vapor from the Halogen Occultation Experiment (HALOE) are analyzed using multiple linear regression (MLR) techniques for their6 seasonal and longer-period terms from 45S to 45N. The distribution of annual average water vapor shows a decrease from a maximum of 6.5 ppmv at 0.2 hPa to about 3.2 ppmv at 0.01 hPa, in accord with the effects of the photolysis of water vapor due to the Lyman-flux. The distribution of the semi-annual cycle amplitudes is nearly hemispherically symmetric at the low latitudes, while that of the annual cycles show larger amplitudes in the northern hemisphere. The diagnosed 11-yr, or solar cycle, max minus min, water vapor values are of the order of several percent at 0.2 hPa to about 23% at 0.01 hPa. The solar cycle terms have larger values in the northern than in the southern hemisphere, particularly in the middle mesosphere, and the associated linear trend terms are anomalously large in the same region. Those anomalies are due, at least in part, to the fact that the amplitudes of the seasonal cycles were varying at northern mid latitudes during 1991-2005, while the corresponding seasonal terms of the MLR model do not allow for that possibility. Although the 11-yr variation in water vapor is essentially hemispherically-symmetric and anti-phased with the solar cycle flux near 0.01 hPa, the concurrent temperature variations produce slightly colder conditions at the northern high latitudes at solar minimum. It is concluded that this temperature difference is most likely the reason for the greater occurrence of polar mesospheric clouds at the northern versus the southern high latitudes at solar minimum during the HALOE time period.

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Chang, Sherwood; Scharberg, Maureen A.

1995-01-01

The InfraRed (IR) spectra of UltraViolet (UV) and thermally processed, methanol-containing interstellar / cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, H-1 and C-13 Nuclear Magnetic Resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC([double bond]O)NH2 (formamide), CH3C([double bond]O)NH2 (acetamide), and R[single bond]C[triple bond]N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to PolyOxyMethylene (POM, ([single bond]CH2O[single bond](sub n)), and (3) ketones (R[single bond]C([double bond]O)[single bond]R') and amides (H2NC([double bond]O)[single bond]R). Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and C-13 isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the 'XCN' band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

Bee guide to complying with the Safe Drinking Water Act. Final report

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

Garland, J.G.; Acker, A.M.

This report provides current information on the Safe Drinking Water Act and recent amendments. The report describes the evolution of the Safe Drinking Water Act and the responsibilities of base personnel involved in compliance with the Act. It also describes the monitoring requirements, analytical requirements, best available technology for controlling contaminants, and public notification requirements for regulated contaminants. The appendixes include proposed contaminants and state water quality agencies. Each Air Force public water distribution system (PWDS) must comply with the SDWA, and the National Primary Drinking Water Regulations (NPDWRs). In the United States and its territories, the provisions of themore » SDWA and the NPDWRs are enforced by the states except in the few instances in which the state has not been delegated primary enforcement responsibility (primacy) by the EPA. States that have primacy may establish drinking water regulations, monitoring schedules, and reporting requirements more stringent than, or in addition to, those in the NPDWRs. Air Force public water systems in these states are required to comply with these additional requirements as well as federal enforcement actions as carried out by the EPA Regional Office.« less

Medicare program; standards for quality of water used in dialysis and revised guidelines on reuse of hemodialysis filters for end-stage renal disease (ESRD) patients--HCFA. Final rule.

PubMed

1995-09-18

This final rule revises the Medicare conditions for coverage of suppliers of end-stage renal disease services. The revisions remove general language in the regulations regarding water quality; incorporate by reference standards for monitoring the quality of water used in dialysis as published by the Association for the Advancement of Medical Instrumentation (AAMI) in its document, "Hemodialysis Systems" (second edition); and update existing regulations to incorporate by reference the second edition of AAMI's voluntary guidelines on "Reuse of Hemodialyzers."

Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification.

PubMed

Ali, Aasim Musa Mohamed; Kallenborn, Roland; Sydnes, Leiv Kristen; Rønning, Helene Thorsen; Alarif, Walied Mohamed; Al-Lihaibi, Sultan

2017-06-01

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ 1/2 ) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ 1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI - -QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.

Vacuum Ultraviolet Photoionization of Complex Chemical Systems

DOE PAGES

Kostko, Oleg; Bandyopadhyay, Biswajit; Ahmed, Musahid

2016-02-24

Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems in this paper. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion–molecule reactionsmore » and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. Finally, new directions in coupling VUV radiation to interrogate complex chemical systems are discussed.« less

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).

Water loss from terrestrial planets orbiting ultracool dwarfs: Implications for the planets of TRAPPIST-1

NASA Astrophysics Data System (ADS)

Bolmont, Emeline; Selsis, Franck; Owen, James E.; Ribas, Ignasi; Raymond, Sean N.; Leconte, Jérémy; Gillon, Michael

2016-10-01

Ultracool dwarfs (UCDs) encompass the population of extremely low mass stars (later than M6-type) and brown dwarfs.Because UCDs cool monotonically, their habitable zone (HZ) sweeps inward in time.Assuming they possess water, planets found in the HZ of UCDs have experienced a runaway greenhouse phase too hot for liquid water prior to entering the HZ.It has been proposed that such planets are desiccated by this hot early phase and enter the HZ as dry, inhospitable worlds.Here we model the water loss during this pre-HZ hot phase taking into account recent upper limits on the XUV emission of UCDs and using 1D radiation-hydrodynamic simulations.We address the whole range of UCDs but also focus on the planets b, c and d recently found around the 0.08 M⊙ dwarf TRAPPIST-1.Despite assumptions maximizing the FUV-photolysis of water and the XUV-driven escape of hydrogen, we find that planets can retain significant amounts of water in the HZ of UCDs, with a sweet spot in the 0.04-0.06 M⊙ range.We also studied the TRAPPIST-1 system using observed constraints on the XUV-flux.We found that TRAPPIST-1b and c can lose as much as 15 Earth Ocean and planet d -- which may be inside the HZ depending on its actual period -- may have lost less than 1 Earth Ocean.Depending on its initial content, they could have enough water to remain habitable.TRAPPIST-1 planets are key targets for atmospheric characterization and could provide strong constraints on the water erosion around UCDs.

Puget Sound Tidal Energy In-Water Testing and Development Project Final Technical Report

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

Collar, Craig W

2012-11-16

Tidal energy represents potential for the generation of renewable, emission free, environmentally benign, and cost effective energy from tidal flows. A successful tidal energy demonstration project in Puget Sound, Washington may enable significant commercial development resulting in important benefits for the northwest region and the nation. This project promoted the United States Department of Energy's Wind and Hydropower Technologies Program's goals of advancing the commercial viability, cost-competitiveness, and market acceptance of marine hydrokinetic systems. The objective of the Puget Sound Tidal Energy Demonstration Project is to conduct in-water testing and evaluation of tidal energy technology as a first step towardmore » potential construction of a commercial-scale tidal energy power plant. The specific goal of the project phase covered by this award was to conduct all activities necessary to complete engineering design and obtain construction approvals for a pilot demonstration plant in the Admiralty Inlet region of the Puget Sound. Public Utility District No. 1 of Snohomish County (The District) accomplished the objectives of this award through four tasks: Detailed Admiralty Inlet Site Studies, Plant Design and Construction Planning, Environmental and Regulatory Activities, and Management and Reporting. Pre-Installation studies completed under this award provided invaluable data used for site selection, environmental evaluation and permitting, plant design, and construction planning. However, these data gathering efforts are not only important to the Admiralty Inlet pilot project. Lessons learned, in particular environmental data gathering methods, can be applied to future tidal energy projects in the United States and other parts of the world. The District collaborated extensively with project stakeholders to complete the tasks for this award. This included Federal, State, and local government agencies, tribal governments, environmental groups, and

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.

Rapid method for monitoring N-nitrosodimethylamine in drinking water at the ng/L level without pre-concentration using high-performance liquid chromatography-chemiluminescence detection.

PubMed

Kodamatani, Hitoshi; Yamasaki, Hitomi; Sakaguchi, Takeru; Itoh, Shinya; Iwaya, Yoshimi; Saga, Makoto; Saito, Keiitsu; Kanzaki, Ryo; Tomiyasu, Takashi

2016-08-19

As a contaminant in drinking water, N-nitrosodimethylamine (NDMA) is of great concern because of its carcinogenicity; it has been limited to levels of ng/L by regulatory bodies worldwide. Consequently, a rapid and sensitive method for monitoring NDMA in drinking water is urgently required. In this study, we report an improvement of our previously proposed HPLC-based system for NDMA determination. The approach consists of the HPLC separation of NDMA, followed by NDMA photolysis to form peroxynitrite and detection with a luminol chemiluminescence reaction. The detection limit for the improved HPLC method was 0.2ng/L, which is 10 times more sensitive than our previously reported system. For tap water measurements, only the addition of an ascorbic acid solution to eliminate residual chlorine and passage through an Oasis MAX solid-phase extraction cartridge are needed. The proposed NDMA determination method requires a sample volume of less than 2mL and a complete analysis time of less than 15min per sample. The method was utilized for the long-term monitoring of NDMA in tap water. The NDMA level measured in the municipal water survey was 4.9ng/L, and a seasonal change of the NDMA concentration in tap water was confirmed. The proposed method should constitute a useful NDMA monitoring method for protecting drinking water quality. Copyright © 2016 Elsevier B.V. All rights reserved.

Identification of transformation products during advanced oxidation of diatrizoate: Effect of water matrix and oxidation process.

PubMed

Azerrad, Sara P; Lütke Eversloh, Christian; Gilboa, Maayan; Schulz, Manoj; Ternes, Thomas; Dosoretz, Carlos G

2016-10-15

Removal of micropollutants from reverse osmosis (RO) brines of wastewater desalination by oxidation processes is influenced by the scavenging capacity of brines components, resulting in the accumulation of transformation products (TPs) rather than complete mineralization. In this work the iodinated contrast media diatrizoate (DTZ) was used as model compound due to its relative resistance to oxidation. Identification of TPs was performed in ultrapure water (UPW) and RO brines applying nonthermal plasma (NTP) and UVA-TiO2 as oxidation techniques. The influence of main RO brines components in the formation and accumulation of TPs, such as chloride, bicarbonate alkalinity and humic acid, was also studied during UVA-TiO2. DTZ oxidation pattern in UPW resulted similar in both UVA-TiO2 and NTP achieving 66 and 61% transformation, respectively. However, DTZ transformation in RO brines was markedly lower in UVA-TiO2 (9%) than in NTP (27%). These differences can be attributed to the synergic effect of RO brines components during NTP. Moreover, reactive species other than hydroxyl radical contributed to DTZ transformation, i.e., direct photolysis in UVA-TiO2 and direct photolysis + O3 in NTP accounted for 16 and 23%, respectively. DTZ transformation led to iodide formation in both oxidation techniques but it further oxidized to iodate by ozone in NTP. In total 14 transformation products were identified in UPW of which 3 were present only in UVA-TiO2 and 2 were present exclusively in NTP; 5 of the 14 TPs were absent in RO brines. Five of them were new and were denoted as TP-474A/B, TP-522, TP-586, TP-602, TP-628. TP-522 (mono-chlorinated) was elucidated only in presence of high chloride titer-synthetic water matrix in NTP, most probably formed by active chlorine species generated in situ. TPs accumulation in RO brines was markedly different in comparison to UPW. This denotes the influence of RO brines components in the formation of reactive species that could further attack

Tryptophan and tryptophan-like substances in cloud water: Occurrence and photochemical fate

NASA Astrophysics Data System (ADS)

Bianco, Angelica; Passananti, Monica; Deguillaume, Laurent; Mailhot, Gilles; Brigante, Marcello

2016-07-01

This work investigates the occurrence and photochemical behaviour of tryptophan (TRP) in the cloud aqueous phase. The concentrations of tryptophan, TRYptophan LIke Substances (TRYLIS) and HUmic LIke Substances (HULIS) in real cloud water, collected between October 2013 and November 2014 at the top of the puy de Dôme station, were determined using the Excitation-Emission-Matrix (EEM) technique. The amount of free and complexed tryptophan (TRP) up to 10-7 M in cloud aqueous phase was quantified by HPLC-UV-fluorescence analysis, and its photoreactivity under sun-simulated conditions was investigated in synthetic water samples mimicking cloud aqueous phase compositions (oceanic and continental origins). TRP undergoes direct photolysis, and its degradation is enhanced in the presence of naturally occurring species able to photo-generate hydroxyl radicals (HOrad). The polychromatic quantum yield of TRP (ϕ290-340nmTRP) is estimated to be 8.37 × 10-4 between 290 and 340 nm, corresponding to the degradation rate (RTRPd) of 1.29 × 10-11 M s-1 under our irradiation conditions. The degradation is accelerated up to 3.65 × 10-10 and 8.26 × 10-10 M s-1 in synthetic oceanic and continental cloud water samples doped with 100 μM hydrogen peroxide, respectively. Hydroxyl radical-mediated transformation leads to the generation of different functionalized and oxidized products, as well as small carboxylic acids, such as formate and acetate. Moreover, fluorescent signals of irradiated solutions indicate the formation of HULIS.

The Exosphere of Ceres Generated by Photolysis and Radiolysis

NASA Astrophysics Data System (ADS)

Tseng, W. L.; Ip, W. H.; Kuan, Y. J.

2016-12-01

Ceres is the largest object (with a diameter of 950 km) among the main-belt asteroids. The OH cloud, the photodissociated products of H2O, was suggested by the IUE (International Ultraviolet Explorer) observations to be present around Ceres (A'Hearn and Feldman, 1992). Recently, Kuppers et al. (2014) reported a direct detection of water vapor by Herschel that > 1026 molecules s-1was produced from localized sources on Ceres' surface. Most excitingly, the Dawn images showed that a haze layer consisting of water-ice particles and dust was found above the Occator crater (Nathues et al., 2015). The haze was also shown to have a diurnal change of brightness, indicating a comet-like sublimation activity. In addition, subsurface outgassing (e.g., cryovolcanism and/or the plume activity similar to that found in Enceladus) is another possible source mechanism, which is not fully understood yet. Following the Ceres' exospheric model of Tu et al. (2014), here we focus on O2, O3 and H2O2 molecules, which are the primary products of radiolytic and photolytic decomposition of water ice, and possibly the CO2 and SO2 molecules produced from the impurities. We will compute the source rates from various production mechanisms and simulate the cloud morphologies. Then we will compare with the available data (e.g., the atomic oxygen emission observed by HST from Roth et al., 2016) and seek for any evidence in the ground-based millimeter/submillimeter observations. Understanding the chemical composition of Ceres and its evolved exosphere, in analogy to comets and the icy satellites, would reveal the secret of the origin and evolution of the solar system. 1. A'Hearn, M.F., Feldman, P.D., (1992) Water vaporization on Ceres. Icarus 98, 389-407. 2. Küppers, M., et al., (2014) Localized sources of water vapour on the dwarf planet (1) Ceres. Nature 505, 525-527. 3. Nathues, A., et al. (2015), Sublimation in bright spots on (1) Ceres, Nature, 528(7581), 237-240. 4. Tu, L., W.-H. Ip, and Y

[Viruses in water].

PubMed

Zvizdić, Sukrija; Rodinis-Pejić, Ines; Avdić-Kamberović, Fadila; Mujkić, Anesa; Hamzić, Sadeta; Puvacić, Sandra; Tandir, Salih; Kudumović, Mensura

2005-01-01

The article elaborates the significance of water, which is necessary for the maintenance of an organism and specifies its daily needs in human beings. Reference data on the early isolations of viruses from sewage water and modern understanding on the occurring virus species are listed. The article considers virus survival in sewage and flowing water and other fresh and marine water systems as well as marine silt or fruit. Finally, we give here an overview of basic features of individual virus kinds that are potential water contaminants.

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

Concept and Connotation of Water Resources Carrying Capacity in Water Ecological Civilization Construction

NASA Astrophysics Data System (ADS)

Chao, Zhilong; Song, Xiaoyu; Feng, Xianghua

2018-01-01

Water ecological civilization construction is based on the water resources carrying capacity, guided by the sustainable development concept, adhered to the human-water harmony thoughts. This paper has comprehensive analyzed the concept and characteristics of the carrying capacity of water resources in the water ecological civilization construction, and discussed the research methods and evaluation index system of water carrying capacity in the water ecological civilization construction, finally pointed out that the problems and solutions of water carrying capacity in the water ecological civilization construction and put forward the future research prospect.

New York harbor water quality survey, 1993. (Includes appendices). Final report

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

Brosnan, T.M.; O`Shea, M.L.

1994-11-30

The 84th Water Quality Survey of New York Harbor was performed by the New York City Department of Environmental Protection in 1993. Common indicators of water quality which were monitored include human health indicators, such as the sewage-related coliform bacteria, and environmental health indicators such as dissolved oxygen, the nutrients nitrogen and phosphorus, and phytoplankton densities as estimated from chlorophyll `a`.

Water conservation study. Badger Army Ammunition Plant, Baraboo, Wisconsin. Final report

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

NONE

1995-05-01

The purpose of this water conservation study is to identify projects which result in energy maintenance and cost savings in the process water distribution system at Badger Army Ammunition Plant (BAAP) in Baraboo, Wisconsin. A leak detection survey was performed on all process water piping with a diameter of 6 inches or greater. The leak detection analysis was performed using a combination of listening devices and preamplified-transducer systems to identify the majority of leak locations. When the location of the leak could not be readily identified using these methods, a leak correlator was used. The leak correlator determines leak locationmore » based on the time it takes for sound to travel from the leak to a waterline connection point.« 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

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.

State and territorial use of ground-water strategy grant funds (Section 106 Clean Water Act). Technical report (Final)

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

Not Available

1987-05-01

This document reports on the activities of States in FY 85 and 86 in developing and implementing State ground-water protection strategies using Clean Water Act Section 106 funds. Every State and all but one territory has participated in the program. Strategies have included emphasis on the need to consolidate State and local agency efforts, and to provide clear policy direction, greater public awareness and education concerning ground-water protection.

d-Amino acids in molecular evolution in space - Absolute asymmetric photolysis and synthesis of amino acids by circularly polarized light.

PubMed

Sugahara, Haruna; Meinert, Cornelia; Nahon, Laurent; Jones, Nykola C; Hoffmann, Søren V; Hamase, Kenji; Takano, Yoshinori; Meierhenrich, Uwe J

2018-07-01

Living organisms on the Earth almost exclusively use l-amino acids for the molecular architecture of proteins. The biological occurrence of d-amino acids is rare, although their functions in various organisms are being gradually understood. A possible explanation for the origin of biomolecular homochirality is the delivery of enantioenriched molecules via extraterrestrial bodies, such as asteroids and comets on early Earth. For the asymmetric formation of amino acids and their precursor molecules in interstellar environments, the interaction with circularly polarized photons is considered to have played a potential role in causing chiral asymmetry. In this review, we summarize recent progress in the investigation of chirality transfer from chiral photons to amino acids involving the two major processes of asymmetric photolysis and asymmetric synthesis. We will discuss analytical data on cometary and meteoritic amino acids and their potential impact delivery to the early Earth. The ongoing and future ambitious space missions, Hayabusa2, OSIRIS-REx, ExoMars 2020, and MMX, are scheduled to provide new insights into the chirality of extraterrestrial organic molecules and their potential relation to the terrestrial homochirality. This article is part of a Special Issue entitled: d-Amino acids: biology in the mirror, edited by Dr. Loredano Pollegioni, Dr. Jean-Pierre Mothet and Dr. Molla Gianluca. Copyright © 2018 Elsevier B.V. All rights reserved.

KEY COMPARISON: Final report of the SIM 60Co absorbed-dose-to-water comparison SIM.RI(I)-K4

NASA Astrophysics Data System (ADS)

Ross, C. K.; Shortt, K. R.; Saravi, M.; Meghzifene, A.; Tovar, V. M.; Barbosa, R. A.; da Silva, C. N.; Carrizales, L.; Seltzer, S. M.

2008-01-01

Transfer chambers were used to compare the standards for 60Co absorbed dose to water maintained by seven laboratories. Six of the laboratories were members of the Sistema Interamericano de Metrología (SIM) regional metrology organization while the seventh was the International Atomic Energy Agency (IAEA) laboratory in Vienna. The National Research Council (NRC) acted as the pilot laboratory for the comparison. Because of the participation of laboratories holding primary standards, the comparison results could be linked to the key comparison reference value maintained by the Bureau International des Poids et Mesures (BIPM). The results for all laboratories were within the expanded uncertainty (two standard deviations) of the reference value. The estimated relative standard uncertainty on the comparison between any pair of laboratories ranged from 0.6% to 1.4%. The largest discrepancy between any two laboratories was 1.3%. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCRI Section I, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

The divergent fates of primitive hydrospheric water on Earth and Mars

NASA Astrophysics Data System (ADS)

Wade, Jon; Dyck, Brendan; Palin, Richard M.; Moore, James D. P.; Smye, Andrew J.

2017-12-01

Despite active transport into Earth’s mantle, water has been present on our planet’s surface for most of geological time. Yet water disappeared from the Martian surface soon after its formation. Although some of the water on Mars was lost to space via photolysis following the collapse of the planet’s magnetic field, the widespread serpentinization of Martian crust suggests that metamorphic hydration reactions played a critical part in the sequestration of the crust. Here we quantify the relative volumes of water that could be removed from each planet’s surface via the burial and metamorphism of hydrated mafic crusts, and calculate mineral transition-induced bulk-density changes at conditions of elevated pressure and temperature for each. The metamorphic mineral assemblages in relatively FeO-rich Martian lavas can hold about 25 per cent more structurally bound water than those in metamorphosed terrestrial basalts, and can retain it at greater depths within Mars. Our calculations suggest that in excess of 9 per cent by volume of the Martian mantle may contain hydrous mineral species as a consequence of surface reactions, compared to about 4 per cent by volume of Earth’s mantle. Furthermore, neither primitive nor evolved hydrated Martian crust show noticeably different bulk densities compared to their anhydrous equivalents, in contrast to hydrous mafic terrestrial crust, which transforms to denser eclogite upon dehydration. This would have allowed efficient overplating and burial of early Martian crust in a stagnant-lid tectonic regime, in which the lithosphere comprised a single tectonic plate, with only the warmer, lower crust involved in mantle convection. This provided an important sink for hydrospheric water and a mechanism for oxidizing the Martian mantle. Conversely, relatively buoyant mafic crust and hotter geothermal gradients on Earth reduced the potential for upper-mantle hydration early in its geological history, leading to water being retained

The divergent fates of primitive hydrospheric water on Earth and Mars.

PubMed

Wade, Jon; Dyck, Brendan; Palin, Richard M; Moore, James D P; Smye, Andrew J

2017-12-20

Despite active transport into Earth's mantle, water has been present on our planet's surface for most of geological time. Yet water disappeared from the Martian surface soon after its formation. Although some of the water on Mars was lost to space via photolysis following the collapse of the planet's magnetic field, the widespread serpentinization of Martian crust suggests that metamorphic hydration reactions played a critical part in the sequestration of the crust. Here we quantify the relative volumes of water that could be removed from each planet's surface via the burial and metamorphism of hydrated mafic crusts, and calculate mineral transition-induced bulk-density changes at conditions of elevated pressure and temperature for each. The metamorphic mineral assemblages in relatively FeO-rich Martian lavas can hold about 25 per cent more structurally bound water than those in metamorphosed terrestrial basalts, and can retain it at greater depths within Mars. Our calculations suggest that in excess of 9 per cent by volume of the Martian mantle may contain hydrous mineral species as a consequence of surface reactions, compared to about 4 per cent by volume of Earth's mantle. Furthermore, neither primitive nor evolved hydrated Martian crust show noticeably different bulk densities compared to their anhydrous equivalents, in contrast to hydrous mafic terrestrial crust, which transforms to denser eclogite upon dehydration. This would have allowed efficient overplating and burial of early Martian crust in a stagnant-lid tectonic regime, in which the lithosphere comprised a single tectonic plate, with only the warmer, lower crust involved in mantle convection. This provided an important sink for hydrospheric water and a mechanism for oxidizing the Martian mantle. Conversely, relatively buoyant mafic crust and hotter geothermal gradients on Earth reduced the potential for upper-mantle hydration early in its geological history, leading to water being retained close to

Delayed photolysis of liposomes: a strategy for the precision timing of bolus drug release using ex-vivo photochemical sensitization

NASA Astrophysics Data System (ADS)

Kozikowski, Raymond T.; Sorg, Brian S.

2012-03-01

Chemotherapy is a standard treatment for metastatic cancer. However drug toxicity limits the dosage that can safely be used, thus reducing treatment efficacy. Drug carrier particles, like liposomes, can help reduce toxicity by shielding normal tissue from drug and selectively depositing drug in tumors. Over years of development, liposomes have been optimized to avoid uptake by the Reticuloendothelial System (RES) as well as effectively retain their drug content during circulation. As a result, liposomes release drug passively, by slow leakage, but this uncontrolled drug release can limit treatment efficacy as it can be difficult to achieve therapeutic concentrations of drug at tumor sites even with tumor-specific accumulation of the carriers. Lipid membranes can be photochemically lysed by both Type I (photosensitizer-substrate) and Type II (photosensitizer-oxygen) reactions. It has been demonstrated in red blood cells (RBCs) in vitro that these photolysis reactions can occur in two distinct steps: a light-initiated reaction followed by a thermally-initiated reaction. These separable activation steps allow for the delay of photohemolysis in a controlled manner using the irradiation energy, temperature and photosensitizer concentration. In this work we have translated this technique from RBCs to liposomal nanoparticles. To that end, we present in vitro data demonstrating this delayed bolus release from liposomes, as well as the ability to control the timing of this event. Further, we demonstrate for the first time the improved delivery of bioavailable cargo selectively to target sites in vivo.

Using the C3M Satellite Data Product to Evaluate and Constrain the Cloud Fields in the HadGEM3-UKCA Model with an Aim to Enhance Understanding of the Effects of Clouds on Atmospheric Composition via Photolysis

NASA Astrophysics Data System (ADS)

Varma, S.; Voulgarakis, A.; Liu, H.; Crawford, J. H.; Zhang, B.

2017-12-01

What drives the variability of trace gases in the troposphere is not well understood, as is the role of clouds in modulating this variability via radiative, transport, deposition, heterogeneous chemistry, and lightning effects that are associated with them. Accurately simulating tropospheric composition and its variability is of utmost importance as both could have a significant effect on the region's temperature and circulation, as well as on surface climate and the amount of UV radiation in the troposphere. In this presentation, we will examine how clouds can influence tropospheric and lower stratospheric composition through modifying solar radiation leading to changes in the local actinic flux and subsequently to photolysis, a key driver of chemistry. We will utilize C3M (a unique 3-D cloud data product merged from multiple A-Train satellites (CERES, CloudSat, CALIPSO, and MODIS) developed at the NASA Langley Research Center to evaluate the cloud fields and their vertical distribution in the HadGEM3-UKCA model developed by the Natural Environment Research Council (NERC, UK) and the Met Office. This evaluation will involve 1) comparing the effective cloud optical depth (ECOD) as calculated from C3M and the model using the approximate random overlap method, 2) applying 3-D scaling factors from C3M to the model's ECOD and analyzing the changes this makes to the model's cloud fields, and 3) running the scaled model and analyzing the impacts of this cloud field adjustment on the model's estimates of photolysis rates and key tropospheric oxidants such as ozone and OH.

Insights Into Atmospheric Aqueous Organic Chemistry Through Controlled Experiments with Cloud Water Surrogates

NASA Astrophysics Data System (ADS)

Turpin, B. J.; Ramos, A.; Kirkland, J. R.; Lim, Y. B.; Seitzinger, S.

2011-12-01

There is considerable laboratory and field-based evidence that chemical processing in clouds and wet aerosols alters organic composition and contributes to the formation of secondary organic aerosol (SOA). Single-compound laboratory experiments have played an important role in developing aqueous-phase chemical mechanisms that aid prediction of SOA formation through multiphase chemistry. In this work we conduct similar experiments with cloud/fog water surrogates, to 1) evaluate to what extent the previously studied chemistry is observed in these more realistic atmospheric waters, and 2) to identify additional atmospherically-relevant precursors and products that require further study. We used filtered Camden and Pinelands, NJ rainwater as a surrogate for cloud water. OH radical (~10-12 M) was formed by photolysis of hydrogen peroxide and samples were analyzed in real-time by electrospray ionization mass spectroscopy (ESI-MS). Discrete samples were also analyzed by ion chromatography (IC) and ESI-MS after IC separation. All experiments were performed in duplicate. Standards of glyoxal, methylglyoxal and glycolaldehyde and their major aqueous oxidation products were also analyzed, and control experiments performed. Decreases in the ion abundance of many positive mode compounds and increases in the ion abundance of many negative mode compounds (e.g., organic acids) suggest that precursors are predominantly aldehydes, organic peroxides and/or alcohols. Real-time ESI mass spectra were consistent with the expected loss of methylglyoxal and subsequent formation of pyruvate, glyoxylate, and oxalate. New insights regarding other potential precursors and products will be provided.

Photochemical Transformation of Munitions Constituents in Marine Waters

DTIC Science & Technology

2012-05-01

include catalysts such as TiO2 or additives such peroxide, Fenton’s reagent (peroxide and iron (II)), and peroxide and ozone, which are meant to speed...photoproducts. The product mixture formed by the photolysis of 2,4- and 2,6-DNT is yellow in color , while the original DNTs are colorless in solution. The...The organisms shown in Figure 12 include one marine fish (Sciaenops ocellatus, 48-hr EC-50 for embryo survival), one marine arthropod (Artemia

Photo-degradation of clofibric acid by ultraviolet light irradiation at 185 nm.

PubMed

Li, Wenzhen; Lu, Shuguang; Chen, Nuo; Gu, Xiaogang; Qiu, Zhaofu; Fan, Ji; Lin, Kuangfei

2009-01-01

As a metabolite of lipid regulators, clofibric acid (CA) was investigated in this study for its ultraviolet (UV) degradation at monochromatic wavelength of 185 nm using Milli-Q water and sewage treatment plant (STP) effluent. The effects of CA initial concentration, solution pH, humic acid (HA), nitrate and bicarbonate anions on CA degradation performances were evaluated. All CA degradation patterns well fitted the pseudo-first-order kinetic model. The results showed that OH generated from water photolysis by UV185 irradiation was involved, resulting in indirect CA photolysis but contributed less to the whole CA removal when compared to the main direct photolysis process. Acid condition favored slightly to CA degradation and other constituents in solution, such as HA (5.0-100.0 mg L(-1)), nitrate and bicarbonate anions (1.0x10(-3) mol L(-1) and 0.1 mol L(-1)), had negative effects on CA degradation. When using real STP effluent CA degradation could reach 97.4% (without filtration) and 99.3% (with filtration) after 1 hr irradiation, showing its potential mean in pharmaceuticals removal in UV disinfection unit. Mineralization tests showed that rapid chloride ion release happened, resulting in no chlorinated intermediates accumulation, and those non-chlorinated intermediate products could further be nearly completely degraded to CO2 and H2O after 6 hrs.

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.

75 FR 38754 - Safety Zone; IJSBA World Finals; Lower Colorado River, Lake Havasu, AZ

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-06

...-AA00 Safety Zone; IJSBA World Finals; Lower Colorado River, Lake Havasu, AZ AGENCY: Coast Guard, DHS... navigable waters of Lake Havasu on the lower Colorado River in support of the IJSBA World Finals. This... International Jet Sports Boating Association is sponsoring the IJSBA World Finals. The event will consist of 300...

Photochemical Cycling of Humic-Like Substances in Atmospheric Aerosols

NASA Astrophysics Data System (ADS)

Rincon, A. G.; Guzman, M. I.; Hoffmann, M. R.; Colussi, A. J.

2007-12-01

Colored, humic-like substances (HULIS) arising from the biodegradation of organic detritus are widespread in natural surface waters, where they ultimately undergo solar photolysis into small alpha-dicarbonylic species, such as glyoxal, glyoxylic and pyruvic acids. Diversely generated and chemically dissimilar HULIS are also found in the atmospheric aerosol. How are significant levels of colored HULIS produced and sustained in the concentrated aerosol phase under intense solar irradiation? Here, this issue is tackled by investigating the solar photolysis of aqueous pyruvic acid (PA) solutions at concentrations representative of the atmospheric aerosol using UV-absorption, high resolution electrospray mass, and nuclear magnetic resonance spectrometries. Under such conditions, PA is not photodegraded but yields polyfunctional polymers, whose mass and UV-absorption spectra remain unaffected after 3, 8 and 22 h photolysis. Unless diluted, these polymers undergo condensation/polymerization in the post-photolysis period into mass < 700 Da species that absorb in the visible, and are bleached upon resuming irradiation. The re- photolyzed solutions recover the mass and UV-absorption spectra of first photolyzed solutions. Whereas initial pH has no effect on the mechanism of reaction, ammonium bisulfate, a major component of the aerosol, markedly influences these processes. These findings suggest that the chemical identity and concentration levels of complex organic substances in the aerosol are the result of dynamic photochemical processing in the condensed phase.

Characterizing Field Biodegradation of N-nitrosodimethylamine (NDMA) in Groundwater with Active Reclaimed Water Recharge

NASA Astrophysics Data System (ADS)

McCraven, S.; Zhou, Q.; Garcia, J.; Gasca, M.; Johnson, T.

2007-12-01

N-Nitrosodimethylamine (NDMA) is an emerging contaminant in groundwater, because of its aqueous miscibility, exceptional animal toxicity, and human carcinogenicity. NDMA detections in groundwater have been tracked to either decomposition of unsymmetrical dimethylhydrazine (UDMH) used in rocket fuel facilities or chlorine disinfection in wastewater reclamation plants. Laboratory experiments on both unsaturated and saturated soil samples have demonstrated that NDMA can be biodegraded by microbial activity, under both aerobic and anaerobic conditions. However, very limited direct evidence for its biodegradation has been found from the field in saturated groundwater. Our research aimed to evaluate photolysis and biodegradation of NDMA occurring along the full travel path - from wastewater reclamation plant effluent, through rivers and spreading grounds, to groundwater. For this evaluation, we established an extensive monitoring network to characterize NDMA concentrations at effluent discharge points, surface water stations, and groundwater monitoring and production wells, during the operation of the Montebello Forebay Groundwater Recharge facilities in Los Angeles County, California. Field monitoring for NDMA has been conducted for more than six years, including 32 months of relatively lower NDMA concentrations in effluent, 43 months of elevated NDMA effluent concentrations, and 7 months with significantly reduced NDMA effluent concentrations. The NDMA effluent concentration increase and significant concentration decrease were caused by changes in treatment processes. The NDMA sampling data imply that significant biodegradation occurred in groundwater, accounting for a 90% mass reduction of NDMA over the six-year monitoring period. In addition, the occurrence of a discrete well monitored effluent release during the study period allowed critical analysis of the fate of NDMA in a well- characterized, localized groundwater flow subsystem. The data indicate that 80% of the

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.

Particle-Laden Leidenfrost Droplets: Final-Stage Observations

NASA Astrophysics Data System (ADS)

Fang, Zecong; Xu, Jie

2015-03-01

Little interest has been paid to the final stage of a Leidenfrost droplet until a recent study by Celestini et al [Phys. Rev. Lett. 109, 034501 (2012)] reporting an unexpected take-off phenomenon of micrometer sized pure liquid droplets (Rl < R water Leidenfrost droplets (R >Ri), which behave quite differently from the previous study. While an originally micrometer sized Leidenfrost droplet takes off due to breakdown of lubrication regime, and hovers above its vapor layer until disappearing in the final stage of evaporation, an originally millimetric Leidenfrost drop is observed to hover and oscillate, taking off and falling back consecutively. We further report another interesting observation on water droplets containing micrometric glass beads. These droplets spontaneously organize and buckle together during evaporation. In addition to oscillation just like pure droplets, these particle-laden drops create an unexpected explosive shoot-up at the end of evaporation.

Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

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

Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu

Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O 3 - and OH-initiated reactions during the day and reactions with NO 3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water,more » 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.« less

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.

Methods to predict seasonal high water table (SHGWT) : final report.

DOT National Transportation Integrated Search

2017-04-03

The research study was sectioned into 5 separate tasks. Task 1 included defining the seasonal high ground water table (SHGWT); describing : methods and techniques used to determine SHGWTs; identify problems associated with estimating SHGWT conditions...