Magnetic heterogeneous catalytic ozonation: a new removal method for phenol in industrial wastewater

PubMed Central

2014-01-01

In this study, a new strategy in catalytic ozonation removal method for degradation of phenol from industrial wastewater was investigated. Magnetic carbon nano composite as a novel catalyst was synthesized, characterized and then used in the catalytic ozonation process (COP) and compared with the single ozonation process (SOP). The influential parameters were all investigated. The results showed that the removal efficiency of phenol and COD (chemical oxygen demand) in COP (98.5%, 69.8%) was higher than those of SOP (78.7%, 50.5%) and the highest catalytic potential was achieved at optimal neutral pH. First order modeling demonstrated that the reactions were dependent on the concentration of catalyst, with kinetic constants varying from 0.023 1/min (catalyst = 0 g/L) to 0.071 1/min (catalyst = 4 g/L), whereby the optimum dosage of catalyst was found to be 2 g/L. Furthermore, the catalytic properties of the catalyst remained almost unchanged after 5-time reuse. The results regarding the biodegradability of the effluent showed that a 5-min reaction time in COP reduced the concentrations of phenol and COD to the acceptable levels for the efficient post-treatment in the SBR in a 4-h cycle period. Finally, this combined system is proven to be a technically effective method for treating phenolic contaminants. PMID:24572145

Effects of ozone-vegetation coupling on surface ozone air quality via biogeochemical and meteorological feedbacks

NASA Astrophysics Data System (ADS)

Sadiq, Mehliyar; Tai, Amos P. K.; Lombardozzi, Danica; Martin, Maria Val

2017-02-01

Tropospheric ozone is one of the most hazardous air pollutants as it harms both human health and plant productivity. Foliage uptake of ozone via dry deposition damages photosynthesis and causes stomatal closure. These foliage changes could lead to a cascade of biogeochemical and biogeophysical effects that not only modulate the carbon cycle, regional hydrometeorology and climate, but also cause feedbacks onto surface ozone concentration itself. In this study, we implement a semi-empirical parameterization of ozone damage on vegetation in the Community Earth System Model to enable online ozone-vegetation coupling, so that for the first time ecosystem structure and ozone concentration can coevolve in fully coupled land-atmosphere simulations. With ozone-vegetation coupling, present-day surface ozone is simulated to be higher by up to 4-6 ppbv over Europe, North America and China. Reduced dry deposition velocity following ozone damage contributes to ˜ 40-100 % of those increases, constituting a significant positive biogeochemical feedback on ozone air quality. Enhanced biogenic isoprene emission is found to contribute to most of the remaining increases, and is driven mainly by higher vegetation temperature that results from lower transpiration rate. This isoprene-driven pathway represents an indirect, positive meteorological feedback. The reduction in both dry deposition and transpiration is mostly associated with reduced stomatal conductance following ozone damage, whereas the modification of photosynthesis and further changes in ecosystem productivity are found to play a smaller role in contributing to the ozone-vegetation feedbacks. Our results highlight the need to consider two-way ozone-vegetation coupling in Earth system models to derive a more complete understanding and yield more reliable future predictions of ozone air quality.

A novel "wastes-treat-wastes" technology: role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochemical wastewater.

PubMed

Chen, Chunmao; Yu, Ji; Yoza, Brandon A; Li, Qing X; Wang, Gang

2015-04-01

Catalytic ozonation is a promising wastewater treatment technology. However, the high cost of the catalyst hinders its application. A novel "wastes-treat-wastes" technology was developed to reuse spent fluid catalytic cracking catalysts (sFCCc) for the ozonation of petrochemical wastewater in this study. Multivalent vanadium (V(4+) and V(5+)), iron (Fe(2+) and Fe(3+)) and nickel (Ni(2+)) oxides that are distributed on the surface of sFCCc and poisoned FCC catalysts are the catalytic components for ozonation. The sFCCc assisted catalytic ozonation (sFCCc-O) of nitrobenzene indicated that the sFCCc significantly promoted hydroxyl radical mediated oxidation. The degradation rate constant of nitrobenzene in sFCCc-O (0.0794 min(-1) at 298 K) was approximately doubled in comparison with that in single ozonation (0.0362 min(-1) at 298 K). The sFCCc-O of petrochemical wastewater increased chemical oxygen demand removal efficiency by three-fold relative to single ozonation. The number of oxygen-containing (Ox) polar contaminants in the effluent (253) from sFCCc-O treatment decreased to about 70% of the initial wastewater (353). The increased oxygen/carbon atomic ratio and decreased number of Ox polar contaminants indicated a high degree of degradation. The present study showed the role and potential of sFCCc for catalytic ozonation of petrochemical wastewater, particularly in an advantage of the cost-effectiveness through "wastes-treat-wastes". Copyright © 2015 Elsevier Ltd. All rights reserved.

Does coupled ocean enhance ozone-hole-induced Southern Hemisphere circulation changes?

NASA Astrophysics Data System (ADS)

Son, S. W.; Han, B. R.; Kim, S. Y.; Park, R.

2017-12-01

The ozone-hole-induced Southern Hemisphere (SH) circulation changes, such as poleward shift of westerly jet and Hadley cell widening, have been typically explored with either coupled general circulation models (CGCMs) prescribing stratospheric ozone or chemistry-climate models (CCMs) prescribing surface boundary conditions. Only few studies have utilized ocean-coupled CCMs with a relatively coarse resolution. To better quantify the role of interactive chemistry and coupled ocean in the ozone-hole-induced SH circulation changes, the present study examines a set of CGCM and CCM simulations archived for the Coupled Model Intercomparison Project phase 5 (CMIP5) and CCM initiative (CCMI). Although inter-model spread of Antarctic ozone depletion is substantially large especially in the austral spring, both CGCMs with relatively simple ozone chemistry and CCMs with fully interactive comprehensive chemistry reasonably well reproduce long-term trends of Antarctic ozone and the associated polar-stratospheric temperature changes. Most models reproduce a poleward shift of SH jet and Hadley-cell widening in the austral summer in the late 20th century as identified in reanalysis datasets. These changes are quasi-linearly related with Antarctic ozone changes, confirming the critical role of Antarctic ozone depletion in the austral-summer zonal-mean circulation changes. The CGCMs with simple but still interactive ozone show slightly stronger circulation changes than those with prescribed ozone. However, the long-term circulation changes in CCMs are largely insensitive to the coupled ocean. While a few models show the enhanced circulation changes when ocean is coupled, others show essentially no changes or even weakened circulation changes. This result suggests that the ozone-hole-related stratosphere-troposphere coupling in the late 20th century may be only weakly sensitive to the coupled ocean.

Ozone decomposition

PubMed Central

Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

2014-01-01

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO2 in the decomposition of high concentration ozone

NASA Astrophysics Data System (ADS)

Ding, Yanhua; Zhang, Xiaolei; Chen, Li; Wang, Xiaorui; Zhang, Na; Liu, Yufeng; Fang, Yongzheng

2017-06-01

The catalytic decomposition of gaseous ozone (O3) is investigated using anatase TiO2 (A-TiO2) and Aluminum-reduced A-TiO2 (ARA-TiO2) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO2, the ARA-TiO2 sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy ;capture; for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O3 without any light irradiation has been greatly improved from 4.8% on A-TiO2 to 100% on ARA-TiO2 under the RH=100% condition. The ozone conversion over T500/ARA-TiO2 catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m3 ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO2 possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti3+/Ti4+couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO2 in the thermal-catalytic field.

Heterogeneous catalytic ozonation of dibutyl phthalate in aqueous solution in the presence of iron-loaded activated carbon.

PubMed

Huang, Yuanxing; Cui, Chenchen; Zhang, Daofang; Li, Liang; Pan, Ding

2015-01-01

Iron-loaded activated carbon was prepared and used as catalyst in heterogeneous catalytic ozonation of dibutyl phthalate (DBP). The catalytic activity of iron-loaded activated carbon was investigated under various conditions and the mechanisms of DBP removal were deduced. Characterization of catalyst indicated that the iron loaded on activated carbon was mainly in the form of goethite, which reduced its surface area, pore volume and pore diameter. The presence of metals on activated carbon positively contributed to its catalytic activity in ozonation of DBP. Iron loading content of 15% and initial water pH of 8 achieved highest DBP removal among all the tried conditions. Catalyst dosage of 10 mg L(-1) led to approximately 25% of increase in DBP (initial concentration 2 mg L(-1)) removal in 60 min as compared with ozone alone, and when catalyst dosage increased to 100 mg L(-1), the DBP removal was further improved by 46%. Based on a comparison of reaction rates for direct and indirect transformation of DBP, the increased removal of DBP in this study likely occurred via transformation of ozone into hydroxyl radicals on the catalyst surface. Copyright © 2014 Elsevier Ltd. All rights reserved.

Catalytic ozonation of aqueous phenol over metal-loaded HZSM-5.

PubMed

Amin, Nor Aishah Saidina; Akhtar, Javaid; Rai, H K

2011-01-01

The performances of HZSM-5 and transition metal-loaded HZSM-5 (Mn, Cu, Fe, Ti) catalysts during catalytic ozonation of phenol have been investigated. It was observed the performance order for removal of phenol and COD was Mn/HZSM-5 > Fe/HZSM-5 > Cu/HZSM-5 > Ti/HZSM-5 > HZSM-5. The presence of metals on HZSM-5 enhanced the phenol removal capability of HZSM-5. Mn loading on HZSM-5 was optimized due to its high phenol removal capability amongst metal-loaded HZSM-5 catalysts. Experimental results suggested that low amount of Mn loading on HZSM-5 was sufficient for HZSM-5 to act as catalyst and adsorbent. A maximum of 95.8 wt% phenols and 70.2 wt% COD were removed over 2 wt% Mn/HZSM-5 in 120 min. It was supposed that transition metals mainly acted as ozone decomposers due to their multiple oxidation states that enhanced the ozonation of phenol.

Catalytic ozonation of p-chlorobenzoic acid by activated carbon and nickel supported activated carbon prepared from petroleum coke.

PubMed

Li, Xukai; Zhang, Qiuyun; Tang, Lili; Lu, Ping; Sun, Fengqiang; Li, Laisheng

2009-04-15

The aim of this research was to investigate catalytic activity of petroleum coke, activated carbon (AC) prepared from this material, Ni supported catalyst on activated carbon (Ni/AC) in the ozonation of aqueous phase p-chlorobenzoic acid (p-CBA). Activated carbon and Ni/AC catalyst were characterized by XRD and SEM. The presence of petroleum coke did not improve the degradation of p-CBA compared to ozonation alone, but it was advantageous for p-CBA mineralization (total organic carbon, TOC, reduction), indicating the generation of highly oxidant species (*OH) in the medium. The presence of either activated carbon or Ni/AC considerably improves TOC removal during p-CBA ozonation. Ni/AC catalyst shows the better catalytic activity and stability based on five repeated tests during p-CBA ozonation. During the ozonation (50 mg/h ozone flow rate) of a 10 mg/L p-CBA (pH 4.31), it can be more mineralized in the presence of Ni/AC catalyst (5.0 g/L), TOC removal rate is over 60% in 60 min, 43% using activated carbon as catalyst, only 30% with ozonation alone.

Impacts of ozone-vegetation coupling and feedbacks on global air quality, ecosystems and food security

NASA Astrophysics Data System (ADS)

Tai, A. P. K.

2016-12-01

Surface ozone is an air pollutant of significant concerns due to its harmful effects on human health, vegetation and crop productivity. Chronic ozone exposure is shown to reduce photosynthesis and interfere with gas exchange in plants, thereby influencing surface energy balance and biogeochemical fluxes with important ramifications for climate and atmospheric composition, including possible feedbacks onto ozone itself that are not well understood. Ozone damage on crops has been well documented, but a mechanistic understanding is not well established. Here we present several results pertaining to the effects of ozone-vegetation coupling on air quality, ecosystems and agriculture. Using the Community Earth System Model (CESM), we find that inclusion of ozone damage on plants reduces the global land carbon sink by up to 5%, while simulated ozone is enhanced by up to 6 ppbv North America, Europe and East Asia. This strong positive feedback on ozone air quality via ozone-vegetation coupling arises mainly from reduced stomatal conductance, which induces two feedback pathways: 1) reduced dry deposition and ozone uptake; and 2) reduced evapotranspiration that enhances vegetation temperature and thus isoprene emission. Using the same ozone-vegetation scheme in a crop model within CESM, we further examine the impacts of historical ozone exposure on global crop production. We contrast our model results with a separate statistical analysis designed to characterize the spatial variability of crop-ozone-temperature relationships and account for the confounding effect of ozone-temperature covariation, using multidecadal global datasets of crop yields, agroclimatic variables and ozone exposures. We find that several crops (especially C4 crops such as maize) exhibit stronger sensitivities to ozone than found by field studies or in CESM simulations. We also find a strong anticorrelation between crop sensitivities and average ozone levels, reflecting biological adaptive ozone

Direct catalytic cross-coupling of organolithium compounds

NASA Astrophysics Data System (ADS)

Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

2013-08-01

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

Catalytic ozonation of dimethyl phthalate and chlorination disinfection by-product precursors over Ru/AC.

PubMed

Wang, Jianbing; Zhou, Yunrui; Zhu, Wanpeng; He, Xuwen

2009-07-15

Catalytic ozonation of dimethyl phthalate (DMP) in aqueous solution (5mg/L) under various reactions was performed to examine the effect of catalyst dosage, catalyst particle size, ozone dosage, and gas flow rate on the mineralization of DMP. The mineralization of DMP can be achieved via ozonation and the presence of Ru/AC could greatly accelerate the mineralization rate of DMP in ozonation process. In the continuous experiment of the Ru/AC catalyzed ozonation of DMP, total organic carbon (TOC) removals were kept stable around 75% during 42 h reaction. No leaching of ruthenium was observed in the treated water samples. The treatment of natural water using Ru/AC+O(3), Ru/AC+O(2) and ozonation alone was studied. In the Ru/AC+O(3) process, TOC removals, the reductions of the haloacetic acid formation potentials (HAAFPs), and the reductions of the trihalomethane formation potentials (THMFPs) of 11 water samples were 22-44%, 39-61% and 50-65%, respectively. Ru/AC+O(3) process was much more effective than ozonation alone for TOC removal and the reduction of disinfection by-product formation potential (DBPFP) in the treatment of natural water. It is a promising water treatment technology.

Ozone and Ozone By-Products in the Cabins of Commercial Aircraft

PubMed Central

Weisel, Clifford; Weschler, Charles J.; Mohan, Kris; Vallarino, Jose; Spengler, John D.

2013-01-01

The aircraft cabin represents a unique indoor environment due to its high surface-to-volume ratio, high occupant density and the potential for high ozone concentrations at cruising altitudes. Ozone was continuously measured and air was sampled on sorbent traps, targeting carbonyl compounds, on 52 transcontinental U.S. or international flights between 2008 and 2010. The sampling was predominantly on planes that did not have ozone scrubbers (catalytic converters). Peak ozone levels on aircraft without catalytic convertors exceeded 100 ppb, with some flights having periods of more than an hour when the ozone levels were > 75ppb. Ozone was greatly reduced on relatively new aircraft with catalytic convertors, but ozone levels on two flights whose aircraft had older convertors were similar to those on planes without catalytic convertors. Hexanal, heptanal, octanal, nonanal, decanal and 6-methyl-5-hepten-2-one (6-MHO) were detected in the aircraft cabin at sub- to low ppb levels. Linear regression models that included the log transformed mean ozone concentration, percent occupancy and plane type were statistically significant and explained between 18 and 25% of the variance in the mixing ratio of these carbonyls. Occupancy was also a significant factor for 6-MHO, but not the linear aldehydes, consistent with 6-MHO’s formation from the reaction between ozone and squalene, which is present in human skin oils. PMID:23517299

Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

PubMed

Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao

2018-01-01

Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al 2 O 3 , Fe 2 O 3 , and MnO 2 ). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp 3 C sites instead of sp 2 C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O 3 ) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O 2 - ) and singlet oxygen ( 1 O 2 ) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Genes of innate immunity and the biological response to inhaled ozone

PubMed Central

Li, Zhuowei; Tighe, Robert M.; Feng, Feifei; Ledford, Julie G.; Hollingsworth, John W.

2013-01-01

Ambient ozone has a significant impact on human health. We have made considerable progress in understanding the fundamental mechanisms that regulate the biological response to ozone. It is increasingly clear that genes of innate immunity play a central role in both infectious and non-infectious lung disease. The biological response to ambient ozone provides a clinically relevant environmental exposure that allows us to better understand the role of innate immunity in non-infectious airways disease. In this brief review, we focus on: (1) specific cell types in the lung modified by ozone; (2) ozone and oxidative stress; (3) the relationship between genes of innate immunity and ozone; (4) the role of extracellular matrix in reactive airways disease; and (5) the effect of ozone on the adaptive immune system. We summarize recent advances in understanding the mechanisms that ozone contributes to environmental airways disease. PMID:23169704

Advanced treatment of sodium dithionite wastewater using the combination of coagulation, catalytic ozonation, and SBR.

PubMed

Zou, Xiao-Ling

2017-10-01

A combined process of coagulation-catalytic ozonation-anaerobic sequencing batch reactor (ASBR)-SBR was developed at lab scale for treating a real sodium dithionite wastewater with an initial chemical oxygen demand (COD) of 21,760-22,450 mg/L. Catalytic ozonation with the prepared cerium oxide (CeO 2 )/granular activated carbon catalyst significantly enhances wastewater biodegradability and reduces wastewater microtoxicity. The results show that, under the optimum conditions, the removal efficiencies of COD and suspended solids are averagely 99.3% and 95.6%, respectively, and the quality of final effluent can meet the national discharge standard of China. The coagulation and ASBR processes remove a considerable proportion of organic matter, while the SBR plays an important role in post-polish of final effluent. The ecotoxicity of the wastewater is greatly reduced after undergoing the hybrid treatment. This work demonstrates that the hybrid system has the potential to be applied for the advanced treatment of high-strength industrial wastewater.

Parameterizing the impacts of ozone-vegetation coupling and feedbacks on ozone air quality in a chemical transport model

NASA Astrophysics Data System (ADS)

Zhou, S.; Tai, A. P. K.; Lombardozzi, D.

2016-12-01

Apart from being an important greenhouse gas, tropospheric ozone is a significant air pollutant that is shown to have harmful effects both on human health and vegetation. Ozone damages vegetation mainly through reducing plant photosynthesis and stomatal conductance. Meanwhile, ozone is also strongly dependent on vegetation via various biogeochemical and physical processes. These interdependences between ozone and vegetation would constitute feedback mechanisms that can potentially alter ozone concentration itself, and should be considered in future climate and air quality projections. In this study, we first implement an empirical scheme for ozone damage on vegetation in the Community Land Model (CLM), and simulate the relative changes in leaf area indices (LAI) and stomatal conductance for three plant groups (consolidated from 15 plant functional types) at various prescribed ozone levels (from 0 ppb to 100 ppb). We find that all plant groups suffer the greatest decreases in LAI and stomatal conductance in regions with their greatest abundance, and grasses and crops show the most severe damage from ozone exposure compared with broadleaf and needleleaf groups, with an LAI reduction of as much as 50% in some areas even at an ozone level of 30 ppb. Using the CLM-simulated results, we develop a semi-empirical parameterization scheme to link prescribed ozone levels to the spatially varying simulated relative changes in LAI and stomatal conductance at model steady state. We implement the scheme in the GEOS-Chem chemical transport model so that ozone-vegetation chemical coupling via ozone dry deposition and biogenic volatile organic compound (VOC) emissions can be simulated online. Model simulations indicate that ozone effect on stomatal conductance (which modifies dry deposition) appears to be the dominant feedback pathway influencing surface ozone, whereas ozone-mediated LAI changes (which affects biogenic VOC emissions) appear to play a lesser role. This work is the

Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water.

PubMed

Ma, Wei; Zong, Panpan; Cheng, Zihong; Wang, Baodong; Sun, Qi

2014-02-15

This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid-solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH=7 with a 2:1 liquid-solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03-0.1 min(-1)) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH=7.0 compared with ozonation alone. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone

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

Ding, Yanhua; Zhang, Xiaolei; Chen, Li

The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} undermore » the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency of O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.« less

Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.

PubMed

Li, Xufang; Chen, Weiyu; Ma, Luming; Wang, Hongwu; Fan, Jinhong

2018-03-01

An Fe-based catalyst was used as a heterogeneous catalyst for the ozonation of industrial wastewater, and key operational parameters (pH and catalyst dosage) were studied. The results indicated that the Fe-based catalyst significantly improved the mineralization of organic pollutants in wastewater. TOC (total organic carbon) removal was high, at 78.7%, with a catalyst concentration of 200 g/L, but only 31.6% with ozonation alone. The Fe-based catalyst significantly promoted ozone decomposition by 70% in aqueous solution. Hydroxyl radicals (·OH) were confirmed to be existed directly via EPR (electron paramagnetic resonance) experiments, and ·OH were verified to account for about 34.4% of TOC removal with NaHCO 3 as a radical scavenger. Through characterization by SEM-EDS (field emission scanning electron microscope with energy-dispersive spectrometer), XRD (X-ray powder diffraction) and XPS (X-ray photoelectron spectroscopy), it was deduced that FeOOH on the surface of the catalyst was the dominant contributor to the catalytic efficiency. The catalyst was certified as having good stability and excellent reusability based on 50 successive operations and could be used as a filler simultaneously. Thereby, it is a promising catalyst for practical industrial wastewater advanced treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

A comparison of different activated carbon performances on catalytic ozonation of a model azo reactive dye.

PubMed

Gül, S; Eren, O; Kır, S; Onal, Y

2012-01-01

The objective of this study is to compare the performances of catalytic ozonation processes of two activated carbons prepared from olive stone (ACOS) and apricot stone (ACAS) with commercial ones (granular activated carbon-GAC and powder activated carbon-PAC) in degradation of reactive azo dye (Reactive Red 195). The optimum conditions (solution pH and amount of catalyst) were investigated by using absorbencies at 532, 220 and 280 nm wavelengths. Pore properties of the activated carbon (AC) such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption. The highest BET surface area carbon (1,275 m(2)/g) was obtained from ACOS with a particle size of 2.29 nm. After 2 min of catalytic ozonation, decolorization performances of ACOS and ACAS (90.4 and 91.3%, respectively) were better than that of GAC and PAC (84.6 and 81.2%, respectively). Experimental results showed that production of porous ACs with high surface area from olive and apricot stones is feasible in Turkey.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

NASA Astrophysics Data System (ADS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Relationship between the structure of Fe-MCM-48 and its activity in catalytic ozonation for diclofenac mineralization.

PubMed

Li, Xukai; Chen, Weirui; Tang, Yiming; Li, Laisheng

2018-05-12

Fe-MCM-48 catalyst with a three-dimensional cubic pore structure was directly synthesized via a hydrothermal method, and the mineralization efficiency of diclofenac (DCF) in the catalytic ozonation process (Fe-MCM-48/O 3 ) was assessed. X-ray diffraction (XRD), N 2 adsorption desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) characterizations revealed that Fe existed in the framework of MCM-48, and Fe-MCM-48 possessed a large surface area and a highly ordered cubic mesoporous structure, which could accelerate reactants and products diffusion. Regarding mineralization efficiency, the addition of Fe-MCM-48 significantly improved total organic carbon (TOC) removal, and approximately 49.9% TOC were removed through the Fe-MCM-48/O 3 process at 60 min, which was 2.0 times higher than that in single ozonation. Due to this catalyst's superior structure, Fe-MCM-48 showed the better catalytic activity compared with Fe-MCM-41 and Fe loaded MCM-48 (Fe/MCM-48, Fe existed on the surface of MCM-48). DCF removal in the Fe-MCM-48/O 3 process was primarily based on ozone direct oxidation. The improvement of mineralization efficiency was attributed to the function of generated hydroxyl radicals (•OH), which indicated that the presence of Fe-MCM-48 accelerated ozone decomposition. Moreover, the negatively charged surface of Fe-MCM-48 and the proper pH value of the DCF solution played an essential role in OH generation. Copyright © 2018 Elsevier Ltd. All rights reserved.

CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECTS OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

EPA Science Inventory

This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and activities of Cu, Mo, Cr and Mn oxides, and mixed metal oxides supported on -alumina, were tes...

CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

EPA Science Inventory

This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

Is There Evidence that Mid-Latitude Stratospheric Ozone Depletion Occurs in Conjunction with North American Monsoon Convection?

NASA Astrophysics Data System (ADS)

Rosenlof, K. H.; Ray, E. A.; Portmann, R. W.

2017-12-01

A recent study suggests that during the period of the summertime North American Monsoon (NAM), ozone depletion could occur as a result of catalytic ozone destruction associated with the cold and wet conditions caused by overshooting convection. Aura Microwave Limb Sounder (MLS) water vapor measurements do show that the NAM region is wetter than other parts of the globe in regards to both the mean and extremes. However, definitive evidence of ozone depletion occurring in that region has not been presented. In this study, we examine coincident measurements of water vapor, ozone, and tropospheric tracers from aircraft data taken during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) aircraft campaign looking specifically for ozone depletion in regions identified as impacted by overshooting convection. Although we do find evidence of lower ozone values in air impacted by convective overshoots, using tropospheric tracers we attribute those observations to input of tropospheric air rather than catalytic ozone destruction. Additionally, we explore the consequences of these lower ozone values on surface UV, and conclude that there is minimal impact on the UV index.

Plasmon-Exciton Coupling Interaction for Surface Catalytic Reactions.

PubMed

Wang, Jingang; Lin, Weihua; Xu, Xuefeng; Ma, Fengcai; Sun, Mengtao

2018-05-01

In this review, we firstly reveal the physical principle of plasmon-exciton coupling interaction with steady absorption spectroscopy, and ultrafast transition absorption spectroscopy, based on the pump-prop technology. Secondly, we introduce the fabrication of electro-optical device of two-dimensional semiconductor-nanostructure noble metals hybrid, based on the plasmon-exciton coupling interactions. Thirdly, we introduce the applications of plasmon-exciton coupling interaction in the field of surface catalytic reactions. Lastly, the perspective of plasmon-exciton coupling interaction and applications closed this review. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biological aerated filter treated textile washing wastewater for reuse after ozonation pre-treatment.

PubMed

Wang, X J; Chen, S L; Gu, X Y; Wang, K Y; Qian, Y Z

2008-01-01

The combination of chemical and biological treatment processes is a promising technique to reduce refractory organics from wastewater. Ozonation can achieve high color removal, enhance biodegradability, and reduce the chemical oxygen demand (COD). The biological technique can further decrease COD of wastewater after ozonation as a pre-treatment. In this study the ozonizing-biological aerated filter processes were used to treat textile washing wastewater for reuse after conventional treatment. The result showed that when the influent qualities were COD about 80 mg/L, color 16 degree and turbidity about 8 NTU, using the combination processes with the dosages of ozone at 30-45 mg/L with the hydraulic retention time (HRT) of biological aerated filter (BAF) at 3-4 hours respectively, gave effluent qualities of COD less than 30 mg/L, color 2 degree and turbidity less than 1NTU. The cost of treatment was less than one yuan/t wastewater, and these processes could enable high quality washing water reuse in textile industry. Copyright IWA Publishing 2008.

Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment.

PubMed

Rubalcaba, A; Suárez-Ojeda, M E; Stüber, F; Fortuny, A; Bengoa, C; Metcalfe, I; Font, J; Carrera, J; Fabregat, A

2007-01-01

Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested batch wise, while catalytic wet air oxidation and H2O2-promoted catalytic wet air oxidation processes were studied in a trickle bed reactor, the last two using over activated carbon as catalyst. Effluent characterisation was made by means of substrate conversion (using high liquid performance chromatography), chemical oxygen demand and total organic carbon. Biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) were obtained from respirometric tests using activated sludge from an urban biological wastewater treatment plant (WWTP). The main goal was to find the proper conditions in terms of biodegradability enhancement, so that these phenolic effluents could be successfully treated in an urban biological WWTP. Results show promising research ways for the development of efficient coupled processes for the treatment of wastewater containing toxic or biologically non-degradable compounds.

Ozone dosing alters the biological potential and therapeutic outcomes of plasma rich in growth factors.

PubMed

Anitua, E; Zalduendo, M M; Troya, M; Orive, G

2015-04-01

Until now, ozone has been used in a rather empirical way. This in-vitro study investigates, for the first time, whether different ozone treatments of plasma rich in growth factors (PRGF) alter the biological properties and outcomes of this autologous platelet-rich plasma. Human plasma rich in growth factors was treated with ozone using one of the following protocols: a continuous-flow method; or a syringe method in which constant volumes of ozone and PRGF were mixed. In both cases, ozone was added before, during and after the addition of calcium chloride. Three ozone concentrations, of the therapeutic range 20, 40 and 80 μg/mL, were tested. Fibrin clot properties, growth factor content and the proliferative effect on primary osteoblasts and gingival fibroblasts were evaluated. Ozone treatment of PRGF using the continuous flow protocol impaired formation of the fibrin scaffold, drastically reduced the levels of growth factors and significantly decreased the proliferative potential of PRGF on primary osteoblasts and gingival fibroblasts. In contrast, treatment of PRGF with ozone using the syringe method, before, during and after the coagulation process, did not alter the biological outcomes of the autologous therapy. These findings suggest that ozone dose and the way that ozone combines with PRGF may alter the biological potential and therapeutic outcomes of PRGF. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Ozone as a laundry agent on orbit and on the ground

NASA Technical Reports Server (NTRS)

Agosto, William N.

1994-01-01

Ozone (03), is the strongest commercial oxidizing agent for aqueous systems and may be ideal for space station laundering operations. It can be generated electronically from air in situ. It kills virtually all microorganisms, attacks many organics and inorganics, and breaks down stable ring structures of benzene and related oils when coupled with ultra violet radiation. It cleans and disinfects in cold water without the need for detergent. It leaves no residues. Ozone permits up to 90% wash water recycling and it eliminates wash time, water volume, and recycling problems of a detergent rinse. Ozone is self purging and converts spontaneously to oxygen. It can be rapidly purged by well established catalytic and thermal processes. Scaling of an ozone laundering system for space station may have commercial applications in a consumer model for home use.

Stratospheric ozone depletion

PubMed Central

Rowland, F. Sherwood

2006-01-01

Solar ultraviolet radiation creates an ozone layer in the atmosphere which in turn completely absorbs the most energetic fraction of this radiation. This process both warms the air, creating the stratosphere between 15 and 50 km altitude, and protects the biological activities at the Earth's surface from this damaging radiation. In the last half-century, the chemical mechanisms operating within the ozone layer have been shown to include very efficient catalytic chain reactions involving the chemical species HO, HO2, NO, NO2, Cl and ClO. The NOX and ClOX chains involve the emission at Earth's surface of stable molecules in very low concentration (N2O, CCl2F2, CCl3F, etc.) which wander in the atmosphere for as long as a century before absorbing ultraviolet radiation and decomposing to create NO and Cl in the middle of the stratospheric ozone layer. The growing emissions of synthetic chlorofluorocarbon molecules cause a significant diminution in the ozone content of the stratosphere, with the result that more solar ultraviolet-B radiation (290–320 nm wavelength) reaches the surface. This ozone loss occurs in the temperate zone latitudes in all seasons, and especially drastically since the early 1980s in the south polar springtime—the ‘Antarctic ozone hole’. The chemical reactions causing this ozone depletion are primarily based on atomic Cl and ClO, the product of its reaction with ozone. The further manufacture of chlorofluorocarbons has been banned by the 1992 revisions of the 1987 Montreal Protocol of the United Nations. Atmospheric measurements have confirmed that the Protocol has been very successful in reducing further emissions of these molecules. Recovery of the stratosphere to the ozone conditions of the 1950s will occur slowly over the rest of the twenty-first century because of the long lifetime of the precursor molecules. PMID:16627294

Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

NASA Astrophysics Data System (ADS)

Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

2017-10-01

Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

Treatment of waste metalworking fluid by a hybrid ozone-biological process.

PubMed

Jagadevan, Sheeja; Graham, Nigel J; Thompson, Ian P

2013-01-15

In metal machining processes, the regulation of heat generation and lubrication at the contact point are achieved by application of a fluid referred to as metalworking fluid (MWF). MWFs inevitably become operationally exhausted with age and intensive use, which leads to compromised properties, thereby necessitating their safe disposal. Disposal of this waste through a biological route is an increasingly attractive option, since it is effective with relatively low energy demands. However, successful biological treatment is challenging since MWFs are chemically complex, and include biocides specifically to retard microbial deterioration whilst the fluids are operational. In this study remediation of the recalcitrant component of a semi-synthetic MWF by a novel hybrid ozone-bacteriological treatment, was investigated. The hybrid treatment proved to be effective and reduced the chemical oxygen demand by 72% (26.9% and 44.9% reduction after ozonation and biological oxidation respectively). Furthermore, a near-complete degradation of three non-biodegradable compounds (viz. benzotriazole, monoethanolamine, triethanolamine), commonly added as biocides and corrosion inhibitors in MWF formulations, under ozonation was observed. Copyright © 2012 Elsevier B.V. All rights reserved.

Ozonation of clofibric acid catalyzed by titanium dioxide.

PubMed

Rosal, Roberto; Gonzalo, María S; Rodríguez, Antonio; García-Calvo, Eloy

2009-09-30

The removal of clofibric acid from aqueous solution has been investigated in catalytic and non-catalytic semicontinuous ozonation runs. Kinetic data were analyzed using second order expressions for the reaction between organics and ozone or hydroxyl radicals. Catalytic runs used a commercial titanium dioxide catalyst consisting of fumed colloidal particles. The kinetic constant of the non-catalytic ozonation of clofibric acid at pH 3 was 8.16 x 10(-3)+/-3.4 x 10(-4)L mmol(-1)s(-1). The extent of mineralization during non-catalytic runs ranged from 50% at pH 7 to 20% at pH 3 in a reaction that essentially took place during the first 10-20 min. The catalyst increased the total extent of mineralization, its effect being more important during the first part of the reaction. The pseudo-homogeneous catalytic rate constant was 2.17 x 10(-2) L mmol(-1)s(-1) at pH 3 and 6.80 x 10(-1)L mmol(-1)s(-1) at pH 5, with up to a threefold increase with respect to non-catalytic constants using catalyst load of 1g/L. A set of stopped-flow experiments were designed to elucidate the role of catalyst, whose effect was probably due to the adsorption of organics on catalytic sites rather than to the promotion of ozone decomposition.

Coupling free radical catalysis, climate change, and human health.

PubMed

Anderson, J G; Clapp, C E

2018-04-25

We present the chain of mechanisms linking free radical catalytic loss of stratospheric ozone, specifically over the central United States in summer, to increased climate forcing by CO2 and CH4 from fossil fuel use. This case directly engages detailed knowledge, emerging from in situ aircraft observations over the polar regions in winter, defining the temperature and water vapor dependence of the kinetics of heterogeneous catalytic conversion of inorganic chlorine (HCl and ClONO2) to free radical form (ClO). Analysis is placed in the context of irreversible changes to specific subsystems of the climate, most notably coupled feedbacks that link rapid changes in the Arctic with the discovery that convective storms over the central US in summer both suppress temperatures and inject water vapor deep into the stratosphere. This places the lower stratosphere over the US in summer within the same photochemical catalytic domain as the lower stratosphere of the Arctic in winter engaging the risk of amplifying the rate limiting step in the ClO dimer catalytic mechanism by some six orders of magnitude. This transitions the catalytic loss rate of ozone in lower stratosphere over the United States in summer from HOx radical control to ClOx radical control, increasing the overall ozone loss rate by some two orders of magnitude over that of the unperturbed state. Thus we address, through a combination of observations and modeling, the mechanistic foundation defining why stratospheric ozone, vulnerable to increased climate forcing, is one of the most delicate aspects of habitability on the planet.

Recovery of the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Kawa, S. Randolph; Montzka, Steve; Schauffler, Sue; Stolarski, Richard S.; Douglass, Anne R.; Pawson, Steven; Nielsen, J. Eric

2006-01-01

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS and OMI instruments. The severity of the hole has been assessed using the minimum total ozone value from the October monthly mean (depth of the hole), the average size during the September-October period, and the ozone mass deficit. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. We use two methods to estimate ozone hole recovery. First, we use projections of halogen levels combined with age-of-air estimates in a parametric model. Second, we use a coupled chemistry climate model to assess recovery. We find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. Furthermore, full recovery to 1980 levels will not occur until approximately 2068. We will also show some error estimates of these dates and the impact of climate change on the recovery.

Two-dimensional model studies of the effect of supersonic aircraft operations on the stratospheric ozone content

NASA Technical Reports Server (NTRS)

Whitten, R. C.; Borucki, W. J.; Poppoff, I. G.; Latt, L.; Widhopf, G. F.; Capone, L. A.; Reigel, C. A.

1981-01-01

For a fleet of 250 aircraft, the change in the ozone column is predicted to be very close to zero; in fact, the ozone overburden may actually increase as a result of show that above 25 to 30 km the ozone abundance decreases via catalytic destruction, but at lower heights it increases, mainly as a result of coupling with odd hydrogen species. Water vapor released in the engine exhaust is predicted to cause ozone decreases; for the hypothetical engines used in the study, the total column ozone changes due to water vapor emission largely offset the predicted ozone increases due to NOx emission. The actual effect of water vapor may be less than calculated because present models do not include thermal feedback. Feedback refers to the cooling effect of additional water vapor that would tend to slow the NOx reactions which destroy ozone.

Low-temperature catalytic oxidation of aldehyde mixtures using wood fly ash: kinetics, mechanism, and effect of ozone.

PubMed

Kolar, Praveen; Kastner, James R

2010-02-01

Poultry rendering emissions contain volatile organic compounds (VOCs) that are nuisance, odorous, and smog and particulate matter precursors. Present treatment options, such as wet scrubbers, do not eliminate a significant fraction of the VOCs emitted including, 2-methylbutanal (2-MB), 3-methylbutanal, and hexanal. This research investigated the low-temperature (25-160 degrees C) catalytic oxidation of 2-MB and hexanal vapors in a differential, plug flow reactor using wood fly ash (WFA) as a catalyst and oxygen and ozone as oxidants. The oxidation rates of 2-MB and hexanal ranged between 3.0 and 3.5 x 10(-9)mol g(-1)s(-1) at 25 degrees C and the activation energies were 2.2 and 1.9 kcal mol(-1), respectively. The catalytic activity of WFA was comparable to other commercially available metal and metal oxide catalysts. We theorize that WFA catalyzed a free radical reaction in which 2-butanone and CO(2) were formed as end products of 2-MB oxidation, while CO(2), pentanal, and butanal were formed as end products of hexanal oxidation. When tested as a binary mixture at 25 and 160 degrees C, no inhibition was observed. Additionally, when ozone was tested as an oxidant at 160 degrees C, 100% removal was achieved within a 2-s reaction time. These results may be used to design catalytic oxidation processes for VOC removal at poultry rendering facilities and potentially replace energy and water intensive air pollution treatment technologies currently in use. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Catalytic membrane reactor for water and wastewater treatment

NASA Astrophysics Data System (ADS)

Heng, Samuel

A double membrane reactor was fabricated and assessed for continuous treatment of water containing organic contaminants by ozonation. This innovative reactor consisted of a zeolite membrane prepared on the inner surface of a porous a-alumina support, which served as water selective extractor and active contactor, and a porous stainless membrane which was the ozone gas diffuser. The coupling of membrane separation and chemical oxidation was found to be highly beneficial to both processes. The total organic carbon (TOC) removal rate at the retentate was enhanced by up to 2.2 times, as compared to membrane ozonation. Simultaneously, clean water (< 2 mg C.L-1 ) was consistently produced on the permeate side, using a feed solution containing up to 1000 mg C.L-1, while the retentate was concentrated and treated. Most significantly, the addition of an adsorbing material, as a bed or a coated layer, onto the pores of the membrane support, was shown to further enhance TOC degradation, permeated TOC concentration, permeate flux, and moreover, ozone yield. The achievements of this project included: (1) The development of a novel low-temperature zeolite membrane activation method that generates consistently high quality membranes (i.e. high reproducibility and fewer defects). (2) The demonstration that gamma-alumina and gamma-alumina supported catalysts do not have significant activity and that the TOC removal enhancement usually observed during catalytic ozonation was due primarily to the contribution of adsorption and metal leaching. Thermogravimetric analysis (TGA) and elemental analysis (EA) of the spent catalyst showed that, during catalytic ozonation, oxygenated by-products of increased adsorbability were concentrated onto the gamma-alumina contactor, and were subsequently degraded. (3) The development of a method for coating high surface area gamma-alumina layers onto the grains of zeolite membrane support used as the active membrane contactor.

Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

PubMed Central

Cho, Hee Yeon

2014-01-01

Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted a lot of attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B–B, Si–Si, B–Si, Si–Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process. PMID:24736839

Evolution of catalytic function

NASA Technical Reports Server (NTRS)

Joyce, G. F.

1993-01-01

An RNA-based evolution system was constructed in the laboratory and used to develop RNA enzymes with novel catalytic function. By controlling the nature of the catalytic task that the molecules must perform in order to survive, it is possible to direct the evolving population toward the expression of some desired catalytic behavior. More recently, this system has been coupled to an in vitro translation procedure, raising the possibility of evolving protein enzymes in the laboratory to produce novel proteins with desired catalytic properties. The aim of this line of research is to reduce darwinian evolution, the fundamental process of biology, to a laboratory procedure that can be made to operate in the service of organic synthesis.

High activity of g-C3N4/multiwall carbon nanotube in catalytic ozonation promotes electro-peroxone process.

PubMed

Guo, Zhuang; Cao, Hongbin; Wang, Yuxian; Xie, Yongbing; Xiao, Jiadong; Yang, Jin; Zhang, Yi

2018-06-01

Three kinds of graphitic carbon nitride materials (bulk, porous and nanosheet g-C 3 N 4 ) were composited with a multiwall carbon nanotube (MWCNT) by a hydrothermal method, and the obtained b-C 3 N 4 /CNT, p-C 3 N 4 /CNT and n-C 3 N 4 /CNT materials were used in the electrodes for electro-peroxone process. It was found that the n-C 3 N 4 /CNT composite exhibited the highest efficiency in oxalate degradation, though it performed the worst in the oxygen-reduction reaction for H 2 O 2 production. The n-C 3 N 4 /CNT composite exhibited higher activity than CNT and other composites in catalytic ozonation experiments, due to the higher pyrrolic-N content modified on the CNT surface and higher surface area. It also has higher electron transfer ability, which benefited to the electro-reduction of both O 2 and O 3 . The result confirmed that catalytic ozonation process was an important means to enhance the degradation efficiency in the electro-peroxone process, besides peroxone process and O 3 -electrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization of ozone decomposition in a soil slurry: kinetics and mechanism.

PubMed

Lim, Hyung-Nam; Choi, Hechul; Hwang, Tae-Moon; Kang, Joon-Wun

2002-01-01

A series of soil slurry experiments were performed in a carefully conceived reactor set-up to investigate the characteristics of the catalytic decomposition of ozone on a sand and iron surface. Real time on-line monitoring of ozone in the reaction module was possible using flow injection analysis coupled with a computer-controlled UV detector and data acquisition system. The effects of the soil media and size, ozone dosage, pH and p-CBA as a probe compound were examined at the given experimental conditions. Two apparent phases existed, and ozone instantaneously decomposed within one second in the first phase. These were defined as the instantaneous ozone demand (ID) phase, and the relatively slow decay stage. The interactions of ozone with the soil organic matter (SOM) and metal oxides were attributed mostly to the instantaneous decomposition of ozone. From the probe (p-CBA) experiments, 60-68% of total p-CBA removal occurred during the ID phase. The generation of hydroxyl radicals (OH.) was demonstrated and was closely related with metal oxides as well as SOM. Metal oxides in soil surface were considered to have relatively faster reaction rate with ozone and provide more favorable reactive sites to generate higher amount of OH. than SOM. Even at one-tenth concentration of the sands, a goethite-induced catalytic reaction outfitted the removal rate ofp-CBA among all the soils tested. More than 40% of total p-CBA removal occurred on the soil surface. It was inferred that the radical reaction with the probe compound seemed to take place not only on the soil surface but also in the solid-liquid interface. Ozone decomposition and the reaction between OH. and p-CBA appeared to be independent of any change in pH.

Process analysis and economics of drinking water production from coastal aquifers containing chromophoric dissolved organic matter and bromide using nanofiltration and ozonation.

PubMed

Sobhani, R; McVicker, R; Spangenberg, C; Rosso, D

2012-01-01

In regions characterized by water scarcity, such as coastal Southern California, groundwater containing chromophoric dissolved organic matter is a viable source of water supply. In the coastal aquifer of Orange County in California, seawater intrusion driven by coastal groundwater pumping increased the concentration of bromide in extracted groundwater from 0.4 mg l⁻¹ in 2000 to over 0.8 mg l⁻¹ in 2004. Bromide, a precursor to bromate formation is regulated by USEPA and the California Department of Health as a potential carcinogen and therefore must be reduced to a level below 10 μg l⁻¹. This paper compares two processes for treatment of highly coloured groundwater: nanofiltration and ozone injection coupled with biologically activated carbon. The requirement for bromate removal decreased the water production in the ozonation process to compensate for increased maintenance requirements, and required the adoption of catalytic carbon with associated increase in capital and operating costs per unit volume. However, due to the absence of oxidant addition in nanofiltration processes, this process is not affected by bromide. We performed a process analysis and a comparative economic analysis of capital and operating costs for both technologies. Our results show that for the case studied in coastal Southern California, nanofiltration has higher throughput and lower specific capital and operating cost, when compared to ozone injection with biologically activate carbon. Ozone injection with biologically activated carbon, compared to nanofiltration, has 14% higher capital cost and 12% higher operating costs per unit water produced while operating at the initial throughput. Due to reduced ozone concentration required to accommodate for bromate reduction, the ozonation process throughput is reduced and the actual cost increase (per unit water produced) is 68% higher for capital cost and 30% higher for operations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Ozone and the stratosphere

NASA Technical Reports Server (NTRS)

Shimazaki, Tatsuo

1987-01-01

It is shown that the stratospheric ozone is effective in absorbing almost all radiation below 300 nm at heights below 300 km. The distribution of global ozone in the troposphere and the lower stratosphere, and the latitudinal variations of the total ozone column over four seasons are considered. The theory of the ozone layer production is discussed together with catalytic reactions for ozone loss and the mechanisms of ozone transport. Special attention is given to the anthropogenic perturbations, such as SST exhaust gases and freon gas from aerosol cans and refrigerators, that may cause an extensive destruction of the stratospheric ozone layer and thus have a profound impact on the world climate and on life.

The Impact of Increasing Carbon Dioxide on Ozone Recovery

NASA Technical Reports Server (NTRS)

Rosenfield, Joan E.; Douglass, Anne R.; Considine, David B.; Einaudi, Franco (Technical Monitor)

2001-01-01

We have used the GSFC coupled two-dimensional (2D) model to study the impact of increasing carbon dioxide from 1980 to 2050 on the recovery of ozone to its pre-1980 amounts. We find that the changes in temperature and circulation arising from increasing CO2 affect ozone recovery in a manner which varies greatly with latitude, altitude, and time of year. Middle and upper stratospheric ozone recovers faster at all latitudes due to a slowing of the ozone catalytic loss cycles. In the lower stratosphere, the recovery of tropical ozone is delayed due to a decrease in production and a speed up in the overturning circulation. The recovery of high northern latitude lower stratospheric ozone is delayed in spring and summer due to an increase in springtime heterogeneous chemical loss, and is speeded up in fall and winter due to increased downwelling. The net effect on the higher northern latitude column ozone is to slow down the recovery from late March to late July, while making it faster at other times. In the high southern latitudes, the impact of CO2 cooling is negligible. Annual mean column ozone is predicted to recover faster at all latitudes, and globally averaged ozone is predicted to recover approximately ten years faster as a result of increasing CO2.

Treatment of soft drink process wastewater by ozonation, ozonation-H₂O₂ and ozonation-coagulation processes.

PubMed

García-Morales, M A; Roa-Morales, G; Barrera-Díaz, C; Balderas-Hernández, P

2012-01-01

In this research, we studied the treatment of wastewater from the soft drink process using oxidation with ozone. A scheme composed of sequential ozonation-peroxide, ozonation-coagulation and coagulation-ozonation treatments to reduce the organic matter from the soft drink process was also used. The samples were taken from the conventional activated sludge treatment of the soft drink process, and the experiments using chemical oxidation with ozone were performed in a laboratory using a reactor through a porous plate glass diffuser with air as a feedstock for the generation of ozone. Once the sample was ozonated, the treatments were evaluated by considering the contact time, leading to greater efficiency in removing colour, turbidity and chemical oxygen demand (COD). The effect of ozonation and coagulant coupled with treatment efficiency was assessed under optimal conditions, and substantial colour and turbidity removal were found (90.52% and 93.33%, respectively). This was accompanied by a 16.78% reduction in COD (initial COD was 3410 mg/L). The absorbance spectra of the oxidised products were compared using UV-VIS spectroscopy to indicate the level of oxidation of the wastewater. We also determined the kinetics of decolouration and the removal of turbidity with the best treatment. The same treatment was applied to the sample taken from the final effluent of the activated sludge system, and a COD removal efficiency of 100% during the first minute of the reaction with ozone was achieved. As a general conclusion, we believe that the coagulant polyaluminum chloride - ozone (PAC- ozone) treatment of wastewater from the manufacturing of soft drinks is the most efficient for removing turbidity and colour and represents an advantageous option to remove these contaminants because their removal was performed in minutes compared to the duration of traditional physical, chemical and biological processes that require hours or days.

Some ozone advanced oxidation processes to improve the biological removal of selected pharmaceutical contaminants from urban wastewater.

PubMed

Espejo, Azahara; Aguinaco, Almudena; Amat, Ana M; Beltrán, Fernando J

2014-01-01

Removal of nine pharmaceutical compounds--acetaminophen (AAF), antipyrine (ANT), caffeine (CAF), carbamazepine (CRB), diclofenac (DCF), hydrochlorothiazide (HCT), ketorolac (KET), metoprolol (MET) and sulfamethoxazole (SMX)-spiked in a primary sedimentation effluent of a municipal wastewater has been studied with sequential aerobic biological and ozone advanced oxidation systems. Combinations of ozone, UVA black light and Fe(III) or Fe3O4 constituted the chemical systems. During the biological treatment (hydraulic residence time, HRT = 24 h), only AAF and CAF were completely eliminated, MET, SMX and HCT reached partial removal rates and the rest of compounds were completely refractory. With any ozone advanced oxidation process applied, the remaining pharmaceuticals disappear in less than 10 min. Fe3O4 or Fe(III) photocatalytic ozonation leads to 35% mineralization compared to 13% reached during ozonation alone after about 30-min reaction. Also, biodegradability of the treated wastewater increased 50% in the biological process plus another 150% after the ozonation processes. Both untreated and treated wastewater was non-toxic for Daphnia magna (D. magna) except when Fe(III) was used in photocatalytic ozonation. In this case, toxicity was likely due to the ferryoxalate formed in the process. Kinetic information on ozone processes reveals that pharmaceuticals at concentrations they have in urban wastewater are mainly removed through free radical oxidation.

Field-analysis of potable water quality and ozone efficiency in ozone-assisted biological filtration systems for surface water treatment.

PubMed

Zanacic, Enisa; Stavrinides, John; McMartin, Dena W

2016-11-01

Potable water treatment in small communities is challenging due to a complexity of factors starting with generally poor raw water sources, a smaller tax and consumption base that limit capital and operating funds, and culminating in what is typically a less sophisticated and robust water treatment plant for production and delivery of safe, high quality potable water. The design and optimization of modular ozone-assisted biological filtration systems can address some of these challenges. In surface water treatment, the removal of organic matter (e.g., dissolved organic carbon - DOC), inorganic nutrients and other exposure-related contaminants (e.g., turbidity and dissolved solids) from the raw water source is essential. Thus, a combination of chemical and biological oxidation processes can produce an effective and efficient water treatment plant design that is also affordable and robust. To that end, the ozone-assisted biological filtration water treatment plants in two communities were evaluated to determine the efficacy of oxidation and contaminant removal processes. The results of testing for in-field system performance indicate that plant performance is particularly negatively impacted by high alkalinity, high organics loading, and turbidity. Both bicarbonate and carbonate alkalinity were observed to impede ozone contact and interaction with DOC, resulting in lower than anticipated DOC oxidation efficiency and bioavailability. The ozone dosage at both water treatment plants must be calculated on a more routine basis to better reflect both the raw water DOC concentration and presence of alkalinities to ensure maximized organics oxidation and minimization of trihalomethanes production. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Application of ozonation for pharmaceuticals and personal care products removal from water.

PubMed

Gomes, João; Costa, Raquel; Quinta-Ferreira, Rosa M; Martins, Rui C

2017-05-15

Due to the shortening on natural water resources, reclaimed wastewater will be an important water supply source. However, suitable technologies must be available to guaranty its proper detoxification with special concern for the emerging pharmaceutical and personal care products that are continuously reaching municipal wastewater treatment plants. While conventional biological systems are not suitable to remove these compounds, ozone, due to its interesting features involving molecular ozone oxidation and the possibility of generating unselective hydroxyl radicals, has a wider range of action on micropollutants removal and water disinfection. This paper aims to review the studies dealing with ozone based processes for water reuse by considering municipal wastewater reclamation as well as natural and drinking water treatment. A comparison with alternative technologies is given. The main drawback of ozonation is related with the low mineralization achieved that may lead to the production of reaction intermediates with toxic features. The use of hydrogen peroxide and light aided systems enhance ozone action over pollutants. Moreover, scientific community is focused on the development of solid catalysts able to improve the mineralization level achieved by ozone. Special interest is now being given to solar light catalytic ozonation systems with interesting results both for chemical and biological contaminants abatement. Nowadays the integration between ozonation and sand biofiltration seems to be the most interesting cost effective methodology for water treatment. However, further studies must be performed to optimize this system by understanding the biofiltration mechanisms. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of the rates of ozonation of biological antioxidants and oleate and linoleate esters

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

Giamalva, D.; Church, D.F.; Pryor, W.A.

1985-12-17

The rates of reaction with ozone of some biological antioxidants and simple polyunsaturated fatty acids (PUFA) have been measured in water or in aqueous micellar solutions. At pH 7.0 the rate constants are ca. 10(6) M-1 sec-1 for urate, alpha-tocopherol, and PUFA, and 6 X 10(7) M-1 sec-1 for ascorbate. When ozone-containing air is breathed, ascorbate in the lung may undergo direct ozonation. However, alpha-tocopherol is probably spared direct reaction with ozone because it doesn't effectively compete with PUFA in pulmonary membranes; rather, tocopherol is used to scavenge radicals produced from the ozone-PUFA reaction.

Sequential ozone advanced oxidation and biological oxidation processes to remove selected pharmaceutical contaminants from an urban wastewater.

PubMed

Espejo, Azahara; Aguinaco, Almudena; García-Araya, J F; Beltrán, Fernando J

2014-01-01

Sequential treatments consisting in a chemical process followed by a conventional biological treatment, have been applied to remove mixtures of nine contaminants of pharmaceutical type spiked in a primary sedimentation effluent of a municipal wastewater. Combinations of ozone, UVA black light (BL) and Fe(III) or Fe₃O₄ catalysts constituted the chemical systems. Regardless of the Advanced Oxidation Process (AOP), the removal of pharmaceutical compounds was achieved in 1 h of reaction, while total organic carbon (TOC) only diminished between 3.4 and 6%. Among selected ozonation systems to be implemented before the biological treatment, the application of ozone alone in the pre-treatment stage is recommended due to the increase of the biodegradability observed. The application of ozone followed by the conventional biological treatment leads high TOC and COD removal rates, 60 and 61%, respectively, and allows the subsequent biological treatment works with shorter hydraulic residence time (HRT). Moreover, the influence of the application of AOPs before and after a conventional biological process was compared, concluding that the decision to take depends on the characterization of the initial wastewater with pharmaceutical compounds.

Global Radiative Forcing of Coupled Tropospheric Ozone and Aerosols in a Unified General Circulation Model

NASA Technical Reports Server (NTRS)

Liao, Hong; Seinfeld, John H.; Adams, Peter J.; Mickley, Loretta J.

2008-01-01

Global simulations of sea salt and mineral dust aerosols are integrated into a previously developed unified general circulation model (GCM), the Goddard Institute for Space Studies (GISS) GCM II', that simulates coupled tropospheric ozone-NOx-hydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m(sup -2) at TOA and +0.07 W m(sup -2) at the Earth's surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as -0.72 and -4.04 W m(sup -2), respectively. While the predicted highest aerosol cooling and heating at TOA are -10 and +12 W m(sup -2) respectively, surface forcing can reach values as high as -30 W m(sup -2), mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%.

[Ru/AC catalyzed ozonation of recalcitrant organic compounds].

PubMed

Wang, Jian-Bing; Hou, Shao-Pei; Zhou, Yun-Rui; Zhu, Wan-Peng; He, Xu-Wen

2009-09-15

Ozonation and Ru/AC catalyzed ozonation of dimethyl phthalate (DMP), phenols and disinfection by-products precursors were studied. It shows that Ru/AC catalyst can obviously enhance the mineralization of organic compounds. In the degradation of DMP, TOC removal was 28.84% by ozonation alone while it was 66.13% by catalytic ozonation. In the oxidation of 23 kinds of phenols, TOC removals were 9.57%-56.08% by ozonation alone while they were 41.81%-82.32% by catalytic ozonation. Compared to ozonation alone, Ru/AC catalyzed ozonation was more effective for the reduction of disinfection by-products formation potentials in source water. The reduction of haloacetic acids formation potentials was more obvious than thichlomethane formation potentials. After the treatment by catalytic ozonation, the haloacetic acids formation potentials decreased from 144.02 microg/L to 58.50 microg/L, which was below the standard value of EPA. However ozonation alone could not make it reach the standard. The treatments of source water by BAC, O3 + BAC, O3/AC + BAC and Ru/AC + O3 + BAC were also studied. In the four processes, TOC removal was 3.80%, 20.14%, 27.45% and 48.30% respectively, COD removal was 4.37%, 27.22%, 39.91% and 50.00% respectively, UV254 removal was 8.16%, 62.24%, 67.03% and 84.95% respectively. Ru/AC + O3 + BAC process is more effective than the other processes for the removal of TOC, COD and UV254 and no ruthenium leaching observed in the solution. It is a promising process for the treatment of micro polluted source water.

The Antarctic ozone hole

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.

1988-01-01

Processes that may be responsible for the thinning in the ozone layer above the South Pole are described. The chlorine catalytic cycle which destroys ozone is described, as are the major types of reactions that are believed to interfere with this cycle by forming chlorine reservoirs. The suspected contributions of polar stratospheric clouds to these processes are examined. Finally, the possibility that the ozone hole may be due more to a shift in atmospheric dynamics than to chemical destruction is addressed.

Diclofenac removal from water with ozone and activated carbon.

PubMed

Beltrán, Fernando J; Pocostales, Pablo; Alvarez, Pedro; Oropesa, Ana

2009-04-30

Diclofenac (DCF) has been treated in water with ozone in the presence of various activated carbons. Activated carbon-free ozonation or single ozonation leads to a complete degradation of DCF in less than 15 min while in the presence of activated carbons higher degradation rates of TOC and DCF are noticeably achieved. Among the activated carbons used, P110 Hydraffin was found the most suitable for the catalytic ozonation of DCF. The influence of pH was also investigated. In the case of the single ozonation the increasing pH slightly increases the TOC removal rate. This effect, however, was not so clear in the presence of activated carbons where the influence of the adsorption process must be considered. Ecotoxicity experiments were performed, pointing out that single ozonation reduces the toxicity of the contaminated water but catalytic ozonation improved those results. As far as kinetics is concerned, DCF is removed with ozone in a fast kinetic regime and activated carbon merely acts as a simple adsorbent. However, for TOC removal the ozonation kinetic regime becomes slow. In the absence of the adsorbent, the apparent rate constant of the mineralization process was determined at different pH values. On the other hand, determination of the rate constant of the catalytic reaction over the activated carbon was not possible due to the effect of mass transfer resistances that controlled the process rate at the conditions investigated.

Using Kalman Filter Chemical Data Assimilation to Study Ozone Catalytic Loss Cycles in January 1992

NASA Technical Reports Server (NTRS)

Lary, David J.

2002-01-01

This paper presents for the first time a global study of the ozone catalytic destruction cycles operating in the stratosphere using a stratospheric analyses for January 1992. The chemical analyses were produced using a Kalman filter data assimilation system. Because a major component of the variability of trace gases is due to the atmospheric motions the analyses have been cast in a flow-tracking coordinate system that moves with the large scale flow pattern. Particular attention is paid to the kinetic aspects of these cycles such as the rate limiting step and chain length. Although it is an important kinetic parameter, the chain length of the various cycles is seldom considered when the various catalytic cycles are discussed. This survey highlights that in the low stratosphere the cycles involving HO2 and halogens (notably bromine) are particularly important. In approximate order of effectiveness the most important ozone loss cycles in the polar lower stratosphere are the BrO/ClO, HO2/BrO, and OH/HO2 cycles. The ClO/ClO cycle clearly delineates the regions of chlorine activation. The chain length of the HO2/ClO, OH/HO2, Br/BrO, and ClO/NO2, clearly delineate the vortex edge region. The chain length of the BrO/NO2 and Cl/NO2 cycles highlight the regions of chemical processing outside the vortex where streamers of chemically processed air are stripped-off and transported away from the vortex. This is also true in the very low stratosphere for the Cl/ClO and BrO/ClO cycles.

Integrated catalytic wet air oxidation and biological treatment of wastewater from Vitamin B 6 production

NASA Astrophysics Data System (ADS)

Kang, Jianxiong; Zhan, Wei; Li, Daosheng; Wang, Xiaocong; Song, Jing; Liu, Dongqi

This study investigated the feasibility of coupling a catalytic wet air oxidation (CWAO), with CuO/Al 2O 3 as catalyst, and an anaerobic/aerobic biological process to treat wastewater from Vitamin B 6 production. Results showed that the CWAO enhanced the biodegradability (BOD 5/COD) from 0.10 to 0.80. The oxidized effluents with COD of 10,000 mg l -1 was subjected to subsequent continuous anaerobic/aerobic oxidation, and 99.3% of total COD removal was achieved. The quality of the effluent obtained met the discharge standards of water pollutants for pharmaceutical industry Chemical Synthesis Products Category (GB21904-2008), and thereby it implies that the integrated CWAO and anaerobic/aerobic biological treatment may offer a promising process to treat wastewater from Vitamin B 6 production.

Elimination of micropollutants and transformation products from a wastewater treatment plant effluent through pilot scale ozonation followed by various activated carbon and biological filters.

PubMed

Knopp, Gregor; Prasse, Carsten; Ternes, Thomas A; Cornel, Peter

2016-09-01

Conventional wastewater treatment plants are ineffective in removing a broad range of micropollutants, resulting in the release of these compounds into the aquatic environment, including natural drinking water resources. Ozonation is a suitable treatment process for micropollutant removal, although, currently, little is known about the formation, behavior, and removal of transformation products (TP) formed during ozonation. We investigated the elimination of 30 selected micropollutants (pharmaceuticals, X-ray contrast media, industrial chemicals, and TP) by biological treatment coupled with ozonation and, subsequently, in parallel with two biological filters (BF) or granular activated carbon (GAC) filters. The selected micropollutants were removed to very different extents during the conventional biological wastewater treatment process. Ozonation (specific ozone consumption: 0.87 ± 0.29 gO3 gDOC(-1), hydraulic retention time: 17 ± 3 min) eliminated a large number of the investigated micropollutants. Although 11 micropollutants could still be detected after ozonation, most of these were eliminated in subsequent GAC filtration at bed volumes (BV) of approximately 25,000 m(3) m(-3). In contrast, no additional removal of micropollutants was achieved in the BF. Ozonation of the analgesic tramadol led to the formation of tramadol-N-oxide that is effectively eliminated by GAC filters, but not by BF. For the antiviral drug acyclovir, the formation of carboxy-acyclovir was observed during activated sludge treatment, with an average concentration of 3.4 ± 1.4 μg L(-1) detected in effluent samples. Subsequent ozonation resulted in the complete elimination of carboxy-acyclovir and led to the formation of N-(4-carbamoyl-2-imino-5-oxo imidazolidin)-formamido-N-methoxyacetetic acid (COFA; average concentration: 2.6 ± 1.0 μg L(-1)). Neither the BF nor the GAC filters were able to remove COFA. These results highlight the importance of considering TP in the

Heterogeneous catalytic ozonation of clofibric acid using Ce/MCM-48: Preparation, reaction mechanism, comparison with Ce/MCM-41.

PubMed

Li, Shangyi; Tang, Yiming; Chen, Weirui; Hu, Zhe; Li, Xukai; Li, Laisheng

2017-10-15

Three-dimensional mesoporous MCM-48 and Ce loaded MCM-48 (Ce/MCM-48) were synthesized by hydrothermal and impregnating methods, respectively. They were characterized by XRD, SEM, TEM, EDS, XPS, N 2 adsorption-desorption techniques, and the results showed that Ce/MCM-48 still retained a highly ordered cubic structure. A series of experiments were conducted to study the catalytic activity of Ce/MCM-48 and Ce/MCM-41 for ozonation of clofibric acid in aqueous solution. Total Organic Carbon (TOC) removal efficiency in Ce/MCM-48/O 3 can be improved to 64% at 120min reaction time, 54% by Ce/MCM-41/O 3 , only 24% by MCM-48/O 3 , 23% by single ozonation. Ce/MCM-48 did not show any adsorption capacity for CA. Effect of initial pH revealed that active sites were surface protonated hydroxyl groups. The restraint of phosphate and sodium hydrogen sulfite (NaHSO 3 ) on the mineralization of CA illustrated more hydroxyl radicals were generated by Ce/MCM-48 catalysts than Ce/MCM-41. The degradation pathway of CA was investigated by the alterations of pH under different conditions. Recycle tests of catalysts demonstrated that compared with Ce/MCM-41, Ce/MCM-48 exhibited more excellent catalytic efficiency and stability because of its unique pore systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Treatment of high strength distillery wastewater (cherry stillage) by integrated aerobic biological oxidation and ozonation.

PubMed

Beltrán, F J; Alvarez, P M; Rodríguez, E M; García-Araya, J F; Rivas, J

2001-01-01

The performance of integrated aerobic digestion and ozonation for the treatment of high strength distillery wastewater (i.e., cherry stillage) is reported. Experiments were conducted in laboratory batch systems operating in draw and fill mode. For the biological step, activated sludge from a municipal wastewater treatment facility was used as inoculum, showing a high degree of activity to distillery wastewater. Thus, BOD and COD overall conversions of 95% and 82% were achieved, respectively. However, polyphenol content and absorbance at 254 nm (A(254)) could not be reduced more than 35% and 15%, respectively, by means of single biological oxidation. By considering COD as substrate, the aerobic digestion process followed a Contois' model kinetics, from which the maximum specific growth rate of microorganisms (mu(max)) and the inhibition factor, beta, were then evaluated at different conditions of temperature and pH. In the combined process, the effect of a post-ozonation stage was studied. The main goals achieved by the ozonation step were the removal of polyphenols and A(254). Therefore, ozonation was shown to be an appropriate technology to aid aerobic biological oxidation in the treatment of cherry stillage.

Stratospheric ozone over the United States in summer linked to observations of convection and temperature via chlorine and bromine catalysis

PubMed Central

Anderson, James G.; Weisenstein, Debra K.; Bowman, Kenneth P.; Homeyer, Cameron R.; Smith, Jessica B.; Wilmouth, David M.; Sayres, David S.; Klobas, J. Eric; Dykema, John A.; Wofsy, Steven C.

2017-01-01

We present observations defining (i) the frequency and depth of convective penetration of water into the stratosphere over the United States in summer using the Next-Generation Radar system; (ii) the altitude-dependent distribution of inorganic chlorine established in the same coordinate system as the radar observations; (iii) the high resolution temperature structure in the stratosphere over the United States in summer that resolves spatial and structural variability, including the impact of gravity waves; and (iv) the resulting amplification in the catalytic loss rates of ozone for the dominant halogen, hydrogen, and nitrogen catalytic cycles. The weather radar observations of ∼2,000 storms, on average, each summer that reach the altitude of rapidly increasing available inorganic chlorine, coupled with observed temperatures, portend a risk of initiating rapid heterogeneous catalytic conversion of inorganic chlorine to free radical form on ubiquitous sulfate−water aerosols; this, in turn, engages the element of risk associated with ozone loss in the stratosphere over the central United States in summer based upon the same reaction network that reduces stratospheric ozone over the Arctic. The summertime development of the upper-level anticyclonic flow over the United States, driven by the North American Monsoon, provides a means of retaining convectively injected water, thereby extending the time for catalytic ozone loss over the Great Plains. Trusted decadal forecasts of UV dosage over the United States in summer require understanding the response of this dynamical and photochemical system to increased forcing of the climate by increasing levels of CO2 and CH4. PMID:28584119

Stratospheric ozone over the United States in summer linked to observations of convection and temperature via chlorine and bromine catalysis.

PubMed

Anderson, James G; Weisenstein, Debra K; Bowman, Kenneth P; Homeyer, Cameron R; Smith, Jessica B; Wilmouth, David M; Sayres, David S; Klobas, J Eric; Leroy, Stephen S; Dykema, John A; Wofsy, Steven C

2017-06-20

We present observations defining ( i ) the frequency and depth of convective penetration of water into the stratosphere over the United States in summer using the Next-Generation Radar system; ( ii ) the altitude-dependent distribution of inorganic chlorine established in the same coordinate system as the radar observations; ( iii ) the high resolution temperature structure in the stratosphere over the United States in summer that resolves spatial and structural variability, including the impact of gravity waves; and ( iv ) the resulting amplification in the catalytic loss rates of ozone for the dominant halogen, hydrogen, and nitrogen catalytic cycles. The weather radar observations of ∼2,000 storms, on average, each summer that reach the altitude of rapidly increasing available inorganic chlorine, coupled with observed temperatures, portend a risk of initiating rapid heterogeneous catalytic conversion of inorganic chlorine to free radical form on ubiquitous sulfate-water aerosols; this, in turn, engages the element of risk associated with ozone loss in the stratosphere over the central United States in summer based upon the same reaction network that reduces stratospheric ozone over the Arctic. The summertime development of the upper-level anticyclonic flow over the United States, driven by the North American Monsoon, provides a means of retaining convectively injected water, thereby extending the time for catalytic ozone loss over the Great Plains. Trusted decadal forecasts of UV dosage over the United States in summer require understanding the response of this dynamical and photochemical system to increased forcing of the climate by increasing levels of CO 2 and CH 4 .

Spatially coupled catalytic ignition of CO oxidation on Pt: mesoscopic versus nano-scale

PubMed Central

Spiel, C.; Vogel, D.; Schlögl, R.; Rupprechter, G.; Suchorski, Y.

2015-01-01

Spatial coupling during catalytic ignition of CO oxidation on μm-sized Pt(hkl) domains of a polycrystalline Pt foil has been studied in situ by PEEM (photoemission electron microscopy) in the 10−5 mbar pressure range. The same reaction has been examined under similar conditions by FIM (field ion microscopy) on nm-sized Pt(hkl) facets of a Pt nanotip. Proper orthogonal decomposition (POD) of the digitized FIM images has been employed to analyze spatiotemporal dynamics of catalytic ignition. The results show the essential role of the sample size and of the morphology of the domain (facet) boundary in the spatial coupling in CO oxidation. PMID:26021411

Stratospheric Ozone Loss Over the US in Summer: Recent Advances in Observations of Temperatures, Convective Injection of Condensed Phase Water, and Analyses of Volcanic Injections That are Used to Inform Model Calculations of Catalytic Mechanisms that Control the Response of O3.

NASA Astrophysics Data System (ADS)

Anderson, J. G.

2016-12-01

In the context of changes to the structure of the Earth's climate, consequences to stratospheric ozone over the US in summer are considered. Key advances in observations directly related to the catalytic loss of ozone in the lower stratosphere include: Analysis of high resolution temperature observations over the central US in July and August from both SEAC4RS in situ observations and radio occultation (RO) observations, Inclusion of gravity wave observations from both SEAC4RS and RO measurements, Climatology of NEXRAD weather radar mapping of the 3D convective injection of condensed phase water over the central US in summer, Analysis of the impact on ozone in the lower stratosphere over the US in summer using the AER 2D model calculations of the key rate limiting radicals and rate limiting catalytic loss rates as a function of water vapor, temperature and sulfate loading in the lower stratosphere, Analysis of the impact on ozone in summer over the US under conditions of volcanic injection, overt sulfate addition for solar radiation management, and/or convective injection of water vapor, Emphasis in the analysis is placed specifically on the geographic region over the Great Plains of the US in summer because of the confluence of temperatures and water vapor concentrations that initiate the heterogeneous catalytic conversion of inorganic chlorine, primarily HCl and ClONO2, to free radical form, ClO. The ClO radical in turn engages gas phase catalytic cycles that remove ozone via the photochemical reaction mechanisms virtually identical to the catalytic photochemical processes that remove ozone over the Arctic each year in late spring. In situ observations, in the lower stratosphere of the Arctic, of the principal reaction networks that establish the relationship between observed ozone loss and the threshold in temperature, water vapor and sulfate loading is used to establish the photochemical coordinate system required to analyze ozone loss in the lower stratosphere

Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: Removal and pathways.

PubMed

Wu, Jin; Ma, Luming; Chen, Yunlu; Cheng, Yunqin; Liu, Yan; Zha, Xiaosong

2016-04-01

Catalytic ozonation of organic pollutants from actual bio-treated dyeing and finishing wastewater (BDFW) with iron shavings was investigated. Catalytic ozonation effectively removed organic pollutants at initial pH values of 7.18-7.52, and the chemical oxygen demand (COD) level decreased from 142 to 70 mg·L(-1) with a discharge limitation of 80 mg·L(-1). A total of 100% and 42% of the proteins and polysaccharides, respectively, were removed with a decrease in their contribution to the soluble COD from 76% to 41%. Among the 218 organic species detected by liquid chromatography-mass spectrometry, 58, 77, 79 and 4 species were completely removed, partially removed, increased and newly generated, respectively. Species including textile auxiliaries and dye intermediates were detected by gas chromatography-mass spectrometry. The inhibitory effect decreased from 51% to 33%, suggesting a reduction in the acute toxicity. The enhanced effect was due to hydroxyl radical (OH) oxidation, co-precipitation and oxidation by other oxidants. The proteins were removed by OH oxidation (6%), by direct ozonation, co-precipitation and oxidation by other oxidants (94%). The corresponding values for polysaccharides were 21% and 21%, respectively. In addition, the iron shavings behaved well in successive runs. These results indicated that the process was favorable for engineering applications for removal of organic pollutants from BDFW. Copyright © 2016 Elsevier Ltd. All rights reserved.

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

NASA Astrophysics Data System (ADS)

Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

2017-02-01

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH)2, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

Robust impact of coupled stratospheric ozone chemistry on the response of the Austral circulation to increased greenhouse gases

NASA Astrophysics Data System (ADS)

Chiodo, G.; Polvani, L. M.

2016-12-01

Due to computational constraints, interactive stratospheric chemistry is commonly neglected in most GCMs participating in inter-comparison projects. The impact of this simplification on the modeled response to external forcings remains largely unexplored. In this work, we examine the impact of the stratospheric chemistry coupling on the SH circulation response to an abrupt quadrupling of CO2. We accomplish this with a version of the Whole Atmosphere Community Climate (WACCM) model, which allows coupling and de-coupling stratospheric chemistry, without altering any other physical parameterization. We find that the chemistry coupling in WACCM significantly reduces (by about 20%) the response of both eddy-driven mid-latitude jet and the Hadley Cell strength, without altering the surface temperature response. This behavior is linked to the representation of stratospheric ozone, and its effects on the meridional temperature gradient at the extratropical tropopause. Our results imply that neglecting stratospheric ozone chemistry results in a potential overestimation of the circulation response to GHGs. Hence, stratospheric ozone chemistry produces a substantial negative feedback on the response of the atmospheric circulation to increased greenhouse gases.

Tropospheric ozone simulated by a global-multi-regional two-way coupling model system

NASA Astrophysics Data System (ADS)

Yan, Y.; Lin, J.; Chen, J.; Hu, L.

2015-12-01

Current global chemical transport models are limited by horizontal resolutions (100-500 km), and they cannot capture small-scale processes affecting tropospheric ozone (O3). Here we use a recently built two-way coupling system of GEOS-Chem to simulate the global tropospheric O3 in 2009. The system couples the global model (~ 200 km) and its three nested models (~ 50 km) covering Asia, North America and Europe, respectively. Benefiting from the high resolution, the nested models better capture small-scale processes than the global model alone. In the coupling system, the nested models provide results to modify the global model simulation within respective nested domains while taking the lateral boundary conditions from the global model. Due to the "coupling" effects, the two-way system significantly improves the tropospheric O3 simulation upon the global model alone, as found by comparisons with a suite of ground (1420 sites from WDCGG, GMD, EMEP, and AQS), aircraft (HIPPO and MOZAIC), and satellite measurements (two OMI products). Compared to the global model alone, the two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean O3 with the ground measurements from 0.53 to 0.68 and reduces the mean model bias from 10.8 to 6.7 ppb. Regionally, the coupled model reduces the bias by 4.6 ppb over Europe, 3.9 ppb over North America, and 3.1 ppb over other regions. The two-way coupling brings O3 vertical profiles much closer to the HIPPO and MOZAIC data, reducing the tropospheric (0-9 km) mean bias by 3-10 ppb at most MOZAIC sites and by 5.3 ppb for HIPPO profiles. The two-way coupled simulation also reduces the global tropospheric column ozone by 3.0 DU (9.5%), bringing them closer to the OMI data in all seasons. Simulation improvements are more significant in the northern hemisphere, and are primarily a result of improved representation of the nonlinear ozone chemistry, including but not limited to urban-rural contrast. The two

Impact of ozonation and biological activated carbon filtration on ceramic membrane fouling.

PubMed

Ibn Abdul Hamid, Khaled; Sanciolo, Peter; Gray, Stephen; Duke, Mikel; Muthukumaran, Shobha

2017-12-01

Ozone pre-treatment (ozonation, ozonisation) and biological activated carbon (BAC) filtration pre-treatment for the ceramic microfiltration (CMF) treatment of secondary effluent (SE) were studied. Ozone pre-treatment was found to result in higher overall removal of UV absorbance (UVA 254 ) and colour, and higher permeability than BAC pre-treatment or the combined use of ozone and BAC (O3+BAC) pre-treatment. The overall removal of colour and UVA 254 by ceramic filtration of the ozone pre-treated water was 97% and 63% respectively, compared to 86% and 48% respectively for BAC pre-treatment and 29% and 6% respectively for the untreated water. Ozone pre-treatment, however, was not effective in removal of dissolved organic carbon (DOC). The permeability of the ozone pre-treated water through the ceramic membrane was found to decrease to 50% of the original value after 200 min of operation, compared to approximately 10% of the original value for the BAC pre-treated, O3+BAC pre-treated water and the untreated water. The higher permeability of the ozone pre-treated water was attributed to the excellent removal of biopolymer particles (100%) and high removal of humic substances (84%). The inclusion of a BAC stage between ozone pre-treatment and ceramic filtration was detrimental. The O3+BAC+CMF process was found to yield higher biopolymer removal (96%), lower humic substance (HS) component removal (66%) and lower normalized permeability (0.1) after 200 min of operation than the O3+CMF process (86%, 84% and 0.5 respectively). This was tentatively attributed to the chemical oxidation effect of ozone on the BAC biofilm and adsorbed components, leading to the generation of foulants that are not generated in the O3+CMF process. This study demonstrated the potential of ozone pre-treatment for reducing organic fouling and thus improving flux for the CMF of SE compared to O3+BAC pre-treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determining the transport mechanism of an enzyme-catalytic complex metabolic network based on biological robustness.

PubMed

Wang, Lei

2013-04-01

Understanding the transport mechanism of 1,3-propanediol (1,3-PD) is of critical importance to do further research on gene regulation. Due to the lack of intracellular information, on the basis of enzyme-catalytic system, using biological robustness as performance index, we present a system identification model to infer the most possible transport mechanism of 1,3-PD, in which the performance index consists of the relative error of the extracellular substance concentrations and biological robustness of the intracellular substance concentrations. We will not use a Boolean framework but prefer a model description based on ordinary differential equations. Among other advantages, this also facilitates the robustness analysis, which is the main goal of this paper. An algorithm is constructed to seek the solution of the identification model. Numerical results show that the most possible transport way is active transport coupled with passive diffusion.

Ozone Production and Loss Rate Measurements in the Middle Stratosphere

NASA Technical Reports Server (NTRS)

Jucks, Kenneth W.; Johnson, David G.; Chance, K. V.; Traub, Wesley A.; Salawitch, R. J.; Stachnik, R. A.

1996-01-01

The first simultaneous measurements of HO(x), NO(x), and Cl(x) radicals in the middle stratosphere show that NO(x) catalytic cycles dominate loss of ozone (O3) for altitudes between 24 and 38 km; Cl(x) catalytic cycles are measured to be less effective than previously expected; and there is no 'ozone deficit' in the photochemically dominated altitude range from 31 and 38 km, contrary to some previous theoretical studies.

Ozone Layer Observations

NASA Technical Reports Server (NTRS)

McPeters, Richard; Bhartia, P. K. (Technical Monitor)

2002-01-01

The US National Aeronautics and Space Administration (NASA) has been monitoring the ozone layer from space using optical remote sensing techniques since 1970. With concern over catalytic destruction of ozone (mid-1970s) and the development of the Antarctic ozone hole (mid-1980s), long term ozone monitoring has become the primary focus of NASA's series of ozone measuring instruments. A series of TOMS (Total Ozone Mapping Spectrometer) and SBUV (Solar Backscatter Ultraviolet) instruments has produced a nearly continuous record of global ozone from 1979 to the present. These instruments infer ozone by measuring sunlight backscattered from the atmosphere in the ultraviolet through differential absorption. These measurements have documented a 15 Dobson Unit drop in global average ozone since 1980, and the declines in ozone in the antarctic each October have been far more dramatic. Instruments that measure the ozone vertical distribution, the SBUV and SAGE (Stratospheric Aerosol and Gas Experiment) instruments for example, show that the largest changes are occurring in the lower stratosphere and upper troposphere. The goal of ozone measurement in the next decades will be to document the predicted recovery of the ozone layer as CFC (chlorofluorocarbon) levels decline. This will require a continuation of global measurements of total column ozone on a global basis, but using data from successor instruments to TOMS. Hyperspectral instruments capable of measuring in the UV will be needed for this purpose. Establishing the relative roles of chemistry and dynamics will require instruments to measure ozone in the troposphere and in the stratosphere with good vertical resolution. Instruments that can measure other chemicals important to ozone formation and destruction will also be needed.

A comparative study of ozonation, iron coated zeolite catalyzed ozonation and granular activated carbon catalyzed ozonation of humic acid.

PubMed

Gümüş, Dilek; Akbal, Feryal

2017-05-01

This study compares ozonation (O 3 ), iron coated zeolite catalyzed ozonation (ICZ-O 3 ) and granular activated carbon catalyzed ozonation (GAC-O 3 ) for removal of humic acid from an aqueous solution. The results were evaluated by the removal of DOC that specifies organic matter, UV 254 absorbance, SUVA (Specific Ultraviolet Absorbance at 254 nm) and absorbance at 436 nm. When ozonation was used alone, DOC removal was 21.4% at an ozone concentration of 10 mg/L, pH 6.50 and oxidation time of 60 min. The results showed that the use of ICZ or GAC as a catalyst increased the decomposition of humic acid compared to ozonation alone. DOC removal efficiencies were 62% and 48.1% at pH 6.5, at a catalyst loading of 0.75 g/L, and oxidation time of 60 min for ICZ and GAC, respectively. The oxidation experiments were also carried out using <100 kDa and <50 kDa molecular size fractions of humic acid in the presence of ICZ or GAC. Catalytic ozonation also yielded better DOC and UV 254 reduction in both <50 kDa and <100 kDa fractions of HA compared to ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Concerns for Ozone Recovery

NASA Technical Reports Server (NTRS)

Liang, Qing; Strahan, Susan E.; Fleming, Eric L.

2017-01-01

Reactive halogen gases containing chlorine (Cl) or bromine (Br) can destroy stratospheric ozone via catalytic cycles. The main sources of atmospheric reactive halogen are the long-lived synthetic chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), carbon tetrachloride (CCl4), methyl chloroform (CH3CCl3), and bromine-containing halons, all of which persist in the atmosphere for years. These ozone-depleting substances are now controlled under the Montreal Protocol and its amendments. Natural methyl bromide (CH3Br) and methyl chloride (CH3Cl) emissions are also important long-lived sources of atmospheric reactive halogen. Rising concentrations of very-short-lived substances (VSLSs) with atmospheric lifetimes of less than half a year may also contribute to future stratospheric ozone depletion. A greater concern for ozone layer recovery is incomplete compliance with the Montreal Protocol, which will impact stratospheric ozone for many decades, as well as rising natural emissions as a result of climate change.

Vibronic coupling and selectivity of vibrational excitation in the negative ion resonances of ozone

NASA Astrophysics Data System (ADS)

Allan, Michael; Popovic̀, Duška B.

1997-04-01

A recent experimental paper reported two shape resonances in electron impact on ozone, A 1 and B 2, both causing vibrational excitation with a distinct pattern of selectivity. The present Letter attempts to rationalize this selectivity using approximate potential curves, calculated for the A 1 and B 2 resonances by adding the SCF energy of neutral ozone to electron attachment energies calculated from ab initio virtual orbital energies using the Koopmans' theorem and an empirical scaling relation. The slopes of the curves explain the efficient excitation of the symmetric stretch by both resonances and the lack of the bending excitation by the B 2 resonance. The A 1 and B 2 resonances are strongly coupled by the b 2 antisymmetric stretch vibration, causing a double minimum on the lower surface. Nonadiabatic effects caused by the strong vibronic coupling explain the observed excitation of the antisymmetric stretch vibration.

Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid.

PubMed

Rosal, Roberto; Gonzalo, María S; Boltes, Karina; Letón, Pedro; Vaquero, Juan J; García-Calvo, E

2009-12-30

The degradation of an aqueous solution of clofibric acid was investigated during catalytic and non-catalytic ozonation. The catalyst, TiO(2), enhanced the production of hydroxyl radicals from ozone and raised the fraction or clofibric acid degraded by hydroxyl radicals. The rate constant for the reaction of clofibric acid and hydroxyl radicals was not affected by the presence of the catalyst. The toxicity of the oxidation products obtained during the reaction was assessed by means of Vibrio fischeri and Daphnia magna tests in order to evaluate the potential formation of toxic by-products. The results showed that the ozonation was enhanced by the presence of TiO(2,) the clofibric acid being removed completely after 15 min at pH 5. The evolution of dissolved organic carbon, specific ultraviolet absorption at 254 nm and the concentration of carboxylic acids monitored the degradation process. The formation of 4-chlorophenol, hydroquinone, 4-chlorocatechol, 2-hydroxyisobutyric acid and three non-aromatic compounds identified as a product of the ring-opening reaction was assessed by exact mass measurements performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-TOF-MS). The bioassays showed a significant increase in toxicity during the initial stages of ozonation following a toxicity pattern closely related to the formation of ring-opening by-products.

Improved simulation of tropospheric ozone by a global-multi-regional two-way coupling model system

NASA Astrophysics Data System (ADS)

Yan, Yingying; Lin, Jintai; Chen, Jinxuan; Hu, Lu

2016-02-01

Small-scale nonlinear chemical and physical processes over pollution source regions affect the tropospheric ozone (O3), but these processes are not captured by current global chemical transport models (CTMs) and chemistry-climate models that are limited by coarse horizontal resolutions (100-500 km, typically 200 km). These models tend to contain large (and mostly positive) tropospheric O3 biases in the Northern Hemisphere. Here we use the recently built two-way coupling system of the GEOS-Chem CTM to simulate the regional and global tropospheric O3 in 2009. The system couples the global model (at 2.5° long. × 2° lat.) and its three nested models (at 0.667° long. × 0.5° lat.) covering Asia, North America and Europe, respectively. Specifically, the nested models take lateral boundary conditions (LBCs) from the global model, better capture small-scale processes and feed back to modify the global model simulation within the nested domains, with a subsequent effect on their LBCs. Compared to the global model alone, the two-way coupled system better simulates the tropospheric O3 both within and outside the nested domains, as found by evaluation against a suite of ground (1420 sites from the World Data Centre for Greenhouse Gases (WDCGG), the United States National Oceanic and Atmospheric Administration (NOAA) Earth System Research Laboratory Global Monitoring Division (GMD), the Chemical Coordination Centre of European Monitoring and Evaluation Programme (EMEP), and the United States Environmental Protection Agency Air Quality System (AQS)), aircraft (the High-performance Instrumented Airborne Platform for Environmental Research (HIAPER) Pole-to-Pole Observations (HIPPO) and Measurement of Ozone and Water Vapor by Airbus In- Service Aircraft (MOZAIC)) and satellite measurements (two Ozone Monitoring Instrument (OMI) products). The two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean surface O3 with the ground measurements

Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene.

PubMed

Hatakeyama, Takuji; Kondo, Yoshiyuki; Fujiwara, Yu-Ichi; Takaya, Hikaru; Ito, Shingo; Nakamura, Eiichi; Nakamura, Masaharu

2009-03-14

A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2018-01-01

The study is the assessment of commercial γ-Al 2 O 3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media. Copyright © 2017 Elsevier B.V. All rights reserved.

Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

PubMed

Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

2018-04-01

As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

pH-insusceptible cobalt-manganese immobilizing mesoporous siliceous MCM-41 catalyst for ozonation of dimethyl phthalate.

PubMed

Tang, Yiming; Pan, Zhaoqi; Li, Laisheng

2017-12-15

Mesoporous siliceous MCM-41 immobilized with Co and Mn metal ions (Co-Mn-MCM-41) was synthesized using a hydrothermal method. The structural regularity and the valence states of the metal species were measured by X-ray diffractometer and X-ray photoelectron spectrometer. The resultant bimetallic Co-Mn-MCM-41 catalyst was tested for the degradation of dimethyl phthalate (DMP) via a catalytic ozonation mechanism, demonstrating that the catalytic properties of Co-Mn-MCM-41 catalyst significantly accelerated the ozonation process. Total organic carbon (TOC) and DMP removal efficiency reached 94% and 99.7% at 15min under the optimal conditions. The oxidation pathways were proposed after identifying the intermediate products from ozonation using a gas chromatography-mass spectrometer. The enhanced catalytic reactivity was attributed to the highly-dispersive cobalt and manganese species in MCM-41 scaffolds, which promoted the ozone decomposition and hydroxyl radicals' generation in catalytic ozonation and accelerated the degradation of DMP. Bimetallic Co-Mn-MCM-41 catalyst remained stable in mild acidic conditions and continued to show high activity after repeated runs. Copyright © 2017 Elsevier Inc. All rights reserved.

Ozone/graphene oxide catalytic oxidation: a novel method to degrade emerging organic contaminant N, N-diethyl-m-toluamide (DEET).

PubMed

Liu, Jia-Nan; Chen, Zhuo; Wu, Qian-Yuan; Li, Ang; Hu, Hong-Ying; Yang, Cheng

2016-08-11

N, N-diethyl-m-toluamide (DEET) is one of the important emerging contaminants that are being increasingly detected in reclaimed water as well as in drinking water sources. However, DEET is refractory to conventional biological treatment and pure ozone which is absent of hydroxyl radical. Current researches on the efficient removal of DEET are still quite limited. This study utilizes a novel method, namely ozone/graphene oxide (O3/GO), to investigate the effects on DEET removal in aqueous systems, especially in reclaimed water. The results indicate that the DEET degradation rate was significantly accelerated through the combined effect of GO and ozonation which can yield abundant hydroxyl radical, compared to pure ozone condition. According to hydroxyl radical scavenging experiments, hydroxyl radical was found to play a dominant role in synergistic removal of DEET. These findings can offer sound suggestions for future research on the removal of emerging organic contaminants. The information could also be beneficial to reclaimed water safety and sustainable management.

Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation.

PubMed

Rosal, Roberto; Rodríguez, Antonio; Perdigón-Melón, José Antonio; Petre, Alice; García-Calvo, Eloy; Gómez, María José; Agüera, Ana; Fernández-Alba, Amadeo R

2010-01-01

This work reports a systematic survey of over seventy individual pollutants in a Sewage Treatment Plant (STP) receiving urban wastewater. The compounds include mainly pharmaceuticals and personal care products, as well as some metabolites. The quantification in the ng/L range was performed by Liquid Chromatography-QTRAP-Mass Spectrometry and Gas Chromatography coupled to Mass Spectrometry. The results showed that paraxanthine, caffeine and acetaminophen were the main individual pollutants usually found in concentrations over 20 ppb. N-formyl-4-amino-antipiryne and galaxolide were also detected in the ppb level. A group of compounds including the beta-blockers atenolol, metoprolol and propanolol; the lipid regulators bezafibrate and fenofibric acid; the antibiotics erythromycin, sulfamethoxazole and trimethoprim, the antiinflammatories diclofenac, indomethacin, ketoprofen and mefenamic acid, the antiepileptic carbamazepine and the antiacid omeprazole exhibited removal efficiencies below 20% in the STP treatment. Ozonation with doses lower than 90 microM allowed the removal of many individual pollutants including some of those more refractory to biological treatment. A kinetic model allowed the determination of second order kinetic constants for the ozonation of bezafibrate, cotinine, diuron and metronidazole. The results show that the hydroxyl radical reaction was the major pathway for the oxidative transformation of these compounds. (c) 2009 Elsevier Ltd. All rights reserved.

Transient and sustained elementary flux mode networks on a catalytic string-based chemical evolution model.

PubMed

Pereira, José A

2014-08-01

Theoretical models designed to test the metabolism-first hypothesis for prebiotic evolution have yield strong indications about the hypothesis validity but could sometimes use a more extensive identification between model objects and real objects towards a more meaningful interpretation of results. In an attempt to go in that direction, the string-based model SSE ("steady state evolution") was developed, where abstract molecules (strings) and catalytic interaction rules are based on some of the most important features of carbon compounds in biological chemistry. The system is open with a random inflow and outflow of strings but also with a permanent string food source. Although specific catalysis is a key aspect of the model, used to define reaction rules, the focus is on energetics rather than kinetics. Standard energy change tables were constructed and used with standard formation reactions to track energy flows through the interpretation of equilibrium constant values. Detection of metabolic networks on the reaction system was done with elementary flux mode (EFM) analysis. The combination of these model design and analysis options enabled obtaining metabolic and catalytic networks showing several central features of biological metabolism, some more clearly than in previous models: metabolic networks with stepwise synthesis, energy coupling, catalysts regulation, SN2 coupling, redox coupling, intermediate cycling, coupled inverse pathways (metabolic cycling), autocatalytic cycles and catalytic cascades. The results strongly suggest that the main biological metabolism features, including the genotype-phenotype interpretation, are caused by the principles of catalytic systems and are prior to modern genetic systems principles. It also gives further theoretical support to the thesis that the basic features of biologic metabolism are a consequence of the time evolution of a random catalyst search working on an open system with a permanent food source. The importance

Partial degradation of five pesticides and an industrial pollutant by ozonation in a pilot-plant scale reactor.

PubMed

Maldonado, M I; Malato, S; Pérez-Estrada, L A; Gernjak, W; Oller, I; Doménech, Xavier; Peral, José

2006-11-16

Aqueous solutions of a mixture of several pesticides (alachlor, atrazine, chlorfenvinphos, diuron and isoproturon), considered PS (priority substances) by the European Commission, and an intermediate product of the pharmaceutical industry (alpha-methylphenylglycine, MPG) chosen as a model industrial pollutant, have been degraded at pilot-plant scale using ozonation. This study is part of a large research project [CADOX Project, A Coupled Advanced Oxidation-Biological Process for Recycling of Industrial Wastewater Containing Persistent Organic Contaminants, Contract No.: EVK1-CT-2002-00122, European Commission, http://www.psa.es/webeng/projects/cadox/index.html] founded by the European Union that inquires into the potential coupling between chemical and biological oxidations for the removal of toxic or non-biodegradable contaminants from water. The evolution of pollutant concentration, TOC mineralization, generation of inorganic species and consumption of O3 have been followed in order to visualize the chemical treatment effectiveness. Although complete mineralization is hard to accomplish, and large amounts of the oxidant are required to lower the organic content of the solutions, the possibility of ozonation cannot be ruled out if partial degradation is the final goal wanted. In this sense, Zahn-Wellens biodegradability tests of the ozonated MPG solutions have been performed, and the possibility of a further coupling with a secondary biological treatment for complete organic removal is envisaged.

Enantioselective Desymmetrization via Carbonyl-Directed Catalytic Asymmetric Hydroboration and Suzuki-Miyaura Cross-Coupling

PubMed Central

Hoang, Gia L.; Yang, Zhao-Di; Smith, Sean M.; Pal, Rhitankar; Miska, Judy L.; Pérez, Damaris E.; Pelter, Libbie S. W.; Zeng, Xiao Cheng; Takacs, James M.

2015-01-01

The rhodium-catalyzed enantioselective desymmetrization of symmetric γ,δ–unsaturated amides via carbonyl-directed catalytic asymmetric hydroboration (directed CAHB) affords chiral secondary organoboronates with up to 98% ee. The chiral γ–borylated products undergo palladium-catalyzed Suzuki-Miyaura cross-coupling via the trifluoroborate salt with stereoretention. PMID:25642639

Issues in Stratospheric Ozone Depletion.

NASA Astrophysics Data System (ADS)

Lloyd, Steven Andrew

Following the announcement of the discovery of the Antarctic ozone hole in 1985 there have arisen a multitude of questions pertaining to the nature and consequences of polar ozone depletion. This thesis addresses several of these specific questions, using both computer models of chemical kinetics and the Earth's radiation field as well as laboratory kinetic experiments. A coupled chemical kinetic-radiative numerical model was developed to assist in the analysis of in situ field measurements of several radical and neutral species in the polar and mid-latitude lower stratosphere. Modeling was used in the analysis of enhanced polar ClO, mid-latitude diurnal variation of ClO, and simultaneous measurements of OH, HO_2, H_2 O and O_3. Most importantly, such modeling was instrumental in establishing the link between the observed ClO and BrO concentrations in the Antarctic polar vortex and the observed rate of ozone depletion. The principal medical concern of stratospheric ozone depletion is that ozone loss will lead to the enhancement of ground-level UV-B radiation. Global ozone climatology (40^circS to 50^ circN latitude) was incorporated into a radiation field model to calculate the biologically accumulated dosage (BAD) of UV-B radiation, integrated over days, months, and years. The slope of the annual BAD as a function of latitude was found to correspond to epidemiological data for non-melanoma skin cancers for 30^circ -50^circN. Various ozone loss scenarios were investigated. It was found that a small ozone loss in the tropics can provide as much additional biologically effective UV-B as a much larger ozone loss at higher latitudes. Also, for ozone depletions of > 5%, the BAD of UV-B increases exponentially with decreasing ozone levels. An important key player in determining whether polar ozone depletion can propagate into the populated mid-latitudes is chlorine nitrate, ClONO_2 . As yet this molecule is only indirectly accounted for in computer models and field

Modeling coupled interactions of carbon, water, and ozone exchange between terrestrial ecosystems and the atmosphere

Treesearch

Ned Nikolova; Karl F. Zeller

2003-01-01

A new biophysical model (FORFLUX) is presented to study the simultaneous exchange of ozone, carbon dioxide, and water vapor between terrestrial ecosystems and the atmosphere. The model mechanistically couples all major processes controlling ecosystem flows trace gases and water implementing recent concepts in plant eco-physiology, micrometeorology, and soil hydrology....

Fiber-Optic Coupled Lidar Receiver System to Measure Stratospheric Ozone

NASA Technical Reports Server (NTRS)

Harper, David Brent; Elsayed-Ali, Hani

1998-01-01

The measurement of ozone in the atmosphere has become increasingly important over the past two decades. Significant increases of ozone concentrations in the lower atmosphere, or troposphere, and decreases in the upper atmosphere, or stratosphere, have been attributed to man-made causes. High ozone concentrations in the troposphere pose a health hazard to plants and animals and can add to global warming. On the other hand, ozone in the stratosphere serves as a protective barrier against strong ultraviolet (UV) radiation from the sun. Man-made CFC's (chlorofluorocarbons) act as a catalyst with a free oxygen atom and an ozone molecule to produce two oxygen molecules therefore depleting the protective layer of ozone in the stratosphere. The beneficial and harmful effects of ozone require the study of ozone creation and destruction processes in the atmosphere. Therefore, to provide an accurate model of these processes, an ozone lidar system must be able to be used frequently with as large a measurement range as possible. Various methods can be used to measure atmospheric ozone concentrations. These include different airborne and balloon measurements, solar occulation satellite techniques, and the use of lasers in lidar (high detection and ranging,) systems to probe the atmosphere. Typical devices such as weather balloons can only measure within the direct vicinity of the instrument and are therefore used infrequently. Satellites use solar occulation techniques that yield low horizontal and vertical resolution column densities of ozone.

Role of coupled dynamics in the catalytic activity of prokaryotic-like prolyl-tRNA synthetases.

PubMed

Sanford, Brianne; Cao, Bach; Johnson, James M; Zimmerman, Kurt; Strom, Alexander M; Mueller, Robyn M; Bhattacharyya, Sudeep; Musier-Forsyth, Karin; Hati, Sanchita

2012-03-13

Prolyl-tRNA synthetases (ProRSs) have been shown to activate both cognate and some noncognate amino acids and attach them to specific tRNA(Pro) substrates. For example, alanine, which is smaller than cognate proline, is misactivated by Escherichia coli ProRS. Mischarged Ala-tRNA(Pro) is hydrolyzed by an editing domain (INS) that is distinct from the activation domain. It was previously shown that deletion of the INS greatly reduced cognate proline activation efficiency. In this study, experimental and computational approaches were used to test the hypothesis that deletion of the INS alters the internal protein dynamics leading to reduced catalytic function. Kinetic studies with two ProRS variants, G217A and E218A, revealed decreased amino acid activation efficiency. Molecular dynamics studies showed motional coupling between the INS and protein segments containing the catalytically important proline-binding loop (PBL, residues 199-206). In particular, the complete deletion of INS, as well as mutation of G217 or E218 to alanine, exhibited significant effects on the motion of the PBL. The presence of coupled dynamics between neighboring protein segments was also observed through in silico mutations and essential dynamics analysis. Altogether, this study demonstrates that structural elements at the editing domain-activation domain interface participate in coupled motions that facilitate amino acid binding and catalysis by bacterial ProRSs, which may explain why truncated or defunct editing domains have been maintained in some systems, despite the lack of catalytic activity.

Ozone pretreatment of olive mill wastewaters (OMW) and its effect on OMW biochemical methane potential (BMP).

PubMed

Tsintavi, E; Pontillo, N; Dareioti, M A; Kornaros, M

2013-01-01

The possibility of coupling a physicochemical pretreatment (ozonation) with a biological treatment (anaerobic digestion) was investigated for the case of olive mill wastewaters (OMW). Batch ozonation experiments were performed in a glass bubble reactor. The parameters which were tested included the ozone concentration in the inlet gas stream, the reactor temperature and the composition of the liquid medium in terms of raw or fractionated OMW used. In the sequel, ozone-pretreated OMW samples were tested for their biochemical methane potential (BMP) under mesophilic conditions and these results were compared to the BMP of untreated OMW. The ozonation process alone resulted in a 57-76% decrease of total phenols and a 5-18% decrease of total carbohydrates contained in OMW, depending on the experimental conditions. Nevertheless, the ozone-pretreated OMW exhibited lower chemical oxygen demand removal and methane production during BMP testing compared to the untreated OMW.

Enhanced treatment of secondary municipal wastewater effluent: comparing (biological) filtration and ozonation in view of micropollutant removal, unselective effluent toxicity, and the potential for real-time control.

PubMed

Chys, Michael; Demeestere, Kristof; Ingabire, Ange Sabine; Dries, Jan; Van Langenhove, Herman; Van Hulle, Stijn W H

2017-07-01

Ozonation and three (biological) filtration techniques (trickling filtration (TF), slow sand filtration (SSF) and biological activated carbon (BAC) filtration) have been evaluated in different combinations as tertiary treatment for municipal wastewater effluent. The removal of 18 multi-class pharmaceuticals, as model trace organic contaminants (TrOCs), has been studied. (Biological) activated carbon filtration could reduce the amount of TrOCs significantly (>99%) but is cost-intensive for full-scale applications. Filtration techniques mainly depending on biodegradation mechanisms (TF and SSF) are found to be inefficient for TrOCs removal as a stand alone technique. Ozonation resulted in 90% removal of the total amount of quantified TrOCs, but a post-ozonation step is needed to cope with an increased unselective toxicity. SSF following ozonation showed to be the only technique able to reduce the unselective toxicity to the same level as before ozonation. In view of process control, innovative correlation models developed for the monitoring and control of TrOC removal during ozonation, are verified for their applicability during ozonation in combination with TF, SSF or BAC. Particularly for the poorly ozone reactive TrOCs, statistically significant models were obtained that correlate TrOC removal and reduction in UVA 254 as an online measured surrogate parameter.

The impact of ozone treatment on changes in biologically active substances of cardamom seeds.

PubMed

Joanna Brodowska, Agnieszka; Śmigielski, Krzysztof; Nowak, Agnieszka; Brodowska, Katarzyna; Catthoor, Rik; Czyżowska, Agata

2014-09-01

The overall objective of this study was to develop a decontamination method against microorganisms in cardamom (Elettaria cardamomum (L.) Maton) seeds using ozone as a decontaminating agent. Ozone treatment was conducted 3 times, at 24-h intervals, and the parameters of the process were determined assuring the least possible losses of biologically active substances (essential oils and polyphenols): ozone concentration 160 to 165.0 g/m(3) ; flow rate 0.1 L/min; pressure 0.5 atm; time 30 min. After each step of decontamination, the microbiological profile of the cardamom seeds was studied, and the contaminating microflora was identified. Next to the microbiological profile, the total polyphenol content (TPC), composition of essential oils, free radical-scavenging capacity, total antioxidant capacity, ferric-reducing antioxidant power (FRAP), and LC-MS polyphenol analysis were determined. This study shows that extract from cardamom seeds after ozone treatment is characterized by a better radical scavenging activity (IC(50) = 24.18 ± 0.04 mg/mL) than the control sample (IC(50) = 31.94 ± 0.05 mg/mL). The extract from cardamom seeds after ozone treatment showed an improved FRAP activity as well (613.64 ± 49.79 mmol TE/g compared to 480.29 ± 30.91 mmol TE/g of control sample). The TPC and the total antioxidant capacity were negatively affected, respectively, 41.2% and 16.2%, compared to the control sample. © 2014 Institute of Food Technologists®

Role of Coupled-Dynamics in the Catalytic Activity of Prokaryotic-like Prolyl-tRNA Synthetases

PubMed Central

Sanford, Brianne; Cao, Bach; Johnson, James M.; Zimmerman, Kurt; Strom, Alexander M.; Mueller, Robyn M.; Bhattacharyya, Sudeep; Musier-Forsyth, Karin; Hati, Sanchita

2012-01-01

Prolyl-tRNA synthetases (ProRSs) have been shown to activate both cognate and some noncognate amino acids and attach them to specific tRNAPro substrates. For example, alanine, which is smaller than cognate proline, is misactivated by Escherichia coli ProRS. Mischarged Ala-tRNAPro is hydrolyzed by an editing domain (INS) that is distinct from the activation domain. It was previously shown that deletion of the INS greatly reduced cognate proline activation efficiency. In the present study, experimental and computational approaches were used to test the hypothesis that INS deletion alters the internal protein dynamics leading to reduce catalytic function. Kinetic studies with two ProRS variants, G217A and E218A, revealed decreased amino acid activation efficiency. Molecular dynamics studies showed motional coupling between the INS and protein segments containing the catalytically important proline-binding loop (PBL, residues 199–206). In particular, the complete deletion of INS, as well as mutation of G217 or E218 to alanine, exhibited significant effects on the motion of the PBL. The presence of coupled-dynamics between neighboring protein segments was also observed through in silico mutations and essential dynamics analysis. Taken together, the present study demonstrates that structural elements at the editing domain-activation domain interface participate in coupled motions that facilitate amino acid binding and catalysis by bacterial ProRSs, which may explain why truncated or defunct editing domains have been maintained in some systems, despite the lack of catalytic activity. PMID:22356126

Cleave and couple: toward fully sustainable catalytic conversion of lignocellulose to value added building blocks and fuels.

PubMed

Sun, Zhuohua; Barta, Katalin

2018-06-21

The structural complexity of lignocellulose offers unique opportunities for the development of entirely new, energy efficient and waste-free pathways in order to obtain valuable bio-based building blocks. Such sustainable catalytic methods - specifically tailored to address the efficient conversion of abundant renewable starting materials - are necessary to successfully compete, in the future, with fossil-based multi-step processes. In this contribution we give a summary of recent developments in this field and describe our "cleave and couple" strategy, where "cleave" refers to the catalytic deconstruction of lignocellulose to aromatic and aliphatic alcohol intermediates, and "couple" involves the development of novel, sustainable transformations for the formation of C-C and C-N bonds in order to obtain a range of attractive products from lignocellulose.

On ozone trend detection: using coupled chemistry-climate simulations to investigate early signs of total column ozone recovery

NASA Astrophysics Data System (ADS)

Keeble, James; Brown, Hannah; Abraham, N. Luke; Harris, Neil R. P.; Pyle, John A.

2018-06-01

Total column ozone values from an ensemble of UM-UKCA model simulations are examined to investigate different definitions of progress on the road to ozone recovery. The impacts of modelled internal atmospheric variability are accounted for by applying a multiple linear regression model to modelled total column ozone values, and ozone trend analysis is performed on the resulting ozone residuals. Three definitions of recovery are investigated: (i) a slowed rate of decline and the date of minimum column ozone, (ii) the identification of significant positive trends and (iii) a return to historic values. A return to past thresholds is the last state to be achieved. Minimum column ozone values, averaged from 60° S to 60° N, occur between 1990 and 1995 for each ensemble member, driven in part by the solar minimum conditions during the 1990s. When natural cycles are accounted for, identification of the year of minimum ozone in the resulting ozone residuals is uncertain, with minimum values for each ensemble member occurring at different times between 1992 and 2000. As a result of this large variability, identification of the date of minimum ozone constitutes a poor measure of ozone recovery. Trends for the 2000-2017 period are positive at most latitudes and are statistically significant in the mid-latitudes in both hemispheres when natural cycles are accounted for. This significance results largely from the large sample size of the multi-member ensemble. Significant trends cannot be identified by 2017 at the highest latitudes, due to the large interannual variability in the data, nor in the tropics, due to the small trend magnitude, although it is projected that significant trends may be identified in these regions soon thereafter. While significant positive trends in total column ozone could be identified at all latitudes by ˜ 2030, column ozone values which are lower than the 1980 annual mean can occur in the mid-latitudes until ˜ 2050, and in the tropics and high

A novel catalytic ceramic membrane fabricated with CuMn2O4 particles for emerging UV absorbers degradation from aqueous and membrane fouling elimination.

PubMed

Guo, Yang; Song, Zilong; Xu, Bingbing; Li, Yanning; Qi, Fei; Croue, Jean-Philippe; Yuan, Donghai

2018-02-15

A novel catalytic ceramic membrane (CM) for improving ozonation and filtration performance was fabricated by surface coating CuMn 2 O 4 particles on a tubular CM. The degradation of ultraviolet (UV) absorbers, reduction of toxicity, elimination of membrane fouling and catalytic mechanism were investigated. The characterization results suggested the particles were well-fixed on membrane surface. The modified membrane showed improved benzophenone-3 removal performance (from 28% to 34%), detoxification (EC 50 as 12.77%) and the stability of catalytic activity. In the degradation performance of model UV absorbers, the developed membrane significantly decreased the UV254 and DOC values in effluent. Compared with a virgin CM, this CM ozonation increased water flux as 29.9% by in-situ degrade effluent organic matters. The CuMn 2 O 4 modified membrane enhanced the ozone self-decompose to generate O 2 - and initiated the chain reaction of ozone decomposition, and subsequently reacted with molecule ozone to produce OH. Additionally, CM was able to promote the interaction between ozone and catalyst/organic chemicals to form H 2 O 2 that promoted the formation of OH. This catalytic ceramic membrane combining with ozonation showed potential applications in emerging pollutant degradation and membrane fouling elimination, and acted as a novel ternary technology for wastewater treatment and water reuse. Copyright © 2017 Elsevier B.V. All rights reserved.

H/D exchange mass spectrometry and statistical coupling analysis reveal a role for allostery in a ferredoxin-dependent bifurcating transhydrogenase catalytic cycle.

PubMed

Berry, Luke; Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R; Nguyen, Diep M N; Schut, Gerrit J; Adams, Michael W W; Peters, John W; Boyd, Eric S; Bothner, Brian

2018-01-01

Recent investigations into ferredoxin-dependent transhydrogenases, a class of enzymes responsible for electron transport, have highlighted the biological importance of flavin-based electron bifurcation (FBEB). FBEB generates biomolecules with very low reduction potential by coupling the oxidation of an electron donor with intermediate potential to the reduction of high and low potential molecules. Bifurcating systems can generate biomolecules with very low reduction potentials, such as reduced ferredoxin (Fd), from species such as NADPH. Metabolic systems that use bifurcation are more efficient and confer a competitive advantage for the organisms that harbor them. Structural models are now available for two NADH-dependent ferredoxin-NADP + oxidoreductase (Nfn) complexes. These models, together with spectroscopic studies, have provided considerable insight into the catalytic process of FBEB. However, much about the mechanism and regulation of these multi-subunit proteins remains unclear. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS) and statistical coupling analysis (SCA), we identified specific pathways of communication within the model FBEB system, Nfn from Pyrococus furiosus, under conditions at each step of the catalytic cycle. HDX-MS revealed evidence for allosteric coupling across protein subunits upon nucleotide and ferredoxin binding. SCA uncovered a network of co-evolving residues that can provide connectivity across the complex. Together, the HDX-MS and SCA data show that protein allostery occurs across the ensemble of iron‑sulfur cofactors and ligand binding sites using specific pathways that connect domains allowing them to function as dynamically coordinated units. Copyright © 2017 Elsevier B.V. All rights reserved.

Heterogeneous catalytic ozonation of hydroquinone using sewage sludge-derived carbonaceous catalysts.

PubMed

Xu, Jinglu; Yu, Yang; Ding, Kang; Liu, Zhiying; Wang, Lei; Xu, Yanhua

2018-03-01

This study converted sewage sludge into a carbonaceous catalyst via pyrolysis and employed it in the ozonation of hydroquinone. The catalyst was characterized by Mössbauer spectroscopy, X-ray photoelectron spectroscopy, temperature programmed desorption, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Intermediate products were detected by gas chromatography-mass spectrometry, and a pathway for hydroquinone degradation was proposed. The results showed that sludge pyrolyzed at 700 °C promoted hydroquinone degradation, compared with commercial activated carbon derived from coal. When the catalyst dose was 0.5 g/L, the hydroquinone (200 mg/L) removal rate reached 97.86% after exposure to ozone (the ozone concentration was 17 mg/L and the flow rate was 50 mL/min) for 60 min. The results indicated that basic groups contributed to the catalysis.

Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds.

PubMed

Marciniec, Bogdan

2007-10-01

In the Account given herein, it has been shown that silylative coupling of olefins, well-recognized as a new catalytic route for the activation of double bond C-H bond of olefins and double bond C-Si bond of vinylsilicon compounds with ethylene elimination, can be extended over both other vinylmetalloid derivatives (double bond C-E) (where E = Ge, B, and others) as well as the activation of triple bond C-H, double bond C aryl-H, and -O-H bond of alcohols and silanols. This general transformation is catalyzed by transition-metal complexes (mainly Ru and Rh) containing or initiating TM-H and/or TM-E bonds (inorganometallics). This new general catalytic route for the activation of double bond C-H and triple bond C-H as well as double bond C-E bonds called metallative coupling or trans-metalation (cross-coupling, ring-closing, and polycondensation) constitutes an efficient method (complementary to metathesis) for stereo- and regioselective synthesis of a variety of molecular and macromolecular compounds of vinyl-E (E = Si, B, and Ge) and ethynyl-E (E = Si and Ge) functionality, also potent organometallic reagents for efficient synthesis of highly pi-conjugated organic compounds. The mechanisms of the catalysis of this deethenative metalation have been supported by equimolar reactions of TM-H and/or TM-E with initial substances and reactions with deuterium-labeled reagents.

Ozone assisted oxidation of gaseous PCDD/Fs over CNTs-containing composite catalysts at low temperature.

PubMed

Wang, Qiulin; Tang, Minghui; Peng, Yaqi; Du, Cuicui; Lu, Shengyong

2018-05-01

Ozone assisted carbon nanotubes (CNTs) supported vanadium oxide/titanium dioxide (V/Ti-CNTs) or vanadium oxide-manganese oxide/titanium dioxide (V-Mn/Ti-CNTs) catalysts towards gaseous PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) catalytic oxidations at low temperature (150 °C) were investigated. The removal efficiency (RE) and decomposition efficiency (DE) of PCDD/Fs achieved with V-Mn/Ti-CNTs alone were 95% and 45% at 150 °C under a space velocity (SV) of 14000 h -1 ; yet, these values reached 99% and 91% when catalyst and low concentration (50 ppm) ozone were used in combined. The ozone promotion effect on catalytic activity was further enhanced with the addition of manganese oxide (MnO x ) and CNTs. Adding MnO x and CNTs in V/Ti catalysts facilitated the ozone decomposition (creating more active species on catalyst surface), thus, improved ozone utilization (demanding relatively lower ozone addition concentration). On the other hand, this study threw light upon ozone promotion mechanism based on the comparison of catalyst properties (i.e. components, surface area, surface acidity, redox ability and oxidation state) before and after ozone treatment. The experimental results indicate that a synergistic effect exists between catalyst and ozone: ozone is captured and decomposed on catalyst surface; meanwhile, the catalyst properties are changed by ozone in return. Reactive oxygen species from ozone decomposition and the accompanied catalyst properties optimization are crucial reasons for catalyst activation at low temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

DOE PAGES

Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko; ...

2015-05-20

It is important to achieve high selectivity for high volume chemical synthesis in order to lower energy consumption through reduction in waste. Here, we report the selective synthesis of methyl esters—methyl acetate and methyl butyrate—through catalytic O 2-assisted cross-coupling of methanol with ethanol or 1-butanol using activated, support-free nanoporous gold (npAu). Both well-controlled studies on ingots in UHV and experiments under ambient pressure catalytic conditions on both ingots and microspherical hollow shell catalysts reveal guiding principles for controlling selectivity. Under UHV conditions, the ester products of the cross-coupling of methanol with both ethanol and 1-butanol evolve near room temperature inmore » temperature-programmed reaction studies, indicating that the reactions occur facilely. Furthermore, under steady-state catalytic operation, high stable activity was observed for cross-coupling in flowing gaseous reactant mixtures at atmospheric pressure and 423 K with negligible combustion. Optimum selectivity for cross-coupling is obtained in methanol-rich mixtures due to a combination of two factors: (1) the relative coverage of the respective alkoxys and (2) the relative facility of their β-H elimination. The relative coverage of the alkoxys is governed by van der Waal’s interactions between the alkyl groups and the surface; here, we demonstrate the importance of these weak interactions in a steady-state catalytic process.« less

Silver nanocluster catalytic microreactors for water purification

NASA Astrophysics Data System (ADS)

Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.

2016-07-01

A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.

The coupled effects of chemistry and diffusion on the stratospheric ozone reduction

NASA Technical Reports Server (NTRS)

Gupta, R. N.; Grose, W. L.

1980-01-01

The effect of diffusive-mixing on O3-depletion is estimated using the five-step chemistry model. The coupled treatment uses an equilibrium turbulence field and retains the key features of the kinetics while keeping the chemistry simple. Results indicate that those calculations of Hilst and Donaldson (1973) employing the conservation of NO2/NO will yield erroneous results, and it is found that any significant level of turbulence will reduce the severity of the NOx catalytic cycle for O3 destruction.

When Will the Antarctic Ozone Hole Recover?

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Kawa, S. Randolph; Montzka, Steve

2005-01-01

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We will show estimates of both when the ozone hole will begin to show first signs of recovery, and when the hole will fully recover to pre-1980 levels.

When will the Antarctic Ozone Hole Recover?

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Kawa, S. Randolph; Montzka, Steve

2006-01-01

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the .TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to, both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. The ozone hole will begin to show first signs of recovery in about 2023, and the hole will fully recover to pre-1980 levels in approximately 2070. This 2070 recovery is 20 years later than recent projections.

Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

NASA Astrophysics Data System (ADS)

Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

2018-01-01

In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

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

Liu, Cong; Evans, Tabitha J.; Cheng, Lei

2015-10-02

These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Majormore » products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.« less

Biodegradability of DBP precursors after drinking water ozonation.

PubMed

de Vera, Glen Andrew; Keller, Jurg; Gernjak, Wolfgang; Weinberg, Howard; Farré, Maria José

2016-12-01

Ozonation is known to generate biodegradable organic matter, which is typically reduced by biological filtration to avoid bacterial regrowth in distribution systems. Post-chlorination generates halogenated disinfection byproducts (DBPs) but little is known about the biodegradability of their precursors. This study determined the effect of ozonation and biofiltration conditions, specifically ozone exposure and empty bed contact time (EBCT), on the control of DBP formation potentials in drinking water. Ozone exposure was varied through addition of H 2 O 2 during ozonation at 1 mgO 3 /mgDOC followed by biological filtration using either activated carbon (BAC) or anthracite. Ozonation led to a 10% decrease in dissolved organic carbon (DOC), without further improvement from H 2 O 2 addition. Raising H 2 O 2 concentrations from 0 to 2 mmol/mmolO 3 resulted in increased DBP formation potentials during post-chlorination of the ozonated water (target Cl 2 residual after 24 h = 1-2 mg/L) as follows: 4 trihalomethanes (THM4, 37%), 8 haloacetic acids (HAA8, 44%), chloral hydrate (CH, 107%), 2 haloketones (HK2, 97%), 4 haloacetonitriles (HAN4, 33%), trichloroacetamide (TCAM, 43%), and adsorbable organic halogen (AOX, 27%), but a decrease in the concentrations of 2 trihalonitromethanes (THNM2, 43%). Coupling ozonation with biofiltration prior to chlorination effectively lowered the formation potentials of all DBPs including CH, HK2, and THNM2, all of which increased after ozonation. The dynamics of DBP formation potentials during BAC filtration at different EBCTs followed first-order reaction kinetics. Minimum steady-state concentrations were attained at an EBCT of about 10-20 min, depending on the DBP species. The rate of reduction in DBP formation potentials varied among individual species before reaching their minimum concentrations. CH, HK2, and THNM2 had the highest rate constants of between 0.5 and 0.6 min -1 followed by HAN4 (0.4 min -1 ), THM4 (0.3 min -1 ), HAA8 (0

Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan.

PubMed

Lin, Ching-Ho

2008-04-01

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and

Estimating when the Antarctic Ozone Hole will Recover

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Douglass, Anne R.; Nielsen, J. Eric; Pawson, Steven; Stolarski, Richard S.

2007-01-01

The Antarctic ozone hole develops each year and culminates by early spring (late September - early October). The severity of the hole has been assessed from satellites using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average area coverage during this September-October period. Profile information shows that ozone is completely destroyed in the 14-2 1 km layer by early October. Ozone is mainly destroyed by halogen (chlorine and bromine) catalytic cycles, and these losses are modulated by temperature variations. Because atmospheric halogen levels are responding to international a'greements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We estimate that the ozone hole will begin to show first signs of size decrease in about 2023, and the hole will fully recover to pre-1980 levels in approximately 2070. Estimates of the ozone hole's recovery from models reveal important differences that will be discussed.

Estimating When the Antarctic Ozone Hole Will Recover

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Douglass, Anne R.; Nielsen, J. Eric; Pawson, Steven; Stolarski, Richard S.

2007-01-01

The Antarctic ozone hole develops each year and culminates by early spring (late September - early October). The severity of the hole has been assessed from satellites using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average area coverage during this September-October period. Profile information shows that ozone is completely destroyed in the 14-21 km layer by early October. Ozone is mainly destroyed by halogen (chlorine and bromine) catalytic cycles, and these losses are modulated by temperature variations. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We estimate that the ozone hole will begin to show first signs of size decrease in about 2023, and the hole will fully recover to pre-1980 levels in approximately 2070. Estimates of the ozone hole's recovery from models reveal important differences that will be discussed.

Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex.

PubMed

Fukuzumi, Shunichi; Mandal, Sukanta; Mase, Kentaro; Ohkubo, Kei; Park, Hyejin; Benet-Buchholz, Jordi; Nam, Wonwoo; Llobet, Antoni

2012-06-20

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.

Coupling biology and oceanography in models.

PubMed

Fennel, W; Neumann, T

2001-08-01

The dynamics of marine ecosystems, i.e. the changes of observable chemical-biological quantities in space and time, are driven by biological and physical processes. Predictions of future developments of marine systems need a theoretical framework, i.e. models, solidly based on research and understanding of the different processes involved. The natural way to describe marine systems theoretically seems to be the embedding of chemical-biological models into circulation models. However, while circulation models are relatively advanced the quantitative theoretical description of chemical-biological processes lags behind. This paper discusses some of the approaches and problems in the development of consistent theories and indicates the beneficial potential of the coupling of marine biology and oceanography in models.

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process.

PubMed

Guo, Jianning; Hu, Jiangyong; Tao, Yi; Zhu, Jia; Zhang, Xihui

2014-04-01

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon (BAC) (Process A) and ceramic membrane-BAC (Process B) were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm (UV254, a parameter indicating organic matter with aromatic structure) were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Bio oil synthesis by coupling biological biomass pretreatment and catalytic hydroliquefaction process.

PubMed

Hamieh, S; Beauchet, R; Lemee, L; Toufaily, J; Koubaissy, B; Hamieh, T; Pouilloux, Y; Pinard, L

2014-03-01

The bio-oil synthesis from a mixture of wastes (7wt.% straw, 38wt.% wood, and 45wt.% grass) was carried out by direct liquefaction reaction using Raney Nickel as catalyst and tetralin as solvent. The green wastes were biologically degraded during 3 months. Longer the destructuration time; higher the yield into oil is. Biological pretreatment of green wastes promotes the liquefaction process. Among the components of degraded biomass, Humin, the major fraction (60-80wt.%) that was favored by the biological treatment, yields to a bio oil extremely energetic with a HHV close to biopetroleum (40MJ kg(-1)), contrariwise, Fulvic acids (2-12wt.%), the minor fraction is refractory to liquefaction reaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

Detection and Attribution of the Recovery of Polar Ozone

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, E. R.; Douglass, A. R.; Nielsen, J. E.; Pawson, S.; Stolarski, R. S.

2008-01-01

The Antarctic ozone hole develops each year and culminates by early spring (late September - early October). The severity of the hole has been assessed from satellites using the minimum total ozone value from the October monthly mean (depth of the hole), calculating the average area coverage during this September-October period, and by estimating ozone mass deficit. Profile information shows that ozone is completely destroyed in the 14-2 1 km layer by early October. Ozone is mainly destroyed by halogen (chlorine and bromine) catalytic cycles, and these losses are modulated by temperature variations. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Both models and projections of ozone depleting substances (ODSs) into the 21St century reveal that polar ozone levels should recover in the 2060- 2070 period. In this talk, we will review current projections of polar ozone recovery. Using models and ODs projections, we explore both the past, near future (2008-2025), and far future (> 2025) levels of polar ozone. Finally, we will discuss various factors that complicate recovery such as greenhouse gas changes (e.g., cooling in the upper stratosphere) and the acceleration of the Brewer-Dobson circulation.

Improved simulation of tropospheric ozone by a global-multi-regional two-way coupling model system

NASA Astrophysics Data System (ADS)

Yan, Y.; Lin, J.; Hu, L.; Chen, J.

2016-12-01

Small-scale nonlinear chemical and physical processes over pollution source regions affect the tropospheric ozone, but these processes are not captured by current global chemical transport models and chemistry-climate models that are limited by coarse horizontal resolutions. These models tend to contain large (and mostly positive) tropospheric O3 biases in the Northern Hemisphere. Here we use a recently built two-way coupling system of the GEOS-Chem CTM to simulate the regional and global tropospheric O3in 2009. The system couples the global model (at 2.5º long. x 2º lat.) and its three nested models (at 0.667º long. x 0.5º lat.) covering Asia, North America and Europe, respectively. Specifically, the nested models take lateral boundary conditions from the global model, better capture small-scale processes, and feed back to modify the global model simulation within the nested domains, with a subsequent effect on their LBCs. Compared to the global model alone, the two-way coupled system better simulates the tropospheric O3 both within and outside the nested domains, as found by evaluation against a suite of ground (1420 sites from WDCGG, GMD, EMEP, and AQS), aircraft (HIPPO and MOZAIC), and satellite measurements (two OMI products). The two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean surface O3 with the ground measurements from 0.53 to 0.68, and it reduces the mean model bias from 10.8 to 6.7 ppb. Regionally, the coupled system reduces the bias by 4.6 ppb over Europe, 3.9 ppb over North America, and 3.1 ppb over other regions. The two-way coupling brings O3vertical profiles much closer to the HIPPO (for remote areas) and MOZAIC (for polluted regions) data, reducing the tropospheric mean bias by 3-10 ppb at most MOZAIC sites and by 5.3 ppb for HIPPO profiles. The two-way coupled simulation also reduces the global tropospheric column ozone by 3.0 DU (9.5%, annual mean), bringing them closer to the OMI data in all

Application of integrated ozone biological aerated filters and membrane filtration in water reuse of textile effluents.

PubMed

He, Yaozhong; Wang, Xiaojun; Xu, Jinling; Yan, Jinli; Ge, Qilong; Gu, Xiaoyang; Jian, Lei

2013-04-01

A combined process including integrated ozone-BAFs (ozone biological aerated filters) and membrane filtration was first applied for recycling textile effluents in a cotton textile mill with capacity of 5000 m(3)/d. Influent COD (chemical oxygen demand) in the range of 82-120 mg/L, BOD5 (5-day biochemical oxygen demand) of 12.6-23.1 mg/L, suspended solids (SSs) of 38-52 mg/L and color of 32-64° were observed during operation. Outflows with COD≤45 mg/L, BOD5≤7.6 mg/L, SS≤15 mg/L, color≤8° were obtained after being decontaminated by ozone-BAF with ozone dosage of 20-25 mg/L. Besides, the average removal rates of PVA (polyvinyl alcohol) and UV254 were 100% and 73.4% respectively. Permeate water produced by RO (reverse osmosis) could be reused in dyeing and finishing processes, while the RO concentrates could be discharged directly under local regulations with COD≤100 mg/L, BOD5≤21 mg/L, SS≤52 mg/L, color≤32°. Results showed that the combined process could guarantee water reuse with high quality, and solve the problem of RO concentrate disposal. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ozone Measurements in the Mesosphere During a Solar Proton Event

NASA Technical Reports Server (NTRS)

Lippert, W.; Felske, D.

1984-01-01

Charged particle precipitation in the Earth's atmosphere produces odd nitrogen and odd hydrogen. These species take part in catalytic reactions which destroy atmospheric ozone in the stratosphere and mesosphere. Modeling efforts regarding the impact of these ionization events on the neutral atmosphere describe ozone depletions in good agreement with observations in the stratosphere and mesosphere. The photochemical effects of the solar proton event (SPE) of August 1972 are discussed, and calculations for higher altitudes (70 to 90 km) are presented that indicate after a brief reduction during and immediately following intense particle precipitation, ozone will later reach higher concentrations than those present before the event.

Discharge cell for ozone generator

DOEpatents

Nakatsuka, Suguru

2000-01-01

A discharge cell for use in an ozone generator is provided which can suppress a time-related reduction in ozone concentration without adding a catalytic gas such as nitrogen gas to oxygen gas as a raw material gas. The discharge cell includes a pair of electrodes disposed in an opposed spaced relation with a discharge space therebetween, and a dielectric layer of a three-layer structure consisting of three ceramic dielectric layers successively stacked on at least one of the electrodes, wherein a first dielectric layer of the dielectric layer contacting the one electrode contains no titanium dioxide, wherein a second dielectric layer of the dielectric layer exposed to the discharge space contains titanium dioxide in a metal element ratio of not lower than 10 wt %.

Combination of ozonation, activated carbon, and biological aerated filter for advanced treatment of dyeing wastewater for reuse.

PubMed

Zou, Xiao-Ling

2015-06-01

Laboratorial scale experiments were performed to investigate and evaluate the performance and removal characteristics of organics, color, and genotoxicity by an integrated process including ozonation, activated carbon (AC), and biological aerated filter (BAF) for recycling biotreated dyeing wastewater (BTDW) collected from a cotton textile factory. Influent chemical oxygen demand (COD) in the range of 156 - 252 mg/L, 5-day biochemical oxygen demand (BOD5) of 13.5 - 21.7 mg/L, and color of 58 - 76° were observed during the 20-day continuous operation. Outflows with average COD of 43 mg/L, BOD5 of 6.6 mg/L, and color of 5.6° were obtained after being decontaminated by the hybrid system with ozone dosage of 0.25 mg O3applied/mg COD0, 40 min ozonation contact time, 30 min hydraulic retention time (HRT) for AC treatment, and 2.5 h HRT for BAF treatment. More than 82 % of the genotoxicity of BTDW was eliminated in the ozonation unit. The genotoxicity of the BAF effluent was less than 1.33 μg 4-nitroquinoline-N-oxide/L. Ozonation could change the organics molecular structures, destroy chromophores, increase the biodegradability, and obviously reduce the genotoxicity of BTDW. Results showed that the combined process could guarantee water reuse with high quality.

Mesospheric ozone destruction by high-energy electron precipitation associated with pulsating aurora

NASA Astrophysics Data System (ADS)

Turunen, Esa; Kero, Antti; Verronen, Pekka T.; Miyoshi, Yoshizumi; Oyama, Shin-Ichiro; Saito, Shinji

2016-10-01

Energetic particle precipitation into the upper atmosphere creates excess amounts of odd nitrogen and odd hydrogen. These destroy mesospheric and upper stratospheric ozone in catalytic reaction chains, either in situ at the altitude of the energy deposition or indirectly due to transport to other altitudes and latitudes. Recent statistical analysis of satellite data on mesospheric ozone reveals that the variations during energetic electron precipitation from Earth's radiation belts can be tens of percent. Here we report model calculations of ozone destruction due to a single event of pulsating aurora early in the morning on 17 November 2012. The presence of high-energy component in the precipitating electron flux (>200 keV) was detected as ionization down to 68 km altitude, by the VHF incoherent scatter radar of European Incoherent Scatter (EISCAT) Scientific Association (EISCAT VHF) in Tromsø, Norway. Observations by the Van Allen Probes satellite B showed the occurrence of rising tone lower band chorus waves, which cause the precipitation. We model the effect of high-energy electron precipitation on ozone concentration using a detailed coupled ion and neutral chemistry model. Due to a 30 min, recorded electron precipitation event we find 14% odd oxygen depletion at 75 km altitude. The uncertainty of the higher-energy electron fluxes leads to different possible energy deposition estimates during the pulsating aurora event. We find depletion of odd oxygen by several tens of percent, depending on the precipitation characteristics used in modeling. The effect is notably maximized at the sunset time following the occurrence of the precipitation.

Detecting the Recovery of the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Kawa, S. Randolph; Montzka, Steve

2004-01-01

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We will show estimates of both when the ozone hole will begin to show first signs of recovery, and when the hole will fully recover to pre-1980 levels.

Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

NASA Astrophysics Data System (ADS)

Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

2013-10-01

A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

Climate Chemistry Coupling: Ozone Loss Linked to the Unique Dynamical Structure of the Summertime Stratosphere Over the U.S. Using In Situ Aircraft, Satellite and NEXRAD Radar Observations

NASA Astrophysics Data System (ADS)

Anderson, J. G.; Wilmouth, D. M.; Smith, J. B.; Dykema, J. A.; Leroy, S. S.; Koby, T.; Clapp, C.; Bowman, K. P.

2015-12-01

A remarkable combination of meteorological and catalytic chemical factors place the summertime lower stratosphere over the U.S. in a unique position at the intersection of climate forcing and potential ozone loss in the stratosphere. The factors that conspire to establish this circumstance engages four independent considerations. First is the occurrence of severe storms in the U.S. Mid-West caused by the intersection of moist airflow from the Gulf of Mexico with airflow from higher latitudes in spring and summer. These storms are characterized by a combination of tornadoes, hail, heavy precipitation and high winds, the frequency and intensity of which are increasing with increased forcing of the climate system by the addition of CO2, CH4, N2O CFCs, and other infrared active species to the atmosphere associated with human activity. Second is the recognition that these severe storms are capable of injecting water vapor deep into the stratosphere over the U.S., with injection depths reaching the altitude of increasing inorganic halogen species formed by the photolytic breakdown of organic chorine and bromine transported into the stratosphere. Third is the recognition that the catalytic conversion of inorganic halogen species to radicals, specifically ClO and BrO, that are the rate limiting catalytic species that destroy ozone, occurs on ubiquitous sulfate-water aerosols wherever and whenever the temperature-water vapor conditions are met. These conditions are met in the Antarctic and Arctic winter vortices by virtue of temperatures below 200K at 5 ppmv water vapor, and in the summertime lower stratosphere over the U.S. by virtue of temperatures between 200 and 205K in combination with convectively injected water vapor concentrations in the range of 8 ppmv or greater. Fourth, is the recognition that the flow pattern of the lower stratosphere over the U.S. in summer is repeatedly under the control of the North American monsoon that forms an anti-cyclonic (clockwise

On the Complex Coupling Between the Production of Ozone and Secondary Organic Aerosol in Polluted Urban Regions

NASA Astrophysics Data System (ADS)

Stewart, D. R.; Stockwell, W. R.; Morris, V. R.; Fitzgerald, R. M.

2016-12-01

The major photochemical processes that produce ozone and aerosols are coupled together strongly in the polluted urban atmosphere. Aerosols are either directly emitted or formed through the same kind of chemistry that leads to the production of ozone. The aerosols produced through atmospheric chemistry are known as secondary aerosols and they may be composed of inorganic (nitrates, sulfates) or organic compounds. Wind blown dust and soot are two examples of primary aerosols. The component of secondary inorganic aerosols includes compounds such as ammonium nitrate, ammonium bisulfate and ammonium sulfate. Secondary organic aerosols are a very important component of PM with strong implications for health. The formation of secondary organic aerosol is linked with ozone photochemistry through the reactions of volatile organic compounds (VOC). The oxidation of VOC produces radicals that convert nitric oxide to nitrogen dioxide that photolyze to produce ozone. Larger VOC (those with more carbon atoms) undergo a number of oxidation cycles that add oxygen atoms to large organic molecules. The vapor pressure of many of these highly oxidized compounds is sufficiently low that they condense to produce secondary organic aerosols. The Community Multi-scale Air Quality model (CMAQ) and other chemical simulations have been made to quantify the relationship between varying emissions of VOC and NOx and the production of inorganic and secondary organic aerosols. The results from this analysis will be presented.

Ozone therapy in periodontics

PubMed Central

Gupta, G; Mansi, B

2012-01-01

Gingival and Periodontal diseases represent a major concern both in dentistry and medicine. The majority of the contributing factors and causes in the etiology of these diseases are reduced or treated with ozone in all its application forms (gas, water, oil). The beneficial biological effects of ozone, its anti-microbial activity, oxidation of bio-molecules precursors and microbial toxins implicated in periodontal diseases and its healing and tissue regeneration properties, make the use of ozone well indicated in all stages of gingival and periodontal diseases. The primary objective of this article is to provide a general review about the clinical applications of ozone in periodontics. The secondary objective is to summarize the available in vitro and in vivo studies in Periodontics in which ozone has been used. This objective would be of importance to future researchers in terms of what has been tried and what the potentials are for the clinical application of ozone in Periodontics. PMID:22574088

Ozone therapy in periodontics.

PubMed

Gupta, G; Mansi, B

2012-02-22

Gingival and Periodontal diseases represent a major concern both in dentistry and medicine. The majority of the contributing factors and causes in the etiology of these diseases are reduced or treated with ozone in all its application forms (gas, water, oil). The beneficial biological effects of ozone, its anti-microbial activity, oxidation of bio-molecules precursors and microbial toxins implicated in periodontal diseases and its healing and tissue regeneration properties, make the use of ozone well indicated in all stages of gingival and periodontal diseases. The primary objective of this article is to provide a general review about the clinical applications of ozone in periodontics. The secondary objective is to summarize the available in vitro and in vivo studies in Periodontics in which ozone has been used. This objective would be of importance to future researchers in terms of what has been tried and what the potentials are for the clinical application of ozone in Periodontics.

The Impact of Ozone Treatment in Dynamic Bed Parameters on Changes in Biologically Active Substances of Juniper Berries

PubMed Central

Brodowska, Agnieszka Joanna; Śmigielski, Krzysztof; Nowak, Agnieszka; Czyżowska, Agata; Otlewska, Anna

2015-01-01

The development of the parameters of ozone decontamination method assuring the least possible losses of biologically active substances (essential oils and polyphenols) and their activity in common juniper (Juniperus communis (L.)) berries was studied. Ozone treatment in dynamic bed was conducted 9 times. The process was conducted under different ozone concentrations (100.0; 130.0; 160.0 g O3/m3) and times (30, 60, 90 min). After each decontamination, the microbiological profile of the juniper berries was studied, and the contaminating microflora was identified. Next to the microbiological profile, the phenolic profile, as well as antioxidant activity of extracts and essential oils were determined. The total polyphenol content (TPC), composition of essential oils, free radical-scavenging capacity, total antioxidant capacity, ferric-reducing antioxidant power (FRAP), beta-carotene bleaching test (BCB) and LC-MS polyphenol analysis were carried out. The study reveals that during short ozone contact times, higher amounts of TPC, 15.47 and 12.91 mg CE/g of extract, for samples 100/30 and 130/30, respectively, were demonstrated. Whereas samples 100/60, 130/60, 100/90, and 160/90 exhibited the lowest amount of phenolics. The highest antioxidant activity was found in the methanol extract obtained from ozonated berries which exhibited the lowest IC50 in all the antioxidant assays, such as DPPH, FRAP, and BCB assays. Ozone treatment showed noteworthy potential and its usage in food manufacturing and as an alternative decontamination method should be considered. PMID:26659905

The Impact of Ozone Treatment in Dynamic Bed Parameters on Changes in Biologically Active Substances of Juniper Berries.

PubMed

Brodowska, Agnieszka Joanna; Śmigielski, Krzysztof; Nowak, Agnieszka; Czyżowska, Agata; Otlewska, Anna

2015-01-01

The development of the parameters of ozone decontamination method assuring the least possible losses of biologically active substances (essential oils and polyphenols) and their activity in common juniper (Juniperus communis (L.)) berries was studied. Ozone treatment in dynamic bed was conducted 9 times. The process was conducted under different ozone concentrations (100.0; 130.0; 160.0 g O3/m3) and times (30, 60, 90 min). After each decontamination, the microbiological profile of the juniper berries was studied, and the contaminating microflora was identified. Next to the microbiological profile, the phenolic profile, as well as antioxidant activity of extracts and essential oils were determined. The total polyphenol content (TPC), composition of essential oils, free radical-scavenging capacity, total antioxidant capacity, ferric-reducing antioxidant power (FRAP), beta-carotene bleaching test (BCB) and LC-MS polyphenol analysis were carried out. The study reveals that during short ozone contact times, higher amounts of TPC, 15.47 and 12.91 mg CE/g of extract, for samples 100/30 and 130/30, respectively, were demonstrated. Whereas samples 100/60, 130/60, 100/90, and 160/90 exhibited the lowest amount of phenolics. The highest antioxidant activity was found in the methanol extract obtained from ozonated berries which exhibited the lowest IC50 in all the antioxidant assays, such as DPPH, FRAP, and BCB assays. Ozone treatment showed noteworthy potential and its usage in food manufacturing and as an alternative decontamination method should be considered.

The Nevada Rural Ozone Initiative: Field measurements of surface ozone in rural settings

NASA Astrophysics Data System (ADS)

Fine, R.; Gustin, M. S.; Weiss-Penzias, P. S.; Jaffe, D. A.; Peterson, C.

2011-12-01

The Nevada Rural Ozone Initiative (NVROI) focuses on measuring ozone and other parameters at rural sites across Nevada. The project was prompted by observations of elevated ozone concentrations at Great Basin National Park (GBNP), a remote location at the eastern boundary of the state. Past CASTNET data collected at GBNP demonstrated that the area will be out of attainment if the new ozone NAAQS are established at any values between 60 and 70 ppb. To examine the ozone sources we have augmented the CASTNET data at GBNP with measurements at additional sites. NVROI field sites are situated between 1390 and 2080 meters above sea level along transects consistent with the prevailing wind directions across the state. Data collection began in July 2011. Measurements indicate significant variability in the diel pattern of ozone concentrations between field sites suggesting that site specific physicochemical characteristics, free tropospheric inputs, and regional transport of air pollutants all influence observed values at these background sites. Ancillary gas, particulate matter, and meteorological parameters will be coupled with trajectory analyses to investigate the influence of local, regional, and long range sources on background ozone concentrations.

Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

EPA Science Inventory

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

N- versus C-domain selectivity of catalytic inactivation of human angiotensin converting enzyme by lisinopril-coupled transition metal chelates.

PubMed

Hocharoen, Lalintip; Joyner, Jeff C; Cowan, J A

2013-12-27

The N- and C-terminal domains of human somatic angiotensin I converting enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates was tested for both reversible binding and irreversible catalytic inactivation of each domain of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and catalytic factors (double-filter effect).

Causes and effects of a hole. [in Antarctic ozone layer

NASA Technical Reports Server (NTRS)

Margitan, J. J.

1987-01-01

Preliminary results from the U.S. National Ozone Expedition (NOZE) to Antarctica are reviewed. The NOZE ozonesonde measurements showed significant vertical structure in the hole, with 80 percent depletion in some of the 1 km layers but only 20 percent in adjacent layers. The depletion was confined to the 12-20 km region, beginning first at higher altitude and progressing downward. This is strong evidence against the theory that the ozone hole is due to solar activity producing odd nitrogen at high altitudes which is transported downwards, leading to enhanced odd-nitrogen catalytic cycles that destroy ozone. Nitrous oxide data show unusually low concentrations within the polar vortex, which is evidence against the theory that the hole is caused by a purely dynamical mechanism in which rising air motions within the polar vortex lead to reduced column densities of ozone. It is tentatively concluded that a chemical mechanism involving man-made chlorofluorocarbons is the likely cause of ozone depletion in the hole.

Efficient catalytic ozonation of bisphenol-A over reduced graphene oxide modified sea urchin-like α-MnO(2) architectures.

PubMed

Li, Gang; Lu, Yongtao; Lu, Cheng; Zhu, Mingshan; Zhai, Chunyang; Du, Yukou; Yang, Ping

2015-08-30

Considering the biological deleterious effect of bisphenol-A (BPA) in water to the human beings, great efforts have been made for the elimination of this contaminant from water sources. Herein, we report a novel nanocomposite composed of three-dimensional (3D) sea urchin-like α-MnO2 nanoarchitectures and reduced graphene oxide (RGO) for the elimination of BPA in water in the presence of ozone. The synthesis of the as-prepared nanocomposite is facile, and the nanocomposites were well characterized by SEM, TEM, XRD, and Raman spectra. The as-synthesized α-MnO2/RGO nanocomposite was found to be a highly efficient catalyst to eliminate BPA from water in the presence of ozone. The intermediates of ozonzation were also detected by gas chromatography-mass spectrometry (GC-MS). Our investigation initiates a new opportunity to explore the high-performance catalysts for the removal of the organic pollutions in water. Copyright © 2015 Elsevier B.V. All rights reserved.

Catalytically and biologically active silver nanoparticles synthesized using essential oil

NASA Astrophysics Data System (ADS)

Vilas, Vidya; Philip, Daizy; Mathew, Joseph

2014-11-01

There are numerous reports on phytosynthesis of silver nanoparticles and various phytochemicals are involved in the reduction and stabilization. Pure explicit phytosynthetic protocol for catalytically and biologically active silver nanoparticles is of importance as it is an environmentally benign green method. This paper reports the use of essential oil of Myristica fragrans enriched in terpenes and phenyl propenes in the reduction and stabilization. FTIR spectra of the essential oil and the synthesized biogenic silver nanoparticles are in accordance with the GC-MS spectral analysis reports. Nanosilver is initially characterized by an intense SPR band around 420 nm, followed by XRD and TEM analysis revealing the formation of 12-26 nm sized, highly pure, crystalline silver nanoparticles. Excellent catalytic and bioactive potential of the silver nanoparticles is due to the surface modification. The chemocatalytic potential of nanosilver is exhibited by the rapid reduction of the organic pollutant, para nitro phenol and by the degradation of the thiazine dye, methylene blue. Significant antibacterial activity of the silver colloid against Gram positive, Staphylococcus aureus (inhibition zone - 12 mm) and Gram negative, Escherichia coli (inhibition zone - 14 mm) is demonstrated by Agar-well diffusion method. Strong antioxidant activity of the biogenic silver nanoparticles is depicted through NO scavenging, hydrogen peroxide scavenging, reducing power, DPPH and total antioxidant activity assays.

Alternative Electrochemical Systems for Ozonation of Water

NASA Technical Reports Server (NTRS)

Andrews, Craig C.; Murphy, Oliver J.

2003-01-01

Electrochemical systems that are especially well suited for the small-scale generation of ozone and ozonated water for local use have been invented. These systems can operate with very little maintenance, and the only inputs needed during operation are electric power and water. Ozonated water produced by these systems can be used in diverse industrial applications: A few examples include sterilization in the brewing industry, general disinfection, and treatment of sewage and recycled water. The basic principle of operation admits of several alternative system configurations. The heart of the system is a stack of electrolytic cells, each containing a proton-exchange membrane (which serves as a solid electrolyte) sandwiched between a catalytic anode and a catalytic cathode. Preferably, the proton-exchange membrane is made of a perfluorinated sulfonic acid polymer. During electrolysis, a mixture of O2 and O3 gases is generated at the anode and H2 is generated at the cathode. Some of the O3 generated at the anode becomes dissolved in the water. The proportion of O3 in the O2/O3 mixture can be maximized by the selection of suitable electrode materials and the use of a high overpotential. Although the proton-exchange membrane conducts protons, it does not conduct electrons. It is also impermeable by gases; consequently, it maintains separation between the O2/O3 mixture evolved at the anode and the H2 evolved at the cathode.

Modeling coupled interactions of carbon, water, and ozone exchange between terrestrial ecosystems and the atmosphere. I: model description.

PubMed

Nikolov, Ned; Zeller, Karl F

2003-01-01

A new biophysical model (FORFLUX) is presented to study the simultaneous exchange of ozone, carbon dioxide, and water vapor between terrestrial ecosystems and the atmosphere. The model mechanistically couples all major processes controlling ecosystem flows trace gases and water implementing recent concepts in plant eco-physiology, micrometeorology, and soil hydrology. FORFLUX consists of four interconnected modules-a leaf photosynthesis model, a canopy flux model, a soil heat-, water- and CO2- transport model, and a snow pack model. Photosynthesis, water-vapor flux and ozone uptake at the leaf level are computed by the LEAFC3 sub-model. The canopy module scales leaf responses to a stand level by numerical integration of the LEAFC3model over canopy leaf area index (LAI). The integration takes into account (1) radiative transfer inside the canopy, (2) variation of foliage photosynthetic capacity with canopy depth, (3) wind speed attenuation throughout the canopy, and (4) rainfall interception by foliage elements. The soil module uses principles of the diffusion theory to predict temperature and moisture dynamics within the soil column, evaporation, and CO2 efflux from soil. The effect of soil heterogeneity on field-scale fluxes is simulated employing the Bresler-Dagan stochastic concept. The accumulation and melt of snow on the ground is predicted using an explicit energy balance approach. Ozone deposition is modeled as a sum of three fluxes- ozone uptake via plant stomata, deposition to non-transpiring plant surfaces, and ozone flux into the ground. All biophysical interactions are computed hourly while model projections are made at either hourly or daily time step. FORFLUX represents a comprehensive approach to studying ozone deposition and its link to carbon and water cycles in terrestrial ecosystems.

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

PubMed Central

Scheffler, Ulf; Mahrwald, Rainer

2014-01-01

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear recognition and strict differentiation of two similar carbonyl compounds (aldehydes → secondary 1,2-diols or ketones → tertiary 1,2-diols). This fine-tuning is still a challenge and an unsolved problem for an organic chemist. There exist several reports on successful execution of this transformation but they cannot be generalized. Herein we describe a catalytic direct pinacol coupling process which proceeds via a retropinacol/cross-pinacol coupling sequence. Thus, unsymmetrical substituted 1,2-diols can be accessed with almost quantitative yields by means of an operationally simple performance under very mild conditions. Artificial techniques, such as syringe-pump techniques or delayed additions of reactants are not necessary. The procedure we describe provides a very rapid access to cross-pinacol products (1,2-diols, vicinal diols). A further extension of this new process, e.g. an enantioselective performance could provide a very useful tool for the synthesis of unsymmetrical chiral 1,2-diols. PMID:24747370

Enhanced pharmaceutical removal from water in a three step bio-ozone-bio process.

PubMed

de Wilt, Arnoud; van Gijn, Koen; Verhoek, Tom; Vergnes, Amber; Hoek, Mirit; Rijnaarts, Huub; Langenhoff, Alette

2018-07-01

Individual treatment processes like biological treatment or ozonation have their limitations for the removal of pharmaceuticals from secondary clarified effluents with high organic matter concentrations (i.e. 17 mg TOC/L). These limitations can be overcome by combining these two processes for a cost-effective pharmaceutical removal. A three-step biological-ozone-biological (BO 3 B) treatment process was therefore designed for the enhanced pharmaceutical removal from wastewater effluent. The first biological step removed 38% of ozone scavenging TOC, thus proportionally reducing the absolute ozone input for the subsequent ozonation. Complementariness between biological and ozone treatment, i.e. targeting different pharmaceuticals, resulted in cost-effective pharmaceutical removal by the overall BO 3 B process. At a low ozone dose of 0.2 g O 3 /g TOC and an HRT of 1.46 h in the biological reactors, the removal of 8 out of 9 pharmaceuticals exceeded 85%, except for metoprolol (60%). Testing various ozone doses and HRTs revealed that pharmaceuticals were ineffectively removed at 0.1 g O3/g TOC and an HRT of 0.3 h. At HRTs of 0.47 and 1.46 h easily and moderately biodegradable pharmaceuticals such as caffeine, gemfibrozil, ibuprofen, naproxen and sulfamethoxazole were over 95% removed by biological treatment. The biorecalcitrant carbamazepine was completely ozonated at a dose of 0.4 g O 3 /g TOC. Ozonation products are likely biodegraded in the last biological reactor as a 17% TOC removal was found. No appreciable acute toxicity towards D. magna, P. subcapitata and V. fischeri was found after exposure to the influents and effluents of the individual BO 3 B reactors. The BO 3 B process is estimated to increase the yearly wastewater treatment tariff per population equivalent in the Netherlands by less than 10%. Overall, the BO 3 B process is a cost-effective treatment process for the removal of pharmaceuticals from secondary clarified effluents. Copyright

Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

2016-09-01

Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

Removal and toxicity reduction of naphthenic acids by ozonation and combined ozonation-aerobic biodegradation.

PubMed

Vaiopoulou, Eleni; Misiti, Teresa M; Pavlostathis, Spyros G

2015-03-01

A commercial naphthenic acids (NAs) mixture (TCI Chemicals) and five model NA compounds were ozonated in a semibatch mode. Ozonation of 25 and 35 mg/L NA mixture followed pseudo first-order kinetics (k(obs)=0.11±0.008 min(-1); r(2)=0.989) with a residual NAs concentration of about 5 mg/L. Ozone reacted preferentially with NAs of higher cyclicity and molecular weight and decreased both cyclicity and the acute Microtox® toxicity by 3.3-fold. The ozone reactivity with acyclic and monocyclic model NAs varied and depended on other structural features, such as branching and the presence of tertiary or quaternary carbons. Batch aerobic degradation of unozonated NA mixture using a NA-enriched culture resulted in 83% NA removal and a 6.7-fold decrease in toxicity, whereas a combination of ozonation-biodegradation resulted in 89% NA removal and a 15-fold decrease in toxicity. Thus, ozonation of NA-bearing waste streams coupled with biodegradation are effective treatment processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development and evaluation of kinetic spectrophotometric assays for horseradish peroxidase by catalytic coupling of paraphenylenediamine and mequinol.

PubMed

Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Kumar Shrestha, Ashwinee

2009-10-01

This paper presents a novel spectrophotometric method to measure peroxidase activity using paraphenylenediamine dihydrochloride (PPDD) and Mequinol (MQ). The PPDD traps the free radical, and gets oxidized to electrophilic 1,4-diimine; this couples with MQ to an give intense violet-colored chromogenic species with the maximum absorbance at 560 nm. This assay was adopted for the quantification of hydrogen peroxide between 10 x 10(-6) to 80 x 10(-6) M. From the kinetic data, a two-substrate ping-pong mechanism of peroxidase was established. Catalytic efficiency and catalytic power of commercial peroxidase were 0.204 x 10(6) M(-1) min(-1) and 2.86 x 10(-4) min(-1), respectively. The catalytic constant (k(cat)) of the proposed method was 0.2080 x 10(3) min(-1). As a simple, rapid, precise and sensitive technique, PPDD-MQ stands as a potential replacement for the traditional guaiacol method. Applications to the plant extracts increase its relevance in the field of biochemical analysis.

Kinetic evaluation of graphene oxide based heterogenous catalytic ozonation for the removal of ibuprofen.

PubMed

Jothinathan, Lakshmi; Hu, Jiangyong

2018-05-01

In this study, the performance of graphene oxide (GO) in ozonation process was kinetically evaluated using the modified R ct concept since GO may act as initiator, promoter and inhibitor in ozone radical chain reaction. The applicability of the modified R ct concept was demonstrated using different GO suspensions (GO alone, GO/TiO 2 , GO/Fe 3 O 4 , GO/TiO 2 /Fe 3 O 4 ) in ozonation process. Results showed that ozone exposure and •OH exposure were found to be higher for GO/Fe 3 O 4 and GO/TiO 2 /Fe 3 O 4 compared to other GO suspensions, which was almost equivalent to O 3 /H 2 O 2 process. The determined initiation and inhibition rate constants of GO alone, were 1 fold higher than GO/Fe 3 O 4 and GO/TiO 2 /Fe 3 O 4 , since the GO alone suspension possesses higher O 3 decomposition but lower organic degradation because that GO does not yield •OH. Moreover, GO/Fe 3 O 4 suspension, along with natural organic matter (NOM), was proven to be helpful in degrading ibuprofen in ozonation process, but the effect was minimal when compared to O 3 /H 2 O 2 process. These results exhibited that the surface modified GO suspensions could be utilized as future alternative AOPs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Improved simulation of tropospheric ozone by a global-multi-regional two-way coupling model system

NASA Astrophysics Data System (ADS)

Yan, Y.-Y.; Lin, J.-T.; Chen, J.; Hu, L.

2015-09-01

Small-scale nonlinear chemical and physical processes over pollution source regions affect the global ozone (O3) chemistry, but these processes are not captured by current global chemical transport models (CTMs) and chemistry-climate models that are limited by coarse horizontal resolutions (100-500 km, typically 200 km). These models tend to contain large (and mostly positive) tropospheric O3 biases in the Northern Hemisphere. Here we use a recently built two-way coupling system of the GEOS-Chem CTM to simulate the global tropospheric O3 in 2009. The system couples the global model (at 2.5° long. × 2° lat.) and its three nested models (at 0.667° long. × 0.5° lat.) covering Asia, North America and Europe, respectively. Benefiting from the high resolution, the nested models better capture small-scale processes than the global model alone. In the coupling system, the nested models provide results to modify the global model simulation within respective nested domains while taking the lateral boundary conditions from the global model. Due to the "coupling" effects, the two-way system significantly improves the tropospheric O3 simulation upon the global model alone, as found by comparisons with a suite of ground (1420 sites from WDCGG, GMD, EMEP, and AQS), aircraft (HIPPO and MOZAIC), and satellite measurements (two OMI products). Compared to the global model alone, the two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean O3 with the ground measurements from 0.53 to 0.68, and it reduces the mean model bias from 10.8 to 6.7 ppb in annual average afternoon O3. Regionally, the coupled model reduces the bias by 4.6 ppb over Europe, 3.9 ppb over North America, and 3.1 ppb over other regions. The two-way coupling brings O3 vertical profiles much closer to the HIPPO (for remote areas) and MOZAIC (for polluted regions) data, reducing the tropospheric (0-9 km) mean bias by 3-10 ppb at most MOZAIC sites and by 5.3 ppb for HIPPO

CALIBRATION OF FULL-SCALE OZONATION SYSTEMS WITH CONSERVATIVE AND REACTIVE TRACERS

EPA Science Inventory

A full-scale ozonation reactor was characterized with respect to the overall oxidation budget by coupling laboratory kinetics with reactor hydraulics. The ozone decomposition kinetics and the ratio of the OH radical to the ozone concentration were determined in laboratory batch ...

Comparative study of activated carbon, natural zeolite, and green sand supports for CuOX and ZnO sites as ozone decomposition catalyst

NASA Astrophysics Data System (ADS)

Azhariyah, A. S.; Pradyasti, A.; Dianty, A. G.; Bismo, S.

2018-03-01

This research was based on ozone decomposition in industrial environment. Ozone is harmful to human. Therefore, catalysts were made as a mask filter to decompose ozone. Comparison studies of catalyst supports were done using Granular Activated Carbon (GAC), Natural Zeolite (NZ), and Green Sand (GS). GAC showed the highest catalytic activity compared to other supports with conversion of 98%. Meanwhile, the conversion using NZ was only 77% and GS had been just 27%. GAC had the highest catalytic activity because it had the largest pore volume, which is 0.478 cm3/g. So GAC was used as catalyst supports. To have a higher conversion in ozone decomposition, GAC was impregnated with metal oxide as the active site of the catalyst. Active site comparison was made using CuOX and ZnO as the active site. Morphology, composition, and crystal phase were analyzed using SEM-EDX, XRF, and XRD methods. Mask filter, which contained catalysts for ozone decomposition, was tested using a fixed bed reactor at room temperature and atmospheric pressure. The result of conversion was analyzed using iodometric method. CuOX/GAC and ZnO/GAC 2%-w showed the highest catalytic activity and conversion reached 100%. From the durability test, CuOX/GAC 2%-w was better than ZnO/GAC 2%-w because the conversion of ozone to oxygen reached 100% with the lowest conversion was 70% for over eight hours.

Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

NASA Astrophysics Data System (ADS)

Mao, J.; Fan, S.; Jacob, D. J.; Travis, K.; Naik, V.; Horowitz, L. W.

2012-12-01

The hydroperoxyl radical (HO2) is a major precursor of OH and tropospheric ozone. OH is the main atmospheric oxidant, while tropospheric ozone is an important surface pollutant and greenhouse gas. Standard gas-phase models for atmospheric chemistry tend to overestimate observed HO2 concentrations, and this has been tentatively attributed to heterogeneous uptake by aerosol particles. It is generally assumed that HO2 uptake by aerosol involves conversion to H2O2, but this is of limited efficacy as an HO2 sink because H2O2 can photolyze to regenerate OH and from there HO2. Joint atmospheric observations of HO2 and H2O2 suggest that HO2 uptake by aerosols may in fact not produce H2O2. Here we propose a catalytic mechanism involving coupling of the transition metal ions (TMI) Cu(I)/Cu(II) and Fe(II)/Fe(III) to rapidly convert HO2 to H2O in aerosols. The implied HO2 uptake significantly affects global model predictions of tropospheric OH, ozone, and other species, improving comparisons to observations, and may have a major and previously unrecognized impact on atmospheric oxidant chemistry.

Massive global ozone loss predicted following regional nuclear conflict

PubMed Central

Mills, Michael J.; Toon, Owen B.; Turco, Richard P.; Kinnison, Douglas E.; Garcia, Rolando R.

2008-01-01

We use a chemistry-climate model and new estimates of smoke produced by fires in contemporary cities to calculate the impact on stratospheric ozone of a regional nuclear war between developing nuclear states involving 100 Hiroshima-size bombs exploded in cities in the northern subtropics. We find column ozone losses in excess of 20% globally, 25–45% at midlatitudes, and 50–70% at northern high latitudes persisting for 5 years, with substantial losses continuing for 5 additional years. Column ozone amounts remain near or <220 Dobson units at all latitudes even after three years, constituting an extratropical “ozone hole.” The resulting increases in UV radiation could impact the biota significantly, including serious consequences for human health. The primary cause for the dramatic and persistent ozone depletion is heating of the stratosphere by smoke, which strongly absorbs solar radiation. The smoke-laden air rises to the upper stratosphere, where removal mechanisms are slow, so that much of the stratosphere is ultimately heated by the localized smoke injections. Higher stratospheric temperatures accelerate catalytic reaction cycles, particularly those of odd-nitrogen, which destroy ozone. In addition, the strong convection created by rising smoke plumes alters the stratospheric circulation, redistributing ozone and the sources of ozone-depleting gases, including N2O and chlorofluorocarbons. The ozone losses predicted here are significantly greater than previous “nuclear winter/UV spring” calculations, which did not adequately represent stratospheric plume rise. Our results point to previously unrecognized mechanisms for stratospheric ozone depletion. PMID:18391218

Solar photocatalytic ozonation of a mixture of pharmaceutical compounds in water.

PubMed

Márquez, Gracia; Rodríguez, Eva M; Beltrán, Fernando J; Álvarez, Pedro M

2014-10-01

Aqueous solutions of mixtures of four pharmaceutical compounds (atenolol, hydrochlorothiazide, ofloxacin and trimethoprim) both in Milli-Q ultrapure water and in a secondary effluent from a municipal wastewater treatment plant have been treated at pH 7 by different oxidation methods, such as conventional ozonation, photolytic ozonation, TiO2 catalytic ozonation, TiO2 photocatalytic oxidation and TiO2 photocatalytic ozonation. Experiments were carried out using a solar compound parabolic concentrator. The performance results have been compared in terms of removal of emerging contaminants (ECs), generation rate of phenolic intermediates, organic matter mineralization, ecotoxicity removal and enhancement of biodegradability. Also, the consumption of ozone to achieve certain treatment goals (95% removal of ECs and 40% mineralization) is discussed. Results reveal that solar photocatalytic ozonation is a promising oxidation method as it led to the best results in terms of EC mineralization (∼85%), toxicity removal (∼90%) and efficient use of ozone (∼2mgO3mgEC(-1) to achieve complete EC removal and ∼18mgO3mgTOC(-1) to achieve 40% EC mineralization, respectively). Copyright © 2014 Elsevier Ltd. All rights reserved.

Ozone kinetics in low-pressure discharges

NASA Astrophysics Data System (ADS)

Guerra, Vasco; Marinov, Daniil; Guaitella, Olivier; Rousseau, Antoine

2012-10-01

Ozone kinetics is quite well established at atmospheric pressure, due to the importance of ozone in atmospheric chemistry and to the development of industrial ozone reactors. However, as the pressure is decreased and the dominant three-body reactions lose importance, the main mechanisms involved in the creation and destruction of ozone are still surrounded by important uncertainties. In this work we develop a self-consistent model for a pulsed discharge and its afterglow operating in a Pyrex reactor with inner radius 1 cm, at pressures in the range 1-5 Torr and discharge currents of 40-120 mA. The model couples the electron Boltzmann equation with a system of equations for the time evolution of the heavy particles. The calculations are compared with time-dependent measurements of ozone and atomic oxygen. Parametric studies are performed in order to clarify the role of vibrationally excited ozone in the overall kinetics and to establish the conditions where ozone production on the surface may become important. It is shown that vibrationally excited ozone does play a significant role, by increasing the time constants of ozone formation. Moreover, an upper limit for the ozone formation at the wall in these conditions is set at 10(-4).

Simple catalytic mechanism for the direct coupling of α-carbonyls with functionalized amines: a one-step synthesis of Plavix.

PubMed

Evans, Ryan W; Zbieg, Jason R; Zhu, Shaolin; Li, Wei; MacMillan, David W C

2013-10-30

The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino-substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst is reconstituted. The practical value of this transformation is highlighted through one-step syntheses of two high-profile pharmaceutical agents, Plavix and amfepramone.

Decrease of summer tropospheric ozone concentrations in Antarctica

NASA Technical Reports Server (NTRS)

Schnell, R. C.; Stone, R. S.; Liu, S. C.; Oltmans, S. J.; Hofmann, D. J.

1991-01-01

It is shown here that surface ozone concentrations at the South Pole in the austral summer decreased by 17 percent over the period 1976-90. Over the same period, solar irradiance at the South Pole in January and February decreased by 7 percent as a result of a 25 percent increase in cloudiness. It is suggested that the trend in the summer ozone concentrations is caused by enhanced photochemical destruction of ozone in the lower troposphere caused by the increased penetration of UV radiation associated with stratospheric ozone depletion, coupled with enhanced transport of ozone-poor marine air from lower latitudes to the South Pole.

Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

PubMed

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.

Iron decreases biological effects of ozone exposure

EPA Science Inventory

CONTEXT: Ozone (0(3)) exposure is associated with a disruption of iron homeostasis and increased availability of this metal which potentially contributes to an oxidative stress and biologicaleffects. OBJECTIVE: We tested the postulate that increased concentrations of iron in c...

Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

NASA Astrophysics Data System (ADS)

Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.; Kinahan, Sean; Corson, Elizabeth; Eshbaugh, Jonathan; Santarpia, Joshua L.

2015-03-01

Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometer (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.

N- vs. C-Domain Selectivity of Catalytic Inactivation of Human Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

PubMed Central

Hocharoen, Lalintip; Joyner, Jeff C.; Cowan, J. A.

2014-01-01

The N- and C-terminal domains of human somatic Angiotensin I Converting Enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates were tested for both reversible binding and irreversible catalytic inactivation of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of the M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and orientation factors (double-filter effect). PMID:24228790

Impact of Ozone Radiative Feedbacks on Global Weather Forecasting

NASA Astrophysics Data System (ADS)

Ivanova, I.; de Grandpré, J.; Rochon, Y. J.; Sitwell, M.

2017-12-01

A coupled Chemical Data Assimilation system for ozone is being developed at Environment and Climate Change Canada (ECCC) with the goals to improve the forecasting of UV index and the forecasting of air quality with the Global Environmental Multi-scale (GEM) Model for Air quality and Chemistry (MACH). Furthermore, this system provides an opportunity to evaluate the benefit of ozone assimilation for improving weather forecasting with the ECCC Global Deterministic Prediction System (GDPS) for Numerical Weather Prediction (NWP). The present UV index forecasting system uses a statistical approach for evaluating the impact of ozone in clear-sky and cloudy conditions, and the use of real-time ozone analysis and ozone forecasts is highly desirable. Improving air quality forecasting with GEM-MACH further necessitates the development of integrated dynamical-chemical assimilation system. Upon its completion, real-time ozone analysis and ozone forecasts will also be available for piloting the regional air quality system, and for the computation of ozone heating rates, in replacement of the monthly mean ozone distribution currently used in the GDPS. Experiments with ozone radiative feedbacks were run with the GDPS at 25km resolution and 84 levels with a lid at 0.1 hPa and were initialized with ozone analysis that has assimilated total ozone column from OMI, OMPS, and GOME satellite instruments. The results show that the use of prognostic ozone for the computation of the heating/cooling rates has a significant impact on the temperature distribution throughout the stratosphere and upper troposphere regions. The impact of ozone assimilation is especially significant in the tropopause region, where ozone heating in the infrared wavelengths is important and ozone lifetime is relatively long. The implementation of the ozone radiative feedback in the GDPS requires addressing various issues related to model biases (temperature and humidity) and biases in equilibrium state (ozone mixing

Ozone depletion - Ultraviolet radiation and phytoplankton biology in Antarctic waters

NASA Technical Reports Server (NTRS)

Smith, R. C.; Prezelin, B. B.; Baker, K. S.; Bidigare, R. R.; Boucher, N. P.; Coley, T.; Karentz, D.; Macintyre, S.; Matlick, H. A.; Menzies, D.

1992-01-01

The near-50-percent thinning of the stratospheric ozone layer over the Antarctic, with increased passage of mid-UV radiation to the surface of the Southern Ocean, has prompted concern over possible radiation damage to the near-surface phytoplankton communities that are the bases of Antarctic marine ecosystems. As the ozone layer thinned, a 6-week study of the marginal ice zone of the Bellingshousen Sea in the austral spring of 1990 noted sea-surface and depth-dependent ratios of mid-UV irradiance to total irradiance increased, and mid-UV inhibition of photosynthesis increased. A 6-12 percent reduction in primary production associated with ozone depletion was estimated to have occurred over the course of the present study.

RESULTS OF RESEARCH RELATED TO STRATOSPHERIC OZONE PROTECTION

EPA Science Inventory

Research on ozone protection has been coordinated under the Biological and Climatic Effects Research (BACER) Program. This is a multiagency, multidisciplinary effort initially funded by The Environmental Protection Agency. Its purpose is to reduce uncertainties regarding ozone de...

Synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles and nanowires

NASA Astrophysics Data System (ADS)

Xie, Yi; Heo, Sung Hwan; Kim, Yong Nam; Yoo, Seung Hwa; Cho, Sung Oh

2010-01-01

We present the synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles (NPs) and TiO2 nanowires (NWs). Through a simple wet chemical process from a mixture of peroxo titanic acid (PTA) solution, thiourea and AgAc, a composite of Ag2S NPs and TiO2 NPs with sizes of less than 7 nm was formed. When the NP composite was further treated with NaOH solution followed by annealing at ambient conditions, a new nanocomposite material comprising Ag2S NPs on TiO2 NWs was created. Due to the coupling with such a low bandgap material as Ag2S, the TiO2 nanocomposites could have a visible-light absorption capability much higher than that of pure TiO2. As a result, the synthesized Ag2S/TiO2 nanocomposites exhibited much higher catalytic efficiency for the decomposition of methyl orange than commercial TiO2 (Degussa P25, Germany) under visible light.

Pretreatment of cyanided tailings by catalytic ozonation with Mn2+/O3.

PubMed

Li, Yulong; Li, Dengxin; Li, Jiebing; wang, Jin; Hussain, Asif; Ji, Hao; Zhai, Yijie

2015-02-01

The increasing amount of cyanided tailings produced as a by-product has gained significant attention in recent years because of the rapid development of the gold industry and extensive exploitation of gold mineral resources. The effective use of these secondary resources is becoming an important and urgent problem for all environmental protection staff. Manganese-catalyzed ozonation for the pre-oxidation of cyanided tailings was studied and the effects of Mn2+ dosage, initial sulfuric acid concentration, ozone volume flow, temperature and agitation speed on pretreatment were examined. The optimum reaction conditions were observed to be: ore pulp density 2.5%, agitation speed 700 r/min, temperature 60°C, Mn2+ dosage 40 g/L, ozone volume flow 80 L/hr, initial sulfuric acid concentration 1 mol/L, and reaction time 6 hr. Under these conditions, the leaching rate of Fe and weight loss could reach 94.85% and 48.89% respectively. The leaching process of cyanided tailings by Mn2+/O3 was analyzed, and it was found that the leaching of pyrite depends on synergetic oxidation by high-valent manganese and O3, in which the former played an important part. Copyright © 2014. Published by Elsevier B.V.

Plasmachemical and heterogeneous processes in ozonizers with oxygen activation by a dielectric barrier discharge

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

Mankelevich, Yu. A., E-mail: ymankelevich@mics.msu.su; Voronina, E. N.; Poroykov, A. Yu.

Plasmachemical and heterogeneous processes of generation and loss of ozone in the atmosphericpressure dielectric barrier discharge in oxygen are studied theoretically. Plasmachemical and electronic kinetics in the stage of development and decay of a single plasma filament (microdischarge) are calculated numerically with and without allowance for the effects of ozone vibrational excitation and high initial ozone concentration. The developed analytical approach is applied to determine the output ozone concentration taking into account ozone heterogeneous losses on the Al{sub 2}O{sub 3} dielectric surface. Using the results of quantummechanical calculations by the method of density functional theory, a multistage catalytic mechanism ofmore » heterogeneous ozone loss based on the initial passivation of a pure Al{sub 2}O{sub 3} surface by ozone and the subsequent interaction of O{sub 3} molecules with the passivated surface is proposed. It is shown that the conversion reaction 2O{sub 3} → 3O{sub 2} of a gas-phase ozone molecule with a physically adsorbed ozone molecule can result in the saturation of the maximum achievable ozone concentration at high specific energy depositions, the nonstationarity of the output ozone concentration, and its dependence on the prehistory of ozonizer operation.« less

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

NASA Astrophysics Data System (ADS)

Nguyen, Thach T.; Koh, Ming Joo; Mann, Tyler J.; Schrock, Richard R.; Hoveyda, Amir H.

2017-12-01

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis.

PubMed

Nguyen, Thach T; Koh, Ming Joo; Mann, Tyler J; Schrock, Richard R; Hoveyda, Amir H

2017-12-20

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity-namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products-and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

OXIDATION OF METHANOL USING OZONE ON TITANIA-SUPPORTED VANADIUM CATALYST

EPA Science Inventory

Catalytic ozone decomposition of methanol has been conducted at mild temperatures of 100 to 250°C using V2O5/TiO2 catalyst prepared by either sol-gel or wet impregnation methods. The catalysts were characterized using XRD, surface area measurements, and desorption of CH3OH. Gas p...

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.

Ozone Sensitivity to Varying Greenhouse Gases and Ozone-Depleting Substances in CCMI-1 Simulations

NASA Technical Reports Server (NTRS)

Morgenstern, Olaf; Stone, Kane A.; Schofield, Robyn; Akiyoshi, Hideharu; Yamashita, Yousuke; Kinnison, Douglas E.; Garcia, Rolando R.; Sudo, Kengo; Plummer, David A.; Scinocca, John;

Ozone sensitivity to varying greenhouse gases and ozone-depleting substances in CCMI-1 simulations

NASA Astrophysics Data System (ADS)

Morgenstern, Olaf; Stone, Kane A.; Schofield, Robyn; Akiyoshi, Hideharu; Yamashita, Yousuke; Kinnison, Douglas E.; Garcia, Rolando R.; Sudo, Kengo; Plummer, David A.; Scinocca, John; Oman, Luke D.; Manyin, Michael E.; Zeng, Guang; Rozanov, Eugene; Stenke, Andrea; Revell, Laura E.; Pitari, Giovanni; Mancini, Eva; Di Genova, Glauco; Visioni, Daniele; Dhomse, Sandip S.; Chipperfield, Martyn P.

2018-01-01

Ozone fields simulated for the first phase of the Chemistry-Climate Model Initiative (CCMI-1) will be used as forcing data in the 6th Coupled Model Intercomparison Project. Here we assess, using reference and sensitivity simulations produced for CCMI-1, the suitability of CCMI-1 model results for this process, investigating the degree of consistency amongst models regarding their responses to variations in individual forcings. We consider the influences of methane, nitrous oxide, a combination of chlorinated or brominated ozone-depleting substances, and a combination of carbon dioxide and other greenhouse gases. We find varying degrees of consistency in the models' responses in ozone to these individual forcings, including some considerable disagreement. In particular, the response of total-column ozone to these forcings is less consistent across the multi-model ensemble than profile comparisons. We analyse how stratospheric age of air, a commonly used diagnostic of stratospheric transport, responds to the forcings. For this diagnostic we find some salient differences in model behaviour, which may explain some of the findings for ozone. The findings imply that the ozone fields derived from CCMI-1 are subject to considerable uncertainties regarding the impacts of these anthropogenic forcings. We offer some thoughts on how to best approach the problem of generating a consensus ozone database from a multi-model ensemble such as CCMI-1.

Effect of radiant catalytic ionization on lean color and lipid oxidation of beef

USDA-ARS?s Scientific Manuscript database

Objectives: The radiant catalytic ionization (RCI) technology utilizes a combination of UV light and low-level oxidizers such as ozone, hydroxyl radicals, and hydrogen peroxide to cause antimicrobial action. There is a potential to use this technology as an antimicrobial intervention against foodbor...

Ozone-UV-catalysis based advanced oxidation process for wastewater treatment.

PubMed

Tichonovas, Martynas; Krugly, Edvinas; Jankunaite, Dalia; Racys, Viktoras; Martuzevicius, Dainius

2017-07-01

A bench-scale advanced oxidation (AO) reactor was investigated for the degradation of six pollutants (2-naphthol, phenol, oxalic acid, phthalate, methylene blue, and D-glucose) in a model wastewater at with the aim to test opportunities for the further upscale to industrial applications. Six experimental conditions were designed to completely examine the experimental reactor, including photolysis, photocatalysis, ozonation, photolytic ozonation, catalytic ozonation, and photocatalytic ozonation. The stationary catalyst construction was made from commercially available TiO 2 nanopowder by mounting it on a glass support and subsequently characterized for morphology (X-ray diffraction analysis and scanning electron microscopy) as well as durability. The ozone was generated in a dielectrical barrier discharge reactor using air as a source of oxygen. The degradation efficiency was estimated by the decrease in total organic carbon (TOC) concentration as well as toxicity using Daphnia magna, and degradation by-products by ultra-performance liquid chromatography-mass spectrometry. The photocatalytic ozonation was the most effective for the treatment of all model wastewater. The photocatalytic ozonation was most effective against ozonation and photolytic ozonation at tested pH values. A complete toxicity loss was obtained after the treatment using photocatalytic ozonation. The possible degradation pathway of the phthalate by oxidation was suggested based on aromatic ring opening reactions. The catalyst used at this experiment confirmed as a durable for continuous use with almost no loss of activity over time. The design of the reactor was found to be very effective for water treatment using photocatalytic ozonation. Such design has a high potential and can be further upscaled to industrial applications due to the simplicity and versatility of manufacturing and maintenance.

A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

PubMed Central

Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

2014-01-01

The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst is reconstituted. The practical value of this transformation is highlighted through one-step syntheses of two high–profile pharmaceutical agents, Plavix and amfepramone. PMID:24107144

Advanced low carbon-to-nitrogen ratio wastewater treatment by electrochemical and biological coupling process.

PubMed

Deng, Shihai; Li, Desheng; Yang, Xue; Zhu, Shanbin; Xing, Wei

2016-03-01

Nitrogen pollution in ground and surface water significantly affects the environment and its organisms, thereby leading to an increasingly serious environmental problem. Such pollution is difficult to degrade because of the lack of carbon sources. Therefore, an electrochemical and biological coupling process (EBCP) was developed with a composite catalytic biological carrier (CCBC) and applied in a pilot-scale cylindrical reactor to treat wastewater with a carbon-to-nitrogen (C/N) ratio of 2. The startup process, coupling principle, and dynamic feature of the EBCP were examined along with the effects of hydraulic retention time (HRT), dissolved oxygen (DO), and initial pH on nitrogen removal. A stable coupling system was obtained after 51 days when plenty of biofilms were cultivated on the CCBC without inoculation sludge. Autotrophic denitrification, with [Fe(2+)] and [H] produced by iron-carbon galvanic cells in CCBC as electron donors, was confirmed by equity calculation of CODCr and nitrogen removal. Nitrogen removal efficiency was significantly influenced by HRT, DO, and initial pH with optimal values of 3.5 h, 3.5 ± 0.1 mg L(-1), and 7.5 ± 0.1, respectively. The ammonia, nitrate, and total nitrogen (TN) removal efficiencies of 90.1 to 95.3 %, 90.5 to 99.0 %, and 90.3 to 96.5 % were maintained with corresponding initial concentrations of 40 ± 2 mg L(-1) (NH3-N load of 0.27 ± 0.01 kg NH3-N m(-3) d(-1)), 20 ± 1 mg L(-1), and 60 ± 2 mg L(-1) (TN load of 0.41 ± 0.02 kg TN m(-3) d(-1)). Based on the Eckenfelder model, the kinetics equation of the nitrogen transformation along the reactor was N e  = N 0 exp (-0.04368 h/L(1.8438)). Hence, EBCP is a viable method for advanced low C/N ratio wastewater treatment.

Statistical estimation of ozone exposure metrics

NASA Astrophysics Data System (ADS)

Blankenship, Erin E.; Stefanski, L. A.

Data from recent experiments at North Carolina State University and other locations provide a unique opportunity to study the effect of ambient ozone on the growth of clover. The data consist of hourly ozone measurements over a 140 day growing season at eight sites in the US, coupled with clover growth response data measured every 28 days. The objective is to model an indicator of clover growth as a function of ozone exposure. A common strategy for dealing with the numerous hourly ozone measurements is to reduce these to a single summary measurement, a so-called exposure metric, for the growth period of interest. However, the mean ozone value is not necessarily the best summarization, as it is widely believed that low levels of ozone have a negligible effect on growth, whereas peak ozone values are deleterious to plant growth. There are also suspected interactions with available sunlight, temperature and humidity. A number of exposure metrics have been proposed that reflect these beliefs by assigning different weights to ozone values according to magnitude, time of day, temperature and humidity. These weighting schemes generally depend on parameters that have, to date, been subjectively determined. We propose a statistical approach based on profile likelihoods to estimate the parameters in these exposure metrics.

Ozone adsorption on carbon nanoparticles

NASA Astrophysics Data System (ADS)

Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

2014-05-01

Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles < 50 nm), under magnetic stirring. The aerosol was then mixed with ozone in an aerosol flow tube. Ozone uptake experiments were performed with different particles concentrations with a fixed ozone concentration. The influence of several factors on kinetics was examined: initial ozone concentration, particle size (50 nm ≤ Dp ≤ 200 nm) and competitive adsorption (with probe molecule and water). The effect of initial ozone concentration was first studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were

Enzyme as catalytic wheel powered by a Markovian engine: conformational coupling and barrier surfing models

NASA Astrophysics Data System (ADS)

Tsong, Tian Yow; Chang, Cheng-Hung

2005-05-01

We examine a typical Michaelis-Menten Enzyme (MME) and redress it to form a transducer of free energy, and electric, acoustic, or other types of energy. This amendment and extension is necessary in lieu of recent experiments in which enzymes are shown to perform pump, motor, and locomotion functions resembling their macroscopic counterparts. Classical textbook depicts enzyme, or an MME, as biocatalyst which can enhance the rate of a chemical reaction by lowering the activation barrier but cannot shift the thermodynamic equilibrium of the biochemical reaction. An energy transducer, on the other hand, must also be able to harvest, store, or divert energy and in doing so alter the chemical equilibrium, change the energy form, fuel an energy consuming process, or perform all these functions stepwise in one catalytic turnover. The catalytic wheel presented in this communication is both a catalyst and an energy transducer and can perform all these tasks with ease. A Conformational Coupling Model for the rotary motors and a Barrier Surfing Model for the track-guided stepping motors and transporters, are presented and compared. It is shown that the core engine of the catalytic wheel, or a Brownian motor, is a Markovian engine. It remains to be seen if this core engine is the basic mechanism for a wide variety of bio-molecular energy transducers, as well as certain other dynamic systems, for example, the Parrondo's Games.

VANADIA CATALYZED VAPOR PHASE OXIDATION OF METHANOL IN THE PRESENCE OF OZONE

EPA Science Inventory

Catalytic oxidation of methanol was carried out in the presence of ozone using vanadia based catalysts. The process can be used to selectively convert alcohols to aldehydes or ketones. It can also be used to control emissions of volatile organic compounds from Kraft mill and ot...

Combined treatment of mezcal vinasses by ozonation and activated sludge.

PubMed

2017-10-18

In Mexico, mezcal production generates huge amounts of vinasses (MV) that cause negative environmental impacts. Thus, MV treatment is necessary before discharge to water bodies. Although there is no information for mezcal vinasses, similar effluents have been treated by biological processes (i.e. anaerobic and aerobic) usually complemented by oxidative chemical pretreatments (ozonation) and physico-chemical methods. In this work MV were first ozonated and followed by batch aerobic biological degradation. In the ozonation stage, organic matter removals were 4.5-11 % as COD, whereas the removal of aromatic compounds and phenols were 16-32 % and 48-83 % respectively. In the aerobic post-treatment, COD depletions up to 85 % were achieved; removals in ozone pre-treated vinasses were higher (80 to 85 %) than that of raw vinasse (69 %). It seems that ozonation preferentially attacked the recalcitrant fraction of organic matter present in the vinasses and increased its aerobic biodegradability.

Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

DOE PAGES

Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.; ...

2015-10-14

Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometermore » (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.« less

Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

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

Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.

Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometermore » (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.« less

Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

PubMed

Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

2015-03-21

Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

Catalytic processes in the atmospheres of earth and Venus

NASA Technical Reports Server (NTRS)

Demore, W. B.; Yung, Y. L.

1982-01-01

Photochemical processes in planetary atmospheres are strongly influenced by catalytic effects of minor constituents. Catalytic cycles in the atmospheres of Earth and Venus are closely related. For example, chlorine oxides (ClOx) act as catalysts in the two atmospheres. On earth, they serve to convert odd oxygen (atomic oxygen and ozone) to molecular oxygen. On Venus they have a similar effect, but in addition they accelerate the reactions of atomic and molecular oxygen with carbon monoxide. The latter process occurs by a unique combination of ClOx catalysis and sulful dioxide photosensitization. The mechanism provides an explanation for the very low extent of carbon dioxide decomposition by sunlight in the Venus atmosphere.

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts.

PubMed

Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

NASA Astrophysics Data System (ADS)

Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.

Ozonation of return activated sludge for disintegration and solubilisation with synthesized titanium oxide as catalyst

NASA Astrophysics Data System (ADS)

Sarif, S. F. Z. Mohd; Alias, S. S.; Ridwan, F. Muhammad; Salim, K. S. Ku; Abidin, C. Z. A.; Ali, U. F. Md.

2018-03-01

Ozonation of activated sludge in the present of titanium dioxide (TiO2) as catalyst to enhance the production of hydroxyl radical was evaluated in comparison to the sole ozonation process. In this process, the catalytic ozontion showed improvement in increasing ozone consumption and improving activated sludge disintegration and solubilisation. The reduction of total suspended solid (TSS), volatile suspended solid (VSS) and soluble chemical oxygen demand (SCOD) solubilisation was better in the catalytic ozonation system. Initial pH 7 of activated sludge was found best to disintegrate and solubilise the sludge flocs. However upon additional of sodium hydroxide (NaOH) in pH adjustment enhanced the solubilisation of organic matter from the flocs and cells, making the initial pH 9 is the best condition for activated sludge solubilisation. Yet the initial pH 7 of activated sludge supernatant was the best condition to achieve SCOD solubilisation due to sludge floc disintegration, when it had stronger correlation between TSS reduction and SCOD solubilisation (R2=0.961). Lower amount of catalyst of 100 mgTiO2/gTSS was found to disintegrate and solubilise the activated sludge better with 30.4% TSS reduction and 25.2% SCOD solubilisation efficiency, compared to 200 mgTiO2/gTSS with 21.9% and 17.1% TSS reduction and SCOD solubilisation, respectively.

The Tropospheric Ozone Assessment Report (TOAR): A community-wide effort to quantify tropospheric ozone in a rapidly changing world

NASA Astrophysics Data System (ADS)

Cooper, O. R.; Schultz, M.; Paoletti, E.; Galbally, I. E.; Naja, M. K.; Tarasick, D. W.; Evans, M. J.; Thompson, A. M.

2017-12-01

Tropospheric ozone is a greenhouse gas and pollutant detrimental to human health and crop and ecosystem productivity. Since 1990 a large portion of the anthropogenic emissions that react in the atmosphere to produce ozone has shifted from North America and Europe to Asia. This rapid shift, coupled with limited ozone monitoring in developing nations, left scientists unable to answer the most basic questions: Which regions of the world have the greatest human and plant exposure to ozone pollution? Is ozone continuing to decline in nations with strong emissions controls? To what extent is ozone increasing in the developing world? How can the atmospheric sciences community facilitate access to the ozone metrics necessary for quantifying ozone's impact on human health and crop/ecosystem productivity? To answer these questions the International Global Atmospheric Chemistry Project (IGAC) initiated the Tropospheric Ozone Assessment Report (TOAR). With over 220 member scientists and air quality specialists from 36 nations, TOAR's mission is to provide the research community with an up-to-date scientific assessment of tropospheric ozone's global distribution and trends from the surface to the tropopause. TOAR has also built the world's largest database of surface ozone observations and generated ozone exposure and dose metrics at thousands of measurement sites around the world, freely accessible for research on the global-scale impact of ozone on climate, human health and crop/ecosystem productivity. Plots of these metrics show the regions of the world with the greatest ozone exposure for humans and crops/ecosystems, at least in areas where observations are available. The results also highlight regions where air quality is improving and where it has degraded. TOAR has also conducted the first intercomparison of tropospheric column ozone from ozonesondes and multiple satellite instruments, which provide similar estimates of the present-day tropospheric ozone burden.

The Ecophysiology Of A Pinus Ponderosa Ecosystem Exposed To High Tropospheric Ozone: Implications For Stomatal And Non-Stomatal Ozone Fluxes

NASA Astrophysics Data System (ADS)

Fares, S.; McKay, M.; Goldstein, A.

2008-12-01

Ecosystems remove ozone from the troposphere through both stomatal and non-stomatal deposition. The portion of ozone taken up through stomata has an oxidative effect causing damage. We used a multi-year dataset to assess the physiological controls over ozone deposition. Environmental parameters, CO2 and ozone fluxes were measured continuously from January 2001 to December 2006 above a ponderosa pine plantation near Blodgett Forest, Georgetown, California. We studied the dynamic of NEE (Net Ecosystem Exchange, -838 g C m-2 yr-1) and water evapotranspiration on an annual and daily basis. These processes are tightly coupled to stomatal aperture which also controlled ozone fluxes. High levels of ozone concentrations (~ 100 ppb) were observed during the spring-summer period, with corresponding high levels of ozone fluxes (~ 30 μmol m-2 h-1). During the summer season, a large portion of the total ozone flux was due to non-stomatal processes, and we propose that a plant physiological control, releasing BVOC (Biogenic Volatile Organic Compounds), is mainly responsible. We analyzed the correlations of common ozone exposure metrics based on accumulation of concentrations (AOT40 and SUM0) with ozone fluxes (total, stomatal and non-stomatal). Stomatal flux showed poorer correlation with ozone concentrations than non-stomatal flux during summer and fall seasons, which largely corresponded to the growing period. We therefore suggest that AOT40 and SUM0 are poor predictors of ozone damage and that a physiologically based metric would be more effective.

Spatial, temporal, and vertical variability of polar stratospheric ozone loss in the Arctic winters 2004/2005-2009/2010

NASA Astrophysics Data System (ADS)

Kuttippurath, J.; Godin-Beekmann, S.; Lefèvre, F.; Goutail, F.

2010-10-01

The polar stratospheric ozone loss during the Arctic winters 2004/2005-2009/2010 is investigated by using high resolution simulations from the chemical transport model Mimosa-Chim and observations from Aura Microwave Limb Sounder (MLS), by applying the passive tracer technique. The winter 2004/2005 shows the coldest temperatures, highest area of polar stratospheric clouds and strongest chlorine activation in 2004/2005-2009/2010. The ozone loss diagnosed from both simulations and measurements inside the polar vortex at 475 K ranges from 0.7 ppmv in the warm winter 2005/2006 to 1.5-1.7 ppmv in the cold winter 2004/2005. Halogenated (chlorine and bromine) catalytic cycles contribute to 75-90% of the ozone loss at this level. At 675 K the lowest loss of 0.3-0.5 ppmv is computed in 2008/2009, and the highest loss of 1.3 ppmv is estimated in 2006/2007 by the model and in 2004/2005 by MLS. Most of the ozone loss (60-75%) at this level results from nitrogen catalytic cycles rather than halogen cycles. At both 475 and 675 K levels the simulated ozone and ozone loss evolution inside the vortex is in reasonably good agreement with the MLS observations. The ozone partial column loss in 350-850 K deduced from the model calculations at the MLS sampling locations inside the polar vortex ranges between 43 DU in 2005/2006 and 109 DU in 2004/2005, while those derived from the MLS observations range between 26 DU and 115 DU for the same winters. The partial column ozone depletion derived in that vertical range is larger than that estimated in 350-550 K by 19±7 DU on average, mainly due to NOx chemistry. The column ozone loss estimates from both Mimosa-Chim and MLS in 350-850 K are generally in good agreement with those derived from ground-based ultraviolet-visible spectrometer total ozone observations for the respective winters, except in 2010.

Industrial wastewater treatment in a new gas-induced ozone reactor.

PubMed

Lin, Sheng H; Wang, Ching H

2003-03-17

The present work was to investigate industrial wastewater treatment by ozonation in a new gas-induced reactor in conjunction with chemical coagulation pretreatment. The reactor was specifically designed in a fashion that gas induction was created on the liquid surface by the high-speed action of an impeller turbine inside a draft tube to maximize the ozone gas utilization. A new design feature of the present reactor system was a fixed granular activated carbon (GAC) bed packed in a circular compartment between the reactor wall and the shaft tube. The fixed GAC bed provided additional adsorption and catalytic degradation of organic pollutants. Combination of the fixed GAC bed and ozonation results in enhanced oxidation of organic pollutants. In addition to enhanced pollutant oxidation, ozonation was found to provide in situ GAC regeneration that was considered crucial in the present reaction system. Kinetic investigations were also made using a proposed complex kinetic model to elucidate the possible oxidation reaction mechanisms of the present gas-induced ozonation system. As a complementary measure, chemical coagulation pretreatment was found able to achieve up to 50% COD and 85% ADMI removal. Experimental tests were conducted to identify its optimum operating conditions. Copyright 2003 Elsevier Science B.V.

Antimicrobial efficacy of radiant catalytic ionization against shiga toxin-producing Escherichia coli on inoculated beef

USDA-ARS?s Scientific Manuscript database

Introduction: Shiga Toxin-producing Escherichia coli (STEC), as a common foodborne pathogen, may cause severe human hemorrhagic colitis infection. The radiant catalytic ionization (RCI) technology utilizes a combination of UV light and low-level oxidizers such as ozone, hydroxyl radicals, and hydrog...

Heterogeneous nano-Fe/Ca/CaO catalytic ozonation for selective surface hydrophilization of plastics containing brominated and chlorinated flame retardants (B/CFRs): separation from automobile shredder residue by froth flotation.

PubMed

Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian

2017-02-01

One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.

Mechanisms of inactivation of bacteriophage phiX174 and its DNA in aerosols by ozone and ozonized cyclohexene.

PubMed Central

de Mik, G.; de Groot, I.

1977-01-01

The mechanisms of inactivation of aerosolized bacteriophage phiX174 in atmospheres containing ozone, cyclohexene, or ozonized cyclohexene were studied by using 32P-labelled phage. The inactivation of the aerosolized phage in clear air or in air containing cyclohexene is due to damage of the protein coat since the deoxyribonucleic acid (DNA) extracted from the inactivated phage retains its biological activity. Inactivation of the phage in air containing ozonized cyclohexene is due both to protein and DNA damage. Sucrose gradient analysis shows that aerosolized inactivated phiX174 releases unbroken DNA. In contrast, the DNA from phage phiX174 inactivated by ozonized cyclohexene is broken. The inactivation of aerosolized phage phiX174-DNA was studied in the same atmospheres using 32P-labelled DNA. phiX174-DNA aerosolized in clear air or air containing cyclohexene at 75% r.h. is inactivated by a factor of 2 in 30 min. The inactivated DNA is broken. Ozone as well as ozonized cyclohexene inactivates KNA very fast causing breaks in the molecule. This is in contrast with the intact bacteriophage in which ozone does not produce breaks in the DNA. PMID:265342

Synthesis of a Silyl Cobalt Hydride and Its Catalytic Performance in Kumada Coupling Reactions.

PubMed

Xu, Shilu; Zhang, Peng; Li, Xiaoyan; Xue, Benjing; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2017-06-01

Four silyl [P,Si]-chelate cobalt complexes (2-5) have been synthesized through the chelate-assisted Si-H activation of bidentate preligand ortho-HSi(Me) 2 (PPh 2 )C 6 H 4 (1) with CoMe(PMe 3 ) 4 and CoCl(PMe 3 ) 3 . The silyl Co I complex, Co(PMe 3 ) 3 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (2), was synthesized by Si-H activation of 1 with CoMe(PMe 3 ) 4 or by combining complex 5 with MeLi and PMe 3 . Complex 2 was treated with CH 3 I or EtBr, generating the silyl Co II products CoI(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (3) and CoBr(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (4). The silyl Co III hydride, CoHCl(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (5), was obtained by the reaction of complex 1 with CoCl(PMe 3 ) 3 . The catalytic performance of complex 5 was explored for Kumada coupling reactions, showing good to excellent catalytic efficiency with 2 mol % catalyst loading for the reactions of aryl chlorides or aryl bromides with Grignard reagents. It is noteworthy that the synthesis of 5 as a chelate complex is easier than that of previously reported [PSiP]-pincer cobalt hydride. With similar catalytic efficiency for Kumada reactions, the catalyst loading (2 %) of 5 was lower than that (5 %) of [PSiP]-pincer cobalt hydride. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Insights in Tropospheric Ozone and its Variability

NASA Technical Reports Server (NTRS)

Oman, Luke D.; Douglass, Anne R.; Ziemke, Jerry R.; Rodriquez, Jose M.

2011-01-01

We have produced time-slice simulations using the Goddard Earth Observing System Version 5 (GEOS-5) coupled to a comprehensive stratospheric and tropospheric chemical mechanism. These simulations are forced with observed sea surface temperatures over the past 25 years and use constant specified surface emissions, thereby providing a measure of the dynamically controlled ozone response. We examine the model performance in simulating tropospheric ozone and its variability. Here we show targeted comparisons results from our simulations with a multi-decadal tropical tropospheric column ozone dataset obtained from satellite observations of total column ozone. We use SHADOZ ozonesondes to gain insight into the observed vertical response and compare with the simulated vertical structure. This work includes but is not limited to ENSO related variability.

Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine

PubMed Central

Cordier, Christopher J.; Lundgren, Rylan J.; Fu, Gregory C.

2013-01-01

Although enantioconvergent alkyl-alkyl couplings of racemic electrophiles have been developed, there have been no reports of the corresponding reactions of racemic nucleophiles. Herein, we describe Negishi cross-couplings of racemic α-zincated N-Boc-pyrrolidine with unactivated secondary halides, thus providing a one-pot, catalytic asymmetric method for the synthesis of a range of 2-alkylpyrrolidines (an important family of target molecules) from N-Boc-pyrrolidine, a commercially available precursor. Preliminary mechanistic studies indicate that two of the most straightforward mechanisms for enantioconvergence (a dynamic kinetic resolution of the organometallic coupling partner and a simple β-hydride elimination/β-migratory insertion pathway) are unlikely to be operative. PMID:23869442

Prevention of PVDF ultrafiltration membrane fouling by coating MnO2 nanoparticles with ozonation

PubMed Central

Yu, Wenzheng; Brown, Matthew; Graham, Nigel. J. D.

2016-01-01

Pre-treatment is normally required to reduce or control the fouling of ultrafiltration (UF) membranes in drinking water treatment process. Current pre-treatment methods, such as coagulation, are only partially effective to prevent long-term fouling. Since biological activities are a major contributor to accumulated fouling, the application of an oxidation/disinfection step can be an effective complement to coagulation. In this study, a novel pre-treatment method has been evaluated at laboratory scale consisting of the addition of low dose ozone into the UF membrane tank after coagulation and the use of a hollow-fibre membrane coated with/without MnO2 nanoparticles over a test period of 70 days. The results showed that there was minimal fouling of the MnO2 coated membrane (0.5 kPa for 70 days), while the uncoated membrane experienced both reversible and irreversible fouling. The difference was attributed to the greatly reduced presence of bacteria and organic matter because of the catalytic decomposition of ozone to hydroxyl radicals and increase of the hydrophilicity of the membrane surface. In particular, the MnO2 coated membrane had a much thinner cake layer, with significantly less polysaccharides and proteins, and much less accumulated organic matter within the membrane pores. PMID:27436142

Prevention of PVDF ultrafiltration membrane fouling by coating MnO2 nanoparticles with ozonation

NASA Astrophysics Data System (ADS)

Yu, Wenzheng; Brown, Matthew; Graham, Nigel. J. D.

2016-07-01

Pre-treatment is normally required to reduce or control the fouling of ultrafiltration (UF) membranes in drinking water treatment process. Current pre-treatment methods, such as coagulation, are only partially effective to prevent long-term fouling. Since biological activities are a major contributor to accumulated fouling, the application of an oxidation/disinfection step can be an effective complement to coagulation. In this study, a novel pre-treatment method has been evaluated at laboratory scale consisting of the addition of low dose ozone into the UF membrane tank after coagulation and the use of a hollow-fibre membrane coated with/without MnO2 nanoparticles over a test period of 70 days. The results showed that there was minimal fouling of the MnO2 coated membrane (0.5 kPa for 70 days), while the uncoated membrane experienced both reversible and irreversible fouling. The difference was attributed to the greatly reduced presence of bacteria and organic matter because of the catalytic decomposition of ozone to hydroxyl radicals and increase of the hydrophilicity of the membrane surface. In particular, the MnO2 coated membrane had a much thinner cake layer, with significantly less polysaccharides and proteins, and much less accumulated organic matter within the membrane pores.

Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.

PubMed

Gianino, Joseph B; Campos, Catherine A; Lepore, Antonio J; Pinkerton, David M; Ashfeld, Brandon L

2014-12-19

A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.

Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

PubMed

Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

2014-11-01

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

PubMed

Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

2018-02-20

The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

Interactive coupling of electronic and optical man-made devices to biological systems

NASA Astrophysics Data System (ADS)

Ozden, Ilker

Fireflies blink synchronously, lasers are "mode-locked" for amplification, cardiac pacemaker cells maintain a steady heartbeat, and crickets chirps get in step. These are examples of coupled oscillators. Coupled non-linear limit-cycle oscillator models are used extensively to provide information about the collective behavior of many physical and biological systems. Depending on the system parameters, namely, the coupling coefficient and the time delay in the coupling, these coupled limit-cycle oscillator exhibit several interesting phenomena; they either synchronize to a common frequency, or oscillate completely independent of each other, or drag each other to a standstill i.e., show "amplitude death". Many neuronal systems exhibit synchronized limit-cycle oscillations in network of electrically coupled cells. The inferior olivary (IO) neuron is an example of such a system. The inferior olive has been widely studied by neuroscientists as it exhibits spontaneous oscillations in its membrane potential, typically in the range of 1--10 Hz. Located in the medulla, the inferior olive is believed to form the neural basis for precise timing and learning in motor circuits by making strong synaptic connections onto Purkinjee cells in the cerebellum. In this thesis work, we report on work, which focuses on the implementation and study of coupling of a biological circuit, which is the inferior olivary system, with a man-made electronic oscillator, the so-called Chua's circuit. We were able to study the interaction between the two oscillators over a wide range coupling conditions. With increasing coupling strength, the oscillators become phase-locked, or synchronized, but with a phase relationship which is either in- or out-of-phase depending on the detailed adjustment in the coupling. Finally, the coupled system reaches the conditions for amplitude death, a rather fundamental result given that the interaction has taken place between purely biological and man-made circuit

Present-day distribution and trends of global tropospheric ozone from satellite observations: Results from the Tropospheric Ozone Assessment Report (TOAR)

NASA Astrophysics Data System (ADS)

Gaudel, A.; Cooper, O. R.; Barret, B.; Boynard, A.; Clerbaux, C.; Pierre-Francois, C.; Huang, G.; Hurtmans, D.; Kerridge, B. J.; Latter, B.; Le Flochmoen, E.; Liu, X.; Neu, J. L.; Siddans, R.; Wespes, C.; Worden, H. M.; Ziemke, J. R.

2017-12-01

Tropospheric ozone is a greenhouse gas and pollutant detrimental to human health and crop and ecosystem productivity. Since 1990 a large portion of the anthropogenic emissions that react in the atmosphere to produce ozone have shifted from North America and Europe to Asia. This rapid shift, coupled with limited ozone monitoring in developing nations, has left scientists unable to answer the most basic questions: Is ozone continuing to decline in nations with strong emission controls? To what extent is ozone increasing in the developing world? IGAC's Tropospheric Ozone Assessment Report (TOAR) has been designed to answer these questions and this presentation will show the results from the TOAR-Climate initiative, focusing on the present-day distribution and trends of global tropospheric ozone from satellite observations. Five satellite products based on OMI (2 products using two different retrieval methods) and IASI (also 2 products using two different retrieval methods) and the OMI/MLS combined product were intercompared. An important result is the close agreement among the five products regarding the quantification of the total mass of all tropospheric ozone, the so called tropospheric ozone burden (TOB). The mean estimate for TOB between 60° N and 60° S is 296 Tg, with all products agreeing within ± 4%. However, on a regional basis the five satellite products have notable differences and there is no agreement in terms of ozone trends over the past decade. Continuing work is exploring the causes of these differences.

An Extended View of Mars Ozone

NASA Technical Reports Server (NTRS)

Fast, Kelly

2011-01-01

We present an ongoing effort to characterize chemistry in Mars' atmosphere in multiple seasons on timescales longer than flight missions through coordinated efforts by GSFC's HIPWAC spectrometer and Mars Express SPICAM, archival measurements, and tests/application of photochemical models. The trace species ozone (O3) is an effective probe of atmospheric chemistry because it is destroyed by chemically active odd hydrogen species (HO(sub x)) that result from water vapor photolysis. Observed ozone abundance on Mars is a critical test for three-dimensional photochemistry coupled general circulation models (GCM) that make specific predictions for the spatial, diurnal, and seasonal behavior of ozone and related chemistry and climatological conditions. Coordinated measurements by HIPWAC and SPICAM quantitatively linked mission data to the 23-year GSFC ozone data record and also revealed unanticipated inter-decadal variability of same-season ozone abundances, a possible indicator of changing cloud activity (heterogeneous sink for HO(sub x)). A detailed study of long-term conditions is critical to characterizing the predictability of Mars' seasonal chemical behavior, particularly in light of the implications of and the lack of explanation for reported methane behavior.

Ground-Level Ozone Following Astrophysical Ionizing Radiation Events: An Additional Biological Hazard?

PubMed

Thomas, Brian C; Goracke, Byron D

2016-01-01

Astrophysical ionizing radiation events such as supernovae, gamma-ray bursts, and solar proton events have been recognized as a potential threat to life on Earth, primarily through depletion of stratospheric ozone and subsequent increase in solar UV radiation at Earth's surface and in the upper levels of the ocean. Other work has also considered the potential impact of nitric acid rainout, concluding that no significant threat is likely. Not yet studied to date is the potential impact of ozone produced in the lower atmosphere following an ionizing radiation event. Ozone is a known irritant to organisms on land and in water and therefore may be a significant additional hazard. Using previously completed atmospheric chemistry modeling, we examined the amount of ozone produced in the lower atmosphere for the case of a gamma-ray burst and found that the values are too small to pose a significant additional threat to the biosphere. These results may be extended to other ionizing radiation events, including supernovae and extreme solar proton events.

Future changes in tropospheric ozone under Representative Concentration Pathways (RCPs)

NASA Astrophysics Data System (ADS)

Kawase, Hiroaki; Nagashima, Tatsuya; Sudo, Kengo; Nozawa, Toru

2011-03-01

We consider future changes in tropospheric ozone based on the Representative Concentration Pathways (RCPs), which are new emission and concentration scenarios for the 5th coupled model intercomparison project. In contrast to the SRES scenarios, all the RCP scenarios assume an emission reduction of NOx by the late 21st Century that has the potential to achieve tropospheric ozone reduction. However, increasing radiative forcing (RF) due to greenhouse gases and changes in CH4 concentration also contribute to differences in the tropospheric ozone distribution among RCP scenarios. In the RCP4.5 and RCP6.0, assuming the stabilization of RF, the increase in tropospheric ozone due to enhanced residual circulation is cancelled out by the ozone reduction due to ozone precursor reductions. In contrast, in the RCP8.5, assuming increasing RF even after 2100, further enhanced residual circulation and significant increase in CH4 cause a dramatic increase in tropospheric ozone.

Balloon-Borne Measurements of Stratospheric Radicals and their Precursors: Implications for the Production and Loss of Ozone

NASA Technical Reports Server (NTRS)

Osterman, G. B.; Salawitch, R. J.; Sen, B.; Toon, G. C.; Stachnik, R. A.; Pickett, H. M.; Margitan, J. J.; Blavier, J.-F.; Peterson, D. B.

1997-01-01

Measurements of hydrogen, nitrogen and chlorine radicals from a balloon flight on 25 September 1993 from Ft. Sumner, NM provide an opportunity to quantify photochemical production and loss of stratospheric ozone. Ozone loss rates determined using measured radical concentrations agree fairly well with loss rates calculated using a photochemical model. Catalytic cycles involving OH and HO2 are shown to dominate photochemical loss of ozone for altitudes between 44 and 50 km. Reactions involving NO and NO2 are the dominant sink for ozone between 25 and 38 km. The total ozone loss rate determined from the measurements balances calculated production rates for altitudes between 30 and 40 km. However, loss of ozone exceeds production by -35% between 42 and 50 km. The imbalance between production and loss of ozone above 42 km is larger than the uncertainty of any one of the critical kinetic parameters or species concentrations. No single adjustment to any of these parameters can simultaneously resolve the imbalance and satisfy constraints imposed by measured OH, HO2, NO2 and ClO. Our results are consistent with an additional mechanism for ozone production above 40 km other than photolysis of ground state O2.

Evaluation of the potential of ozone as a power plant biocide

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

Mattice, J.S.; Trabalka, J.R.; Adams, S.M.

1978-09-01

A review of the literature on the chemistry and biological effects of ozone was conducted to evaluate the potential of ozone to function as a power plant biocide. Evaluation of this potential is dependent upon determining the ability of ozone to maintain the integrity of both the condenser cooling system and the associated ecosystem. The well-known bactericidal capacity of ozone and the limited biofouling control studies conducted thus far suggest that ozone can control both slime and macroinvertebrate fouling at power plants. However, full-scale demonstrations of the minimum levels of ozone required and of solution of the practical aspects ofmore » application have not been performed.« less

A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

PubMed

Largeron, Martine; Fleury, Maurice-Bernard

2015-02-23

The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ozone Depletion from Nearby Supernovae

NASA Technical Reports Server (NTRS)

Gehrels, Neil; Laird, Claude M.; Jackman, Charles H.; Cannizzo, John K.; Mattson, Barbara J.; Chen, Wan; Bhartia, P. K. (Technical Monitor)

2002-01-01

Estimates made in the 1970's indicated that a supernova occurring within tens of parsecs of Earth could have significant effects on the ozone layer. Since that time improved tools for detailed modeling of atmospheric chemistry have been developed to calculate ozone depletion, and advances have been made also in theoretical modeling of supernovae and of the resultant gamma ray spectra. In addition, one now has better knowledge of the occurrence rate of supernovae in the galaxy, and of the spatial distribution of progenitors to core-collapse supernovae. We report here the results of two-dimensional atmospheric model calculations that take as input the spectral energy distribution of a supernova, adopting various distances from Earth and various latitude impact angles. In separate simulations we calculate the ozone depletion due to both gamma rays and cosmic rays. We find that for the combined ozone depletion from these effects roughly to double the 'biologically active' UV flux received at the surface of the Earth, the supernova must occur at approximately or less than 8 parsecs.

An extreme anomaly in stratospheric ozone over Europe in 1940-1942

NASA Astrophysics Data System (ADS)

Brönnimann, S.; Luterbacher, J.; Staehelin, J.; Svendby, T. M.

2004-04-01

Reevaluated historical total ozone data reveal extraordinarily high values over several European sites in 1940-1942, concurrent with extreme climatic anomalies at the Earth's surface. Using historical radiosonde data, reconstructed upper-level fields, and total ozone data from Arosa (Switzerland), Dombås, and Tromsø (Norway), this unusual case of stratosphere-troposphere coupling is analyzed. At Arosa, numerous strong total ozone peaks in all seasons were due to unusually frequent upper troughs over central Europe and related ozone redistribution in the lower stratosphere. At the Norwegian sites, high winter total ozone was most likely caused by major stratospheric warmings in Jan./Feb. 1940, Feb./Mar. 1941, and Feb. 1942. Results demonstrate that the dynamically driven interannual variability of total ozone can be much larger than that estimated based on the past 25-40 years.

Coupling of Transport and Chemical Processes in Catalytic Combustion

NASA Technical Reports Server (NTRS)

Bracco, F. V.; Bruno, C.; Royce, B. S. H.; Santavicca, D. A.; Sinha, N.; Stein, Y.

1983-01-01

Catalytic combustors have demonstrated the ability to operate efficiently over a much wider range of fuel air ratios than are imposed by the flammability limits of conventional combustors. Extensive commercial use however needs the following: (1) the design of a catalyst with low ignition temperature and high temperature stability, (2) reducing fatigue due to thermal stresses during transient operation, and (3) the development of mathematical models that can be used as design optimization tools to isolate promising operating ranges for the numerous operating parameters. The current program of research involves the development of a two dimensional transient catalytic combustion model and the development of a new catalyst with low temperature light-off and high temperature stablity characteristics.

Coupling between Catalytic Loop Motions and Enzyme Global Dynamics

PubMed Central

Kurkcuoglu, Zeynep; Bakan, Ahmet; Kocaman, Duygu; Bahar, Ivet; Doruker, Pemra

2012-01-01

Catalytic loop motions facilitate substrate recognition and binding in many enzymes. While these motions appear to be highly flexible, their functional significance suggests that structure-encoded preferences may play a role in selecting particular mechanisms of motions. We performed an extensive study on a set of enzymes to assess whether the collective/global dynamics, as predicted by elastic network models (ENMs), facilitates or even defines the local motions undergone by functional loops. Our dataset includes a total of 117 crystal structures for ten enzymes of different sizes and oligomerization states. Each enzyme contains a specific functional/catalytic loop (10–21 residues long) that closes over the active site during catalysis. Principal component analysis (PCA) of the available crystal structures (including apo and ligand-bound forms) for each enzyme revealed the dominant conformational changes taking place in these loops upon substrate binding. These experimentally observed loop reconfigurations are shown to be predominantly driven by energetically favored modes of motion intrinsically accessible to the enzyme in the absence of its substrate. The analysis suggests that robust global modes cooperatively defined by the overall enzyme architecture also entail local components that assist in suitable opening/closure of the catalytic loop over the active site. PMID:23028297

Climate Impacts on Tropospheric Ozone and Hydroxyl

NASA Technical Reports Server (NTRS)

Shindell, Drew T.; Bell, N.; Faluvegi, G.

2003-01-01

Climate change may influence tropospheric ozone and OH via several main pathways: (1) altering chemistry via temperature and humidity changes, (2) changing ozone and precursor sources via surface emissions, stratosphere-troposphere exchange, and light- ning, and (3) affecting trace gas sinks via the hydrological cycle and dry deposition. We report results from a set of coupled chemistry-climate model simulations designed to systematically study these effects. We compare the various effects with one another and with past and projected future changes in anthropogenic and natural emissions of ozone precursors. We find that white the overall impact of climate on ozone is probably small compared to emission changes, some significant seasonal and regional effects are apparent. The global effect on hydroxyl is quite large, however, similar in size to the effect of emission changes. Additionally, we show that many of the chemistry-climate links that are not yet adequately modeled are potentially important.

A Contribution Toward Understanding the Biospherical Significance of Antarctic Ozone Depletion

NASA Astrophysics Data System (ADS)

Lubin, Dan; Mitchell, B. Greg; Frederick, John E.; Alberts, Amy D.; Booth, C. R.; Lucas, Timothy; Neuschuler, David

1992-05-01

Measurements of biologically active UV radiation made by the National Science Foundation (NSF) scanning spectroradiometer (UV-monitor) at Palmer Station, Antarctica, during the Austral springs of 1988, 1989, and 1990 are presented and compared. Column ozone abundance above Palmer Station is computed from these measurements using a multiple wavelength algorithm. Two contrasting action spectra (biological weighting functions) are used to estimate the biologically relevant dose from the spectral measurements: a standard weighting function for damage to DNA, and a new action spectrum representing the potential for photosynthesis inhibition in Antarctic phytoplankton. The former weights only UV-B wavelengths (280-320 nm) and gives the most weight to wavelengths shorter than 300 nm, while the latter includes large contributions out to 355 nm. The latter is the result of recent Antarctic field work and is relevant in that phytoplankton constitute the base of the Antarctic food web. The modest ozone hole of 1988, in which the ozone abundance above Palmer Station never fell below 200 Dobson units (DU), brought about summerlike doses of DNA-effective UV radiation 2 months early, but UV doses which could inhibit photosynthesis in phytoplankton did not exceed a clear-sky "maximum normal" dose for that time of year. The severe ozone holes of 1989 and 1990, in which the ozone abundance regularly fell below 200 DU, brought about increases in UV surface irradiance weighted by either action spectrum. Ozone abundances and dose-weighted irradiances provided by the NSF UV-monitor are used to derive the radiation amplification factors (RAFs) for both DNA-effective irradiance and phytoplankton-effective irradiance. The RAF for DNA-effective irradiance is nonlinear in ozone abundance and is in excess of the popular "two for one" rule, while the RAF for phytoplankton-effective irradiance approximately follows a "one for one" rule.

The use of ozone, ozone plus UV radiation, and aerobic microorganisms in the purification of some agro-industrial wastewaters.

PubMed

Benitez, F Javier; Acero, Juan L; Gonzalez, Teresa; Garcia, Juan

2002-08-01

The oxidation of the pollutant organic matter present in wastewaters generated during different stages in the black table-olive industry was investigated by using ozone alone or combined with UV radiation; by using aerobic microorganisms; and finally, by aerobic degradation of the previously ozonated wastewaters. In the ozonation processes, the removal of substrate (COD) and aromatic compounds, the decreases in BOD5 and pH, and the ozone consumed in the reaction were evaluated. A kinetic study was conducted that led to the evaluation of the stoichiometric ratio for the chemical reaction, as well as the rate constants for the substrate reduction and ozone disappearance. In the single aerobic degradation treatment, the evolution of substrate and biomass was monitored during the process, and a kinetic study was performed by applying the Contois model to the experimental data, giving the specific biokinetic constant, the cell yield coefficient, and the rate constant for the microorganism death phase. Finally, a combined process was performed, consisting in the aerobic degradation of pre-ozonated wastewaters, and the effect of such chemical pretreatment on the substrate removal and kinetic parameters of the later biological stage is discussed.

Simultaneous waste activated sludge disintegration and biological hydrogen production using an ozone/ultrasound pretreatment.

PubMed

Yang, Shan-Shan; Guo, Wan-Qian; Cao, Guang-Li; Zheng, He-Shan; Ren, Nan-Qi

2012-11-01

This paper offers an effective pretreatment method that can simultaneously achieve excess sludge reduction and bio-hydrogen production from sludge self-fermentation. Batch tests demonstrated that the combinative use of ozone/ultrasound pretreatment had an advantage over the individual ozone and ultrasound pretreatments. The optimal condition (ozone dose of 0.158 g O(3)/g DS and ultrasound energy density of 1.423 W/mL) was recommended by response surface methodology. The maximum hydrogen yield was achieved at 9.28 mL H(2)/g DS under the optimal condition. According to the kinetic analysis, the highest hydrogen production rate (1.84 mL/h) was also obtained using combined pretreatment, which well fitted the predicted equation (the squared regression statistic was 0.9969). The disintegration degrees (DD) were limited to 19.57% and 46.10% in individual ozone and ultrasound pretreatments, while it reached up to 60.88% in combined pretreatment. The combined ozone/ultrasound pretreatment provides an ideal and environmental friendly solution to the problem of sludge disposal. Copyright © 2012 Elsevier Ltd. All rights reserved.

On the interannual oscillations in the northern temperate total ozone

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

Krzyscin, J.W.

1994-07-01

The interannual variations in total ozone are studied using revised Dobson total ozone records (1961-1990) from 17 stations located within the latitude band 30 deg N - 60 deg N. To obtain the quasi-biennial oscillation (QBO), El Nino-Southern Oscillation (ENSO), and 11-year solar cycle manifestation in the `northern temperate` total ozone data, various multiple regression models are constructed by the least squares fitting to the observed ozone. The statistical relationships between the selected indices of the atmospheric variabilities and total ozone are described in the linear and nonlinear regression models. Nonlinear relationships to the predictor variables are found. That is,more » the total ozone variations are statistically modeled by nonlinear terms accounting for the coupling between QBO and ENSO, QBO and solar activity, and ENSO and solar activity. It is suggested that large reduction of total ozone values over the `northern temperate` region occurs in cold season when a strong ENSO warm event meets the west phase of the QBO during the period of high solar activity.« less

Effect of urea deproteinization on catalytic hydrogenation of natural rubber latex

NASA Astrophysics Data System (ADS)

Cifriadi, A.; Chalid, M.; Puspitasari, S.

2017-07-01

Natural rubber is unsaturated biopolymer which has low resistance to heat, oxygen, and ozone. Chemical modification of natural rubber by catalytic hydrogenation can improve its oxidative property. In this study, the catalytic hydrogenation of natural rubber was investigated in latex phase after reduction of protein content with urea. Hydrogenation of deproteinized natural rubber latex was performed by using diimide which generated insitu from hydrazine hydrate/hydrogen peroxide and catalyst (boric acid, cupric sulfate and cupric acetate) at 70°C for 5 h. The hydrogenation system was stabilized with sodium dodecyl sulphate. The hydrogenation of deproteinized natural rubber (HDPNR) was confirmed by FTIR analysis. The result indicated that cupric sulphate was extremely active catalyst which was showed by the elimination of C=C transmittance bands at 1660 cm-1 on HDPNR spectra and highest degree of hydrogenation. Furthermore, urea deproteinization increased possibility of side reactions during catalytic hydrogenation as seen on the reduction of gel content compared to undeproteinized natural rubber.

Tropospheric jet response to Antarctic ozone depletion: An update with Chemistry-Climate Model Initiative (CCMI) models

NASA Astrophysics Data System (ADS)

Son, Seok-Woo; Han, Bo-Reum; Garfinkel, Chaim I.; Kim, Seo-Yeon; Park, Rokjin; Abraham, N. Luke; Akiyoshi, Hideharu; Archibald, Alexander T.; Butchart, N.; Chipperfield, Martyn P.; Dameris, Martin; Deushi, Makoto; Dhomse, Sandip S.; Hardiman, Steven C.; Jöckel, Patrick; Kinnison, Douglas; Michou, Martine; Morgenstern, Olaf; O’Connor, Fiona M.; Oman, Luke D.; Plummer, David A.; Pozzer, Andrea; Revell, Laura E.; Rozanov, Eugene; Stenke, Andrea; Stone, Kane; Tilmes, Simone; Yamashita, Yousuke; Zeng, Guang

2018-05-01

The Southern Hemisphere (SH) zonal-mean circulation change in response to Antarctic ozone depletion is re-visited by examining a set of the latest model simulations archived for the Chemistry-Climate Model Initiative (CCMI) project. All models reasonably well reproduce Antarctic ozone depletion in the late 20th century. The related SH-summer circulation changes, such as a poleward intensification of westerly jet and a poleward expansion of the Hadley cell, are also well captured. All experiments exhibit quantitatively the same multi-model mean trend, irrespective of whether the ocean is coupled or prescribed. Results are also quantitatively similar to those derived from the Coupled Model Intercomparison Project phase 5 (CMIP5) high-top model simulations in which the stratospheric ozone is mostly prescribed with monthly- and zonally-averaged values. These results suggest that the ozone-hole-induced SH-summer circulation changes are robust across the models irrespective of the specific chemistry-atmosphere-ocean coupling.

CATALYTIC OXIDATION OF AIR POLLUTANTS FROM PULP AND PAPER INDUSTRY USING OZONE

EPA Science Inventory

Major pollutants from pulp and paper mills include volatile organic compounds (VOCs) such as methanol and total reduced sulfur compounds (TRS) such as dimethyl sulfide. The conventional treatment technologies including incineration or catalytic thermal oxidation are energy intens...

Development and evaluation of an ozone deposition scheme for coupling to a terrestrial biosphere model

NASA Astrophysics Data System (ADS)

Franz, Martina; Simpson, David; Arneth, Almut; Zaehle, Sönke

2017-01-01

Ozone (O3) is a toxic air pollutant that can damage plant leaves and substantially affect the plant's gross primary production (GPP) and health. Realistic estimates of the effects of tropospheric anthropogenic O3 on GPP are thus potentially important to assess the strength of the terrestrial biosphere as a carbon sink. To better understand the impact of ozone damage on the terrestrial carbon cycle, we developed a module to estimate O3 uptake and damage of plants for a state-of-the-art global terrestrial biosphere model called OCN. Our approach accounts for ozone damage by calculating (a) O3 transport from 45 m height to leaf level, (b) O3 flux into the leaf, and (c) ozone damage of photosynthesis as a function of the accumulated O3 uptake over the lifetime of a leaf. A comparison of modelled canopy conductance, GPP, and latent heat to FLUXNET data across European forest and grassland sites shows a general good performance of OCN including ozone damage. This comparison provides a good baseline on top of which ozone damage can be evaluated. In comparison to literature values, we demonstrate that the new model version produces realistic O3 surface resistances, O3 deposition velocities, and stomatal to total O3 flux ratios. A sensitivity study reveals that key metrics of the air-to-leaf O3 transport and O3 deposition, in particular the stomatal O3 uptake, are reasonably robust against uncertainty in the underlying parameterisation of the deposition scheme. Nevertheless, correctly estimating canopy conductance plays a pivotal role in the estimate of cumulative O3 uptake. We further find that accounting for stomatal and non-stomatal uptake processes substantially affects simulated plant O3 uptake and accumulation, because aerodynamic resistance and non-stomatal O3 destruction reduce the predicted leaf-level O3 concentrations. Ozone impacts on GPP and transpiration in a Europe-wide simulation indicate that tropospheric O3 impacts the regional carbon and water cycling less

New Insights on "Next Day" Ozone Increases in the Northeastern U.S. using Continuous Vertical Profiles of Ozone

NASA Astrophysics Data System (ADS)

Sullivan, J. T.; McGee, T. J.; Rabenhorst, S. D.; Delgado, R.; Dreessen, J.; Sumnicht, G. K.; Twigg, L.

2016-12-01

A unique multi-day air quality event occurred throughout the Mid-Atlantic region from June 9-12, 2015. The June event was coupled to the advection of widespread smoke and debris from western Canada throughout the region. Observations indicated that the aged smoke impacted the Planetary Boundary Layer (PBL) and greatly enhanced ozone concentrations at the surface. Many ground sites in the region, particularly in Maryland, recorded 8-hr ozone concentrations that were in exceedance of the 75 ppb EPA National Ambient Air Quality Standard (NAAQS). After the high O3 episode occurred, a nocturnal low-level jet developed throughout the Mid-Atlantic region, which was spatially correlated with next day high O3 at several sites within the New England region. During this event, nearly continuous vertical profiles of ozone are presented at Beltsville, MD from the NASA Goddard Space Flight Center TROPospheric OZone DIfferential Absorption Lidar (GSFC TROPOZ DIAL), which has been developed and validated within the Tropospheric Ozone Lidar Network (TOLNet). Lidar observations reveal a well-mixed polluted PBL, nocturnal residual layer, and subsequent mixing down of the residual layer in the morning. Additional measurements of surface ozone, aerosol lidar profiles, wind profiles, and balloon borne profiles are also presented. Model output and trajectory analyses are also presented to illustrate the complex flow regimes that occurred during the daytime and nighttime to help redistribute the polluted air mass.

Ozone Depletion at Mid-Latitudes: Coupling of Volcanic Aerosols and Temperature Variability to Anthropogenic Chlorine

NASA Technical Reports Server (NTRS)

Solomon, S.; Portmann, R. W.; Garcia, R. R.; Randel, W.; Wu, F.; Nagatani, R.; Gleason, J.; Thomason, L.; Poole, L. R.; McCormick, M. P.

1998-01-01

Satellite observations of total ozone at 40-60 deg N are presented from a variety of instruments over the time period 1979-1997. These reveal record low values in 1992-3 (after Pinatubo) followed by partial but incomplete recovery. The largest post-Pinatubo reductions and longer-term trends occur in spring, providing a critical test for chemical theories of ozone depletion. The observations are shown to be consistent with current understanding of the chemistry of ozone depletion when changes in reactive chlorine and stratospheric aerosol abundances are considered along with estimates of wave-driven fluctuations in stratospheric temperatures derived from global temperature analyses. Temperature fluctuations are shown to make significant contributions to model calculated northern mid-latitude ozone depletion due to heterogeneous chlorine activation on liquid sulfate aerosols at temperatures near 200-210 K (depending upon water vapor pressure), particularly after major volcanic eruptions. Future mid-latitude ozone recovery will hence depend not only on chlorine recovery but also on temperature trends and/or variability, volcanic activity, and any trends in stratospheric sulfate aerosol.

Degradation of methylparaben in water by corona plasma coupled with ozonation.

PubMed

Dobrin, D; Magureanu, M; Bradu, C; Mandache, N B; Ionita, P; Parvulescu, V I

2014-11-01

The degradation of methylparaben (MeP) in water was investigated using a pulsed corona discharge generated in oxygen, above the liquid. A comparison was made between results obtained in semi-batch corona (SBC) configuration (stationary solution, continuous gas flow) and results obtained in a semi-batch corona with recirculation combined with ozonation (SBCR + O3), where the liquid is continuously circulated between a solution reservoir and the plasma reactor and the effluent gas containing ozone is bubbled through the solution in the reservoir. It was found that MeP was completely degraded after 10-15 min of treatment in both configurations. Oxidation by ozone alone, in the absence of plasma, was a slower process. The energy efficiency for MeP removal (Y MeP) and for mineralization (Y TOC) was significantly higher in the SBCR + O3 configuration (Y MeP = 7.1 g/kWh at 90 % MeP removal and Y TOC = 0.41 g/kWh at 50 % total organic carbon (TOC) removal) than in the SBC configuration (Y MeP = 0.6 g/kWh at 90 % MeP removal and Y TOC = 0.11 g/kWh at 50 % TOC removal).

The total ozone and UV solar radiation over Stara Zagora, Bulgaria

NASA Astrophysics Data System (ADS)

Mendeva, B. D.; Gogosheva, Ts. N.; Petkov, B. H.; Krastev, D. G.

The results from direct ground-based solar UV irradiance measurements and the total ozone content (TOC) over Stara Zagora (42° 25'N, 25° 37'E), Bulgaria are presented. During the period 1999-2003 the TOC data show seasonal variations, typical for the middle latitudes - maximum in the spring and minimum in the autumn. The comparison between TOC ground-based data and Global Ozone Monitoring Experiment (GOME) satellite-borne ones shows a seasonal dependence of the differences between them. A strong negative relationship between the total ozone and the 305 nm wavelength irradiance was found. The dependence between the two variables is significant ( r = -0.62 ± 0.18) at 98% confidence level. The direct sun UV doses for some specific biological effects (erythema and eyes) are obtained. The estimation of the radiation amplification factor RAF shows that the ozone reduction by 1% increases the erythemal dose by 2.3%. The eye-damaging doses are more influenced by the TOC changes and in this case RAF = -2.7%. The amount of these biological doses depended on the solar altitude over the horizon. This dependence was not so strong when the total ozone content in the atmosphere was lower.

From biological and social network metaphors to coupled bio-social wireless networks

PubMed Central

Barrett, Christopher L.; Eubank, Stephen; Anil Kumar, V.S.; Marathe, Madhav V.

2010-01-01

Biological and social analogies have been long applied to complex systems. Inspiration has been drawn from biological solutions to solve problems in engineering products and systems, ranging from Velcro to camouflage to robotics to adaptive and learning computing methods. In this paper, we present an overview of recent advances in understanding biological systems as networks and use this understanding to design and analyse wireless communication networks. We expand on two applications, namely cognitive sensing and control and wireless epidemiology. We discuss how our work in these two applications is motivated by biological metaphors. We believe that recent advances in computing and communications coupled with advances in health and social sciences raise the possibility of studying coupled bio-social communication networks. We argue that we can better utilise the advances in our understanding of one class of networks to better our understanding of the other. PMID:21643462

A Total Ozone Dependent Ozone Profile Climatology Based on Ozone-Sondes and Aura MLS Data

NASA Astrophysics Data System (ADS)

Labow, G. J.; McPeters, R. D.; Ziemke, J. R.

2014-12-01

A new total ozone-based ozone profile climatology has been created for use in satellite and/or ground based ozone retrievals. This climatology was formed by combining data from the Microwave Limb Sounder (MLS) with data from balloon sondes and binned by zone and total ozone. Because profile shape varies with total column ozone, this climatology better captures the ozone variations than the previously used seasonal climatologies, especially near the tropopause. This is significantly different than ozone climatologies used in the past as there is no time component. The MLS instrument on Aura has excellent latitude coverage and measures ozone profiles daily from the upper troposphere to the lower mesosphere at ~3.5 km resolution. Almost a million individual MLS ozone measurements are merged with data from over 55,000 ozonesondes which are then binned as a function of total ozone. The climatology consists of average ozone profiles as a function of total ozone for six 30 degree latitude bands covering altitudes from 0-75 km (in Z* pressure altitude coordinates). This new climatology better represents the profile shape as a function of total ozone than previous climatologies and shows some remarkable and somewhat unexpected correlations between total ozone and ozone in the lower altitudes, particularly in the lower and middle troposphere. These data can also be used to infer biases and errors in either the MLS retrievals or ozone sondes.

Impact of iodine chemistry on coastal ozone levels at the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Tuite, K.; Stutz, J.; Brockway, N.; Colosimo, S. F.; Tsai, J. Y.; Grossmann, K.; Alvarez, S. L.; Flynn, J. H., III; Erickson, M.; Caicedo, V.; Griffin, R. J.; Wallace, H. W., IV; Schulze, B.; Sheesley, R. J.; Usenko, S.; Yarwood, G.; Nopmongcol, U.

2016-12-01

Reactive iodine (Ix = I + IO) is known to destroy ozone through catalytic cycles in the marine boundary layer (MBL) and can thus have a significant impact on tropospheric ozone in coastal regions. As air quality standards for ozone become stricter, accurate background levels are increasingly important for the development of ozone reduction strategies. The Texas Gulf coast is an example for the significance of MBL background ozone, as onshore flows from the Gulf of Mexico contribute to the ozone levels in Houston and other coastal areas. The Gulf coast often experiences ozone mixing ratios below 20 ppb during summer onshore flow conditions, which are currently overestimated by regional and global air quality models. Modeling with the Comprehensive Air quality Model with extensions (CAMx) and GEOS-Chem including halogen chemistry identified iodine emissions from the Gulf of Mexico as a possible explanation. However, ambient measurements of Ix species for the Gulf of Mexico are needed to test this hypothesis and, if confirmed, refine models. We measured IO, O3, and other trace gases at the Gulf coast near Galveston, TX, using UCLA's long path DOAS instrument and a suite of in-situ instruments. During the study period from May 15 through July 12, 2016, several multi-day events with MBL ozone levels below 20 ppb were encountered. Here we present the observational data with a focus on time periods with onshore flow from the Gulf. A chemical steady state analysis will be used to assess whether the observed Ix mixing ratios can explain these low ozone mixing ratios. Our results will be compared to the CAMx and GEOS-Chem model simulations.

Catalytic devices

DOEpatents

Liu, Ming; Zhang, Xiang

2018-01-23

This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

Diagnosing ozone recovery using the O3-N2O relationship

NASA Astrophysics Data System (ADS)

Butler, A. H.; Gao, R. S.; Maycock, A.; Portmann, R. W.; Thornberry, T. D.; Rosenlof, K. H.; Fahey, D. W.

2016-12-01

The ubiquitous compact correlation between collocated values of stratospheric ozone (O3) and the tracer nitrous oxide (N2O) results from the stratospheric photochemical processes that produce ozone and destroy N2O combined with common transport and mixing processes. Changes in the correlation slope under certain circumstances reflect changes in the production and loss balance of ozone. This approach has been used extensively to diagnose and quantify ozone loss in polar spring. Using a coupled atmosphere-ocean model with interactive chemistry (CESM/WACCM), we show that this relationship can be used to diagnose ozone recovery in the lower extratropical stratosphere. We then consider in situ measurements of O3 and N2O from ATTREX, GloPac, and HIPPO as well as satellite measurements from ACE and Aura MLS to consider whether ozone recovery can be detected in observations during the period 2004-2016.

Antarctic ozone - Meteoric control of HNO3

NASA Technical Reports Server (NTRS)

Prather, Michael J.; Rodriguez, Jose M.

1988-01-01

Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

High School and College Student Perceptions of the Ozone Depletion Problem.

ERIC Educational Resources Information Center

Groves, Fred; Pugh, Ava

This paper examines the knowledge of high school biology students (n=107), undergraduate elementary education majors (n=42), and graduate students in an advanced elementary science methods course (n=22) about ozone depletion. The questionnaire used contained 30 items pertaining to ozone depletion which were divided into three subscales: (1)…

Application of ozone in the treatment of periodontal disease

PubMed Central

Srikanth, Adusumilli; Sathish, Manthena; Sri Harsha, Anumolu Venkatanaga

2013-01-01

Gingivitis and periodontitis are most common inflammatory diseases of supporting tissues of teeth. Role of microbial etiology and host response in progression of gingival and periodontal diseases has been well established. Because of the beneficial biological effects of ozone, due to its antimicrobial and immunostimulating effect, it is well indicated in the treatment of gingival and periodontal diseases. The objective of this article is to provide a general review about clinical applications of ozone in treatment of periodontal diseases and to summarize the available in vitro and in vivo studies in Periodontics in which ozone has been used. PMID:23946585

On the Size of the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Nash, Eric R.; Kawa, S. Randolph

2002-01-01

The Antarctic ozone hole is a region of extremely large ozone depletion that is roughly centered over the South Pole. Since 1979, the area coverage of the ozone hole has grown from near zero size to over 24 Million sq km. In the 8-year period from 1981 to 1989, the area expanded by 18 Million sq km. During the last 5 years, the hole has been observed to exceed 25 Million sq km over brief periods. In the spring of 2002, the size of the ozone hole barely reached 20 Million sq km for only a couple of days. We will review these size observations, the size trends, and the interannual variability of the size. The area is derived from the area enclosed by the 220 DU total ozone contour. We will discuss the rationale for the choice of 220 DU: 1) it is located near the steep gradient between southern mid-latitudes and the polar region, and 2) 220 DU is a value that is lower than the pre-1979 ozone observations over Antarctica during the spring period. The phenomenal growth of the ozone hole was directly caused by the increases of chlorine and bromine compounds in the stratosphere. In this talk, we will show the relationship of the ozone hole's size to the interannual variability of Antarctic spring temperatures. In addition, we will show the relationship of these same temperatures to planetary-scale wave forcings.

Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

PubMed

Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

2016-12-01

The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of ozonated sewage effluent on reproduction and behavioral endpoints in zebrafish (Danio rerio).

PubMed

Pohl, Johannes; Björlenius, Berndt; Brodin, Tomas; Carlsson, Gunnar; Fick, Jerker; Larsson, D G Joakim; Norrgren, Leif; Örn, Stefan

2018-04-25

Pharmaceutical residues and other micro-contaminants may enter aquatic environments through effluent from sewage treatment plants (STPs) and could cause adverse effects in wild fish. One strategy to alleviate this situation is to improve wastewater treatment by ozonation. To test the effectiveness of full-scale wastewater effluent ozonation at a Swedish municipal STP, the added removal efficiency was measured for 105 pharmaceuticals. In addition, gene expression, reproductive and behavioral endpoints were analyzed in zebrafish (Danio rerio) exposed on-site over 21 days to ozonated or non-ozonated effluents as well as to tap water. Ozone treatment (7 g O 3 /m 3 ) removed pharmaceuticals by an average efficiency of 77% in addition to the conventional treatment, leaving 11 screened pharmaceuticals above detection limits. Differences in biological responses of the exposure treatments were recorded in gene expression, reproduction and behavior. Hepatic vitellogenin gene expression was higher in male zebrafish exposed to the ozonated effluent compared to the non-ozonated effluent and tap water treatments. The reproductive success was higher in fish exposed to ozonated effluent compared to non-ozonated effluent and to tap water. The behavioral measurements showed that fish exposed to the ozonated STP effluent were less active in swimming the first minute after placed in a novel vessel. Ozonation is a capable method for removing pharmaceuticals in effluents. However, its implementation should be thoroughly evaluated for any potential biological impact. Future research is needed for uncovering the factors which produced the in vivo responses in fish. Copyright © 2018 Elsevier B.V. All rights reserved.

Simulation of tropospheric ozone with MOZART-2: An evaluation study over East Asia

NASA Astrophysics Data System (ADS)

Liu, Qianxia; Zhang, Meigen; Wang, Bin

2005-07-01

Climate changes induced by human activities have attracted a great amount of attention. With this, a coupling system of an atmospheric chemistry model and a climate model is greatly needed in China for better understanding the interaction between atmospheric chemical components and the climate. As the first step to realize this coupling goal, the three-dimensional global atmospheric chemistry transport model MOZART-2 (the global Model of Ozone and Related Chemical Tracers, version 2) coupled with CAM2 (the Community Atmosphere Model, version 2) is set up and the model results are compared against observations obtained in East Asia in order to evaluate the model performance. Comparison of simulated ozone mixing ratios with ground level observations at Minamitorishima and Ryori and with ozonesonde data at Naha and Tateno in Japan shows that the observed ozone concentrations can be reproduced reasonably well at Minamitorishima but they tend to be slightly overestimated in winter and autumn while underestimated a little in summer at Ryori. The model also captures the general features of surface CO seasonal variations quite well, while it underestimates CO levels at both Minamitorishima and Ryori. The underestimation is primarily associated with the emission inventory adopted in this study. Compared with the ozonesonde data, the simulated vertical gradient and magnitude of ozone can be reasonably well simulated with a little overestimation in winter, especially in the upper troposphere. The model also generally captures the seasonal, latitudinal and altitudinal variations in ozone concentration. Analysis indicates that the underestimation of tropopause height in February contributes to the overestimation of winter ozone in the upper and middle troposphere at Tateno.

The impact of climate change on ozone-related mortality in Sydney.

PubMed

Physick, William; Cope, Martin; Lee, Sunhee

2014-01-13

Coupled global, regional and chemical transport models are now being used with relative-risk functions to determine the impact of climate change on human health. Studies have been carried out for global and regional scales, and in our paper we examine the impact of climate change on ozone-related mortality at the local scale across an urban metropolis (Sydney, Australia). Using three coupled models, with a grid spacing of 3 km for the chemical transport model (CTM), and a mortality relative risk function of 1.0006 per 1 ppb increase in daily maximum 1-hour ozone concentration, we evaluated the change in ozone concentrations and mortality between decades 1996-2005 and 2051-2060. The global model was run with the A2 emissions scenario. As there is currently uncertainty regarding a threshold concentration below which ozone does not impact on mortality, we calculated mortality estimates for the three daily maximum 1-hr ozone concentration thresholds of 0, 25 and 40 ppb. The mortality increase for 2051-2060 ranges from 2.3% for a 0 ppb threshold to 27.3% for a 40 ppb threshold, although the numerical increases differ little. Our modeling approach is able to identify the variation in ozone-related mortality changes at a suburban scale, estimating that climate change could lead to an additional 55 to 65 deaths across Sydney in the decade 2051-2060. Interestingly, the largest increases do not correspond spatially to the largest ozone increases or the densest population centres. The distribution pattern of changes does not seem to vary with threshold value, while the magnitude only varies slightly.

The Impact of Climate Change on Ozone-Related Mortality in Sydney

PubMed Central

Physick, William; Cope, Martin; Lee, Sunhee

2014-01-01

Coupled global, regional and chemical transport models are now being used with relative-risk functions to determine the impact of climate change on human health. Studies have been carried out for global and regional scales, and in our paper we examine the impact of climate change on ozone-related mortality at the local scale across an urban metropolis (Sydney, Australia). Using three coupled models, with a grid spacing of 3 km for the chemical transport model (CTM), and a mortality relative risk function of 1.0006 per 1 ppb increase in daily maximum 1-hour ozone concentration, we evaluated the change in ozone concentrations and mortality between decades 1996–2005 and 2051–2060. The global model was run with the A2 emissions scenario. As there is currently uncertainty regarding a threshold concentration below which ozone does not impact on mortality, we calculated mortality estimates for the three daily maximum 1-hr ozone concentration thresholds of 0, 25 and 40 ppb. The mortality increase for 2051–2060 ranges from 2.3% for a 0 ppb threshold to 27.3% for a 40 ppb threshold, although the numerical increases differ little. Our modeling approach is able to identify the variation in ozone-related mortality changes at a suburban scale, estimating that climate change could lead to an additional 55 to 65 deaths across Sydney in the decade 2051–2060. Interestingly, the largest increases do not correspond spatially to the largest ozone increases or the densest population centres. The distribution pattern of changes does not seem to vary with threshold value, while the magnitude only varies slightly. PMID:24419047

Application of Ozone MBBR Process in Refinery Wastewater Treatment

NASA Astrophysics Data System (ADS)

Lin, Wang

2018-01-01

Moving Bed Biofilm Reactor (MBBR) is a kind of sewage treatment technology based on fluidized bed. At the same time, it can also be regarded as an efficient new reactor between active sludge method and the biological membrane method. The application of ozone MBBR process in refinery wastewater treatment is mainly studied. The key point is to design the ozone +MBBR combined process based on MBBR process. The ozone +MBBR process is used to analyze the treatment of concentrated water COD discharged from the refinery wastewater treatment plant. The experimental results show that the average removal rate of COD is 46.0%~67.3% in the treatment of reverse osmosis concentrated water by ozone MBBR process, and the effluent can meet the relevant standard requirements. Compared with the traditional process, the ozone MBBR process is more flexible. The investment of this process is mainly ozone generator, blower and so on. The prices of these items are relatively inexpensive, and these costs can be offset by the excess investment in traditional activated sludge processes. At the same time, ozone MBBR process has obvious advantages in water quality, stability and other aspects.

Chlorine oxide in the stratospheric ozone layer Ground-based detection and measurement

NASA Technical Reports Server (NTRS)

Parrish, A.; De Zafra, R. L.; Solomon, P. M.; Barrett, J. W.; Carlson, E. R.

1981-01-01

Stratospheric chlorine oxide, a significant intermediate product in the catalytic destruction of ozone by atomic chlorine, has been detected and measured by a ground-based 204 GHz, millimeter-wave receiver. Data taken at latitude 42 deg N on 17 days between January 10 and February 18, 1980 yield an average chlorine oxide column density of approximately 1.05 x 10 to the 14th/sq cm or approximately 2/3 that of the average of eight in situ balloon flight measurements (excluding the anomalously high data of July 14, 1977) made over the past four years at 32 deg N. Less chlorine oxide below 35 km and a larger vertical gradient than predicted by theoretical models of the stratospheric ozone layer are found.

The Effects of Acid Passivation, Tricresyl Phosphate Pre-Soak, and UV/Ozone Treatment on the Tribology of Perfluoropolyether-Lubricated 440C Stainless Steel Couples

NASA Technical Reports Server (NTRS)

Shogrin, Bradley A.; Jones, William R., Jr.; Herrera-Fierro, Pilar

1997-01-01

The boundary-lubrication performance of perfluoropolyether (PFPE) thin films in the presence of passivated 440 C stainless steel is presented. The study utilized a standard ball-on-disc tribometer. Stainless steel surfaces were passivated with one of four techniques: 1) submersion in a chromic acid bath for 30 minutes at 46 C, 2) submersion in a chromic acid bath for 60 minutes at 56 C, 3) submersion in a tricresyl phosphate (TCP) bath for 2 days at 107 C, or 4) UV/Ozone treated for 15 minutes. After passivation, each disc had a 400 A film of PFPE (hexafluoropropene oxide) applied to it reproducibly (+/- 20%) and uniformly (+/- 15%) using a film deposition device. The lifetimes of these films were quantified by measuring the number of sliding wear cycles required to induce an increase in the friction coefficient from an initial value characteristic of the lubricated wear couple to a final, or failure value, characteristic of an unlubricated, unpassivated wear couple. The lubricated lifetime of the 440 C couple was not altered as a result of the various passivation techniques. The resulting surface chemistry of each passivation technique was examined using X-ray Photoelectron Spectroscopy (XPS). It was found that chromic acid passivation altered the Cr to Fe ratio of the surface. TCP passivation resulted in a FePO4 layer on the surface, while UV/Ozone passivation only removed the carbonaceous contamination layer. None of the passivation techniques were found to dramatically increase the oxide film thickness.

Characterization of natural organic matter treated by iron oxide nanoparticle incorporated ceramic membrane-ozonation process.

PubMed

Park, Hosik; Kim, Yohan; An, Byungryul; Choi, Heechul

2012-11-15

In this study, changes in the physical and structural properties of natural organic matter (NOM) were observed during hybrid ceramic membrane processes that combined ozonation with ultrafiltration ceramic membrane (CM) or with a reactive ceramic membrane (RM), namely, an iron oxide nanoparticles (IONs) incorporated-CM. NOM from feed water and NOM from permeate treated with hybrid ceramic membrane processes were analyzed by employing several NOM characterization techniques. Specific ultraviolet absorbance (SUVA), high-performance size exclusion chromatography (HPSEC) and fractionation analyses showed that the hybrid ceramic membrane process effectively removed and transformed relatively high contents of aromatic, high molecular weight and hydrophobic NOM fractions. Fourier transform infrared spectroscopy (FTIR) and 3-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy revealed that this process caused a significant decrease of the aromaticity of humic-like structures and an increase in electron withdrawing groups. The highest removal efficiency (46%) of hydroxyl radical probe compound (i.e., para-Chlorobenzoic acid (pCBA)) in RM-ozonation process compared with that in CM without ozonation process (8%) revealed the hydroxyl radical formation by the surface-catalyzed reaction between ozone and IONs on the surface of RM. In addition, experimental results on flux decline showed that fouling of RM-ozonation process (15%) was reduced compared with that of CM without ozonation process (30%). These results indicated that the RM-ozonation process enhanced the destruction of NOM and reduced the fouling by generating hydroxyl radicals from the catalytic ozonation in the RM-ozonation process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Ozone generation by negative corona discharge: the effect of Joule heating

NASA Astrophysics Data System (ADS)

Yanallah, K.; Pontiga, F.; Fernández-Rueda, A.; Castellanos, A.; Belasri, A.

2008-10-01

Ozone generation in pure oxygen using a wire-to-cylinder corona discharge reactor is experimentally and numerically investigated. Ozone concentration is determined by means of direct UV spectroscopy and the effects of Joule heating and ozone decomposition on the electrodes are analysed for different discharge gaps. The numerical model combines the physical processes in the corona discharge with the chemistry of ozone formation and destruction. The chemical kinetics model and the electrical model are coupled through Poisson's equation, and the current-voltage (CV) characteristic measured in experiments is used as input data to the numerical simulation. The numerical model is able to predict the radial distributions of electrons, ions, atoms and molecules for each applied voltage of the CV characteristic. In particular, the evolution of ozone density inside the discharge cell has been investigated as a function of current intensity and applied voltage.

Observations of Ozone-aerosol Correlated Behaviour in the Lower Stratosphere During the EASOE Campaign

NASA Technical Reports Server (NTRS)

Digirolamo, P.; Cacciani, M.; Disarra, A.; Fiocco, G.; Fua, D.; Joergensen, T. S.; Knudsen, B.; Larsen, N.

1992-01-01

The question of possible interactions between ozone and stratospheric aerosol has been open for a long time. Measurements carried out after the Mt. Agung and El Chicon eruptions showed evidence of negative correlations between the presence of volcanic stratospheric aerosols and ozone concentration. Evidence for negative correlations in the polar winter has been also found. It is only after the discovery of the Antarctic ozone hole that catalytic effects related to low temperature heterogeneous chemistry have become the object of much investigation, now extended to the role of volcanic aerosol in the ozone reduction. These phenomena can be the object of various interpretations, not mutually exclusive, including the effect of transport, diffuse radiation as well as heterogeneous chemistry. The present paper provides preliminary results of simultaneous measurements of ozone and aerosol, carried out at Thule, Greenland, during the winter 1991-92. The European Stratospheric Ozone Experiment (EASOE) was aimed at monitoring the winter Arctic stratosphere in order to obtain a deeper insight of the ozone destruction processes taking place in the polar regions. A large amount of aerosol was injected into the lower stratosphere by the recent eruption of Volcano Pinatubo. A lidar system, already operational in Thule since November 1990, has provided detailed measurements of the stratospheric aerosol concentration during EASOE. In the same period, a large number of ozonesondes were launched. Although no PSC formation was detected over Thule, the simultaneous measurement of the stratospheric aerosol and ozone profiles give the possibility to study interactions occurring in the stratosphere between these two constituents.

Natural zeolite reactivity towards ozone: the role of compensating cations.

PubMed

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Wintertime ozone fluxes and profiles above a subalpine spruce-fir forest

Treesearch

Karl Zeller

2000-01-01

High rural concentrations of ozone (O3) are thought to be stratospheric in origin, advected from upwind urban sources, or photochemically generated locally by natural trace gas emissions. Ozone is known to be transported vertically downward from the above-canopy atmospheric surface layer and destroyed within stomata or on other biological and mineral surfaces. However...

Application of quantitative structure activity relationship (QSAR) models to predict ozone toxicity in the lung.

PubMed

Kafoury, Ramzi M; Huang, Ming-Ju

2005-08-01

The sequence of events leading to ozone-induced airway inflammation is not well known. To elucidate the molecular and cellular events underlying ozone toxicity in the lung, we hypothesized that lipid ozonation products (LOPs) generated by the reaction of ozone with unsaturated fatty acids in the epithelial lining fluid and cell membranes play a key role in mediating ozone-induced airway inflammation. To test our hypothesis, we ozonized 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) and generated LOPs. Confluent human bronchial epithelial cells were exposed to the derivatives of ozonized POPC-9-oxononanoyl, 9-hydroxy-9-hydroperoxynonanoyl, and 8-(5-octyl-1,2,4-trioxolan-3-yl-)octanoyl-at a concentration of 10 muM, and the activity of phospholipases A2 (PLA2), C (PLC), and D (PLD) was measured (1, 0.5, and 1 h, respectively). Quantitative structure-activity relationship (QSAR) models were utilized to predict the biological activity of LOPs in airway epithelial cells. The QSAR results showed a strong correlation between experimental and computed activity (r = 0.97, 0.98, 0.99, for PLA2, PLC, and PLD, respectively). The results indicate that QSAR models can be utilized to predict the biological activity of the various ozone-derived LOP species in the lung. Copyright 2005 Wiley Periodicals, Inc.

Liquid-phase study of ozone inactivation of Venezuelan equine encephalomyelitis virus.

PubMed

Akey, D H; Walton, T E

1985-10-01

Ozone, in a liquid-phase application, was evaluated as a residue-free viral inactivant that may be suitable for use in an arboviral research laboratory. Commonly used sterilizing agents may leave trace residues, be flammable or explosive, and require lengthy periods for gases or residues to dissipate after decontamination of equipment such as biological safety cabinets. Complete liquid-phase inactivation of Venezuelan equine encephalomyelitis virus was attained at 0.025 mg of ozone per liter within 45 min of exposure. The inactivation of 10(6.5) median cell culture infective doses (CCID50 of Venezuelan equine encephalomyelitis virus per milliliter represented a reduction of 99.99997% of the viral particles from the control levels of 10(7.25-7.5) CCID50/ml. A dose-response relationship was demonstrated. Analysis by polynomial regression of the logarithmic values for both ozone concentrations and percent reduction of viral titers had a highly significant r2 of 0.8 (F = 63.6; df = 1, 16). These results, together with those of Akey (J. Econ. Entomol. 75:387-392, 1982) on the use of ozone to kill a winged arboviral vector, indicate that ozone is a promising candidate as a sterilizing agent in some applications for biological safety cabinets and other equipment used in vector studies with arboviruses.

A numerical study of tropospheric ozone in the springtime in East Asia

NASA Astrophysics Data System (ADS)

Zhang, Meigen; Xu, Yongfu; Itsushi, Uno; Hajime, Akimoto

2004-04-01

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is applied to East Asia to study the transport and photochemical transformation of tropospheric ozone in March 1998. The calculated mixing ratios of ozone and carbon monoxide are compared with ground level observations at three remote sites in Japan and it is found that the model reproduces the observed features very well. Examination of several high episodes of ozone and carbon monoxide indicates that these elevated levels are found in association with continental outflow, demonstrating the critical role of the rapid transport of carbon monoxide and other ozone precursors from the continental boundary layer. In comparison with available ozonesonde data, it is found that the model-calculated ozone concentrations are generally in good agreement with the measurements, and the stratospheric contribution to surface ozone mixing ratios is quite limited.

A Markovian engine for a biological energy transducer: the catalytic wheel.

PubMed

Tsong, Tian Yow; Chang, Cheng-Hung

2007-04-01

The molecular machines in biological cells are made of proteins, DNAs and other classes of molecules. The structures of these molecules are characteristically "soft", highly flexible, and yet their interactions with other molecules or ions are specific and selective. This chapter discusses a prevalent form, the catalytic wheel, or the energy transducer of cells, examines its mechanism of action, and extracts from it a set of simple but general rules for understanding the energetics of the biomolecular devices. These rules should also benefit design of manmade nanometer scale machines such as rotary motors or track-guided linear transporters. We will focus on an electric work that, by matching system dynamics and then enhancing the conformational fluctuation of one or several driver proteins, converts stochastic input of energy into rotation or locomotion of a receptor protein. The spatial (or barrier) and temporal symmetry breakings required for selected driver/receptor combinations are examined. This electric ratchet consists of a core engine that follows the Markovian dynamic, alleviates difficulties encountered in rigid mechanical model, and tailors to the soft-matter characteristics of the biomolecules.

Leaf-level to Canopy Exchange of NOx and Ozone in a Forest at the University of Michigan Biological Station

NASA Astrophysics Data System (ADS)

Wang, W.; Ganzeveld, L.; Helmig, D.; Hueber, J.; Rossabi, S.; Vogel, C. S.

2017-12-01

During the month-long PROPHET-AMOS campaign in July, 2016 we investigated NOx and ozone dynamics at the University of Michigan AmeriFlux Tower (US-UMB tower) and the PROPHET Tower research sites at the University of Michigan Biological Station (UMBS), using a multi-pronged experimental approach. The two sites are within 100 m of each other, located in a mixed forest on the northern lower peninsula of Michigan, USA. In a previous study, it was found that invoking a leaf-level compensation point for NOx uptake and emission provided better agreement between observed and model-simulated in- and above-canopy NOx concentrations in this forest. To further examine the role of foliar exchange relative to other in-canopy sources and sinks of NOx, we conducted detailed vertical gradient measurements of NOx and ozone at ten heights from the forest floor to above the canopy, along with micrometeorological conditions at the AmeriFlux Tower. In parallel, to investigate the leaf-level exchanges of NOx and ozone, we carried out branch enclosure experiments near the PROPHET tower on the dominant tree species of this forest. We combine these observations with micrometeorological data from the AmeriFlux Tower to constrain simulations with the Multi-Layer Canopy Chemical Exchange Model (MLC-CHEM) for investigation of sources, sinks, and dynamics that determine NOx concentrations, vertical gradients, and fluxes in this forest. We will compare our results with previous studies and other observations during the PHOPHET-AMOS campaign.

Characterization of surface dielectric barrier discharge influenced by intermediate frequency for ozone production

NASA Astrophysics Data System (ADS)

Abdelaziz, Ayman A.; Ishijima, Tatsuo; Seto, Takafumi; Osawa, Naoki; Wedaa, Hassan; Otani, Yoshio

2016-06-01

The aim of this study is to investigate the effect of the intermediate frequency (1-10 kHz) of the sinusoidal driving voltage on the characteristics of a developed surface dielectric barrier discharge (SDBD)-based reactor having spikes on its discharge electrode. Moreover, its influence on the production of ozone and nitrogen oxide byproducts is evaluated. The results show that SDBD is operated in the filamentary mode at all the frequencies. Nevertheless, the pulses of the discharge current at high frequencies are much denser and have higher amplitudes than those at low frequencies. The analysis of the power consumed in the reactor shows that a small portion of the input power is dissipated in the dielectric material of SDBD source, whereas the major part of the power is consumed in the plasma discharge. The results of the ozone production show that higher frequencies have a slightly adverse effect on the ozone production at relatively high energy density values, where the ozone concentration is slightly decreased when the frequency is increased at the same energy density. The temperature of the discharge channels and gas is not a crucial factor for the decomposition of ozone in this reactor, while the results of the measurements of nitrogen oxides characteristics indicate that the formation of NO and NO2 has a significant adverse effect on the production efficiency of ozone due to their oxidation to another nitrogen oxides and their catalytic effect.

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.

On the Climate Impacts of Upper Tropospheric and Lower Stratospheric Ozone

NASA Astrophysics Data System (ADS)

Xia, Yan; Huang, Yi; Hu, Yongyun

2018-01-01

The global warming simulations of the general circulation models (GCMs) are generally performed with different ozone prescriptions. We find that the differences in ozone distribution, especially in the upper tropospheric and lower stratospheric (UTLS) region, account for important model discrepancies shown in the ozone-only historical experiment of the Coupled Model Intercomparison Project Phase 5 (CMIP5). These discrepancies include global high cloud fraction, stratospheric temperature, and stratospheric water vapor. Through a set of experiments conducted by an atmospheric GCM with contrasting UTLS ozone prescriptions, we verify that UTLS ozone not only directly radiatively heats the UTLS region and cools the upper parts of the stratosphere but also strongly influences the high clouds due to its impact on relative humidity and static stability in the UTLS region and the stratospheric water vapor due to its impact on the tropical tropopause temperature. These consequences strongly affect the global mean effective radiative forcing of ozone, as noted in previous studies. Our findings suggest that special attention should be paid to the UTLS ozone when evaluating the climate effects of ozone depletion in the 20th century and recovery in the 21st century. UTLS ozone difference may also be important for understanding the intermodel discrepancy in the climate projections of the CMIP6 GCMs in which either prescribed or interactive ozone is used.

SH2-catalytic domain linker heterogeneity influences allosteric coupling across the SFK family.

PubMed

Register, A C; Leonard, Stephen E; Maly, Dustin J

2014-11-11

Src-family kinases (SFKs) make up a family of nine homologous multidomain tyrosine kinases whose misregulation is responsible for human disease (cancer, diabetes, inflammation, etc.). Despite overall sequence homology and identical domain architecture, differences in SH3 and SH2 regulatory domain accessibility and ability to allosterically autoinhibit the ATP-binding site have been observed for the prototypical SFKs Src and Hck. Biochemical and structural studies indicate that the SH2-catalytic domain (SH2-CD) linker, the intramolecular binding epitope for SFK SH3 domains, is responsible for allosterically coupling SH3 domain engagement to autoinhibition of the ATP-binding site through the conformation of the αC helix. As a relatively unconserved region between SFK family members, SH2-CD linker sequence variability across the SFK family is likely a source of nonredundant cellular functions between individual SFKs via its effect on the availability of SH3 and SH2 domains for intermolecular interactions and post-translational modification. Using a combination of SFKs engineered with enhanced or weakened regulatory domain intramolecular interactions and conformation-selective inhibitors that report αC helix conformation, this study explores how SH2-CD sequence heterogeneity affects allosteric coupling across the SFK family by examining Lyn, Fyn1, and Fyn2. Analyses of Fyn1 and Fyn2, isoforms that are identical but for a 50-residue sequence spanning the SH2-CD linker, demonstrate that SH2-CD linker sequence differences can have profound effects on allosteric coupling between otherwise identical kinases. Most notably, a dampened allosteric connection between the SH3 domain and αC helix leads to greater autoinhibitory phosphorylation by Csk, illustrating the complex effects of SH2-CD linker sequence on cellular function.

Mechano-biological Coupling of Cellular Responses to Microgravity

NASA Astrophysics Data System (ADS)

Long, Mian; Wang, Yuren; Zheng, Huiqiong; Shang, Peng; Duan, Enkui; Lü, Dongyuan

2015-11-01

Cellular response to microgravity is a basic issue in space biological sciences as well as space physiology and medicine. It is crucial to elucidate the mechano-biological coupling mechanisms of various biological organisms, since, from the principle of adaptability, all species evolved on the earth must possess the structure and function that adapts their living environment. As a basic element of an organism, a cell usually undergoes mechanical and chemical remodeling to sense, transmit, transduce, and respond to the alteration of gravitational signals. In the past decades, new computational platforms and experimental methods/techniques/devices are developed to mimic the biological effects of microgravity environment from the viewpoint of biomechanical approaches. Mechanobiology of plant gravisensing in the responses of statolith movements along the gravity vector and the relevant signal transduction and molecular regulatory mechanisms are investigated at gene, transcription, and protein levels. Mechanotransduction of bone or immune cell responses and stem cell development and tissue histogenesis are elucidated under microgravity. In this review, several important issues are briefly discussed. Future issues on gravisensing and mechanotransducing mechanisms are also proposed for ground-based studies as well as space missions.

Potential For Stratospheric Ozone Depletion During Carboniferous

NASA Astrophysics Data System (ADS)

Bill, M.; Goldstein, A. H.

Methyl bromide (CH3Br) constitutes the largest source of bromine atoms to the strato- sphere whereas methyl chloride (CH3Cl) is the most abundant halocarbon in the tro- posphere. Both gases play an important role in stratospheric ozone depletion. For in- stance, Br coupled reactions are responsible for 30 to 50 % of total ozone loss in the polar vortex. Currently, the largest natural sources of CH3Br and CH3Cl appear to be biological production in the oceans, inorganic production during biomass burning and plant production in salt marsh ecosystems. Variations of paleofluxes of CH3Br and CH3Cl can be estimated by analyses of oceanic paleoproductivity, stratigraphic analyses of frequency and distribution of fossil charcoal indicating the occurrence of wildfires, and/or by paleoreconstruction indicating the extent of salt marshes. Dur- ing the lower Carboniferous time (Tournaisian-Visean), the southern margin of the Laurasian continent was characterized by charcoal deposits. Estimation on frequency of charcoal layers indicates that wildfires occur in a range of 3-35 years (Falcon-Lang 2000). This suggests that biomass burning could be an important source of CH3Br and CH3Cl during Tournaisian-Viesan time. During Tounaisian and until Merame- cian carbon and oxygen isotope records have short term oscillations (Bruckschen et al. 1999, Mii et al. 1999). Chesterian time (mid- Carboniferous) is marked by an in- crease in delta18O values ( ~ 2 permil) and an increase of glacial deposit frequency suggesting lower temperatures. The occurrence of glacial deposits over the paleopole suggests polar conditions and the associated special features of polar mete- orology such as strong circumpolar wind in the stratosphere (polar vortex) and polar stratospheric clouds. Thus, conditions leading to polar statospheric ozone depletion can be found. Simultaneously an increase in delta13C values is documented. We interpret the positive shift in delta13C as a result of higher bioproductivity

"On the Possibilities of Climate Control" in 1962: Harry Wexler on Geoengineering and Ozone Destruction

NASA Astrophysics Data System (ADS)

Fleming, J. R.

2007-12-01

In 1962, in the early days of GCMs and satellites, Harry Wexler, Chief of the Scientific Services Division of the U.S. Weather Bureau and one of the most influential meteorologists of the 20th century, turned his attention to techniques that could raise or lower the overall temperature of the planet or rearrange its thermal structure. He also investigated possible inadvertent and purposeful damage to the ozone layer involving catalytic reactions of chorine and bromine. This work pre-dated the Nobel Prize-winning work on ozone depletion of P. Crutzen, M. Molina, and S. Rowland by about a decade. Wexler revealed his concerns about geoengineering and ozone destruction in a series of lectures "On the Possibilities of Climate Control" presented to technical audiences in Boston, Hartford, and Los Angeles in 1962. Using newly available results from GCMs and satellite heat budget experiments, Wexler pointed out that strategic manipulations of the Earth's shortwave and longwave radiation budgets could result in rather large-scale effects on general circulation patterns in short or longer periods, even approaching that of climatic change. These techniques, included increasing world temperature by several degrees by detonating up to ten H-bombs in the Arctic Ocean; decreasing world temperature by launching powder into an equatorial orbit to shade the Earth and make it look somewhat like Saturn and its rings; warming the lower atmosphere and cooling the stratosphere by artificial injections of water vapor or other substances; and notably, destroying all stratospheric ozone above the Arctic circle or near the equator using a relatively small amount of a catalytic agent such as chlorine or bromine. Wexler was preparing a new lecture in the summer of 1962 on "The Climate of Earth and Its Modifications," and might, under normal circumstances, have prepared his ideas for publication, as he had done earlier. However, he was cut down in his prime by a sudden heart attack on August 11

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

DOE PAGES

Zugic, Branko; Wang, Lucun; Heine, Christian; ...

2016-12-19

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

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

Zugic, Branko; Wang, Lucun; Heine, Christian

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

The development of manganese oxide coated ceramic membranes for combined catalytic ozonation and ultrafiltration of drinking water

NASA Astrophysics Data System (ADS)

Corneal, Lindsay Marie

A novel method for the preparation of hydrated MnO2 by the ozonation of MnCl2 in water is described. The hydrated MnO 2 was used to coat titania water filtration membranes using a layer-by-layer technique. The coated membranes were then sintered in air at 500°C for 45 minutes. Upon sintering, the MnO2 is converted to alpha-Mn 2O3 (as characterized by x-ray and electron diffraction). Atomic force microscopy (AFM) imaging showed no significant change in the roughness or height of the surface features of coated membranes, while scanning electron microscopy (SEM) imaging showed an increase in grain size with increasing number of coating layers. Energy dispersive x-ray spectroscopy (EDS) mapping and line scans revealed manganese present throughout the membrane, indicating that manganese dispersed into the porous membrane during the coating process and diffused into the titania grains during sintering. Selected area diffraction (SAD) of the coated and sintered membrane was used to index the surface layer as alpha-Mn2O3. The surface layer was uneven, although there was a trend of increasing thickness with increasing coating layers. The coating acts as a catalyst for the oxidation of organic matter when coated membranes are used in a hybrid ozonation-membrane filtration system. A trend of decreasing total organic carbon (TOC) in the permeate water was observed with increasing number of coating layers. The catalytic activity also manifests itself as improved recovery of the water flux due to oxidation of foulants on the membrane surface. Ceramic nanoparticle coatings on ceramic water filtration membranes must undergo high temperature sintering. However, this means that the underlying membrane, which has been engineered for a given molecular weight cut-off (MWCO), also undergoes a high temperature heat treatment that serves to increase pore size that have resulted in increases in permeability of titania membranes. Coating the titania membrane with manganese oxide followed

TREATMENT OF LANDFILL LEACHATE BY COUPLING COAGULATION-FLOCCULATION OR OZONATION TO GRANULAR ACTIVATED CARBON ADSORPTION.

PubMed

Oloibiri, Violet; Ufomba, Innocent; Chys, Michael; Audenaert, Wim; Demeestere, Kristof; Van Hulle, Stijn W H

2015-01-01

A major concern for landfilling facilities is the treatment of their leachate. To optimize organic matter removal from this leachate, the combination of two or more techniques is preferred in order to meet stringent effluent standards. In our study, coagulation-flocculation and ozonation are compared as pre- treatment steps for stabilized landfill leachate prior to granular activated carbon (GAC) adsorption. The efficiency of the pre treatment techniques is evaluated using COD and UVA254 measurements. For coagulation- flocculation, different chemicals are compared and optimal dosages are determined. After this, iron (III) chloride is selected for subsequent adsorption studies due to its high percentage of COD and UVA254 removal and good sludge settle-ability. Our finding show that ozonation as a single treatment is effective in reducing COD in landfill leachate by 66% compared to coagulation flocculation (33%). Meanwhile, coagulation performs better in UVA254 reduction than ozonation. Subsequent GAC adsorption of ozonated effluent, coagulated effluent and untreated leachate resulted in 77%, 53% and 8% total COD removal respectively (after 6 bed volumes). The effect of the pre-treatment techniques on GAC adsorption properties is evaluated experimentally and mathematically using Thomas and Yoon-Nelson models. Mathematical modelling of the experimental GAC adsorption data shows that ozonation increases the adsorption capacity and break through time with a factor of 2.5 compared to coagulation-flocculation.

Historical Tropospheric and Stratospheric Ozone Radiative Forcing Using the CMIP6 Database

NASA Astrophysics Data System (ADS)

Checa-Garcia, Ramiro; Hegglin, Michaela I.; Kinnison, Douglas; Plummer, David A.; Shine, Keith P.

2018-04-01

We calculate ozone radiative forcing (RF) and stratospheric temperature adjustments for the period 1850-2014 using the newly available Coupled Model Intercomparison Project phase 6 (CMIP6) ozone data set. The CMIP6 total ozone RF (1850s to 2000s) is 0.28 ± 0.17 W m-2 (which is 80% higher than our CMIP5 estimation), and 0.30 ± 0.17 W m-2 out to the present day (2014). The total ozone RF grows rapidly until the 1970s, slows toward the 2000s, and shows a renewed growth thereafter. Since the 1990s the shortwave RF exceeds the longwave RF. Global stratospheric ozone RF is positive between 1930 and 1970 and then turns negative but remains positive in the Northern Hemisphere throughout. Derived stratospheric temperature changes show a localized cooling in the subtropical lower stratosphere due to tropospheric ozone increases and cooling in the upper stratosphere due to ozone depletion by more than 1 K already prior to the satellite era (1980) and by more than 2 K out to the present day (2014).

Direct Electron Transfer of Enzymes in a Biologically Assembled Conductive Nanomesh Enzyme Platform.

PubMed

Lee, Seung-Woo; Lee, Ki-Young; Song, Yong-Won; Choi, Won Kook; Chang, Joonyeon; Yi, Hyunjung

2016-02-24

Nondestructive assembly of a nanostructured enzyme platform is developed in combination of the specific biomolecular attraction and electrostatic coupling for highly efficient direct electron transfer (DET) of enzymes with unprecedented applicability and versatility. The biologically assembled conductive nanomesh enzyme platform enables DET-based flexible integrated biosensors and DET of eight different enzyme with various catalytic activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unequivocal detection of ozone recovery in the Antarctic Ozone Hole through significant increases in atmospheric layers with minimum ozone

NASA Astrophysics Data System (ADS)

de Laat, Jos; van Weele, Michiel; van der A, Ronald

2015-04-01

An important new landmark in present day ozone research is presented through MLS satellite observations of significant ozone increases during the ozone hole season that are attributed unequivocally to declining ozone depleting substances. For many decades the Antarctic ozone hole has been the prime example of both the detrimental effects of human activities on our environment as well as how to construct effective and successful environmental policies. Nowadays atmospheric concentrations of ozone depleting substances are on the decline and first signs of recovery of stratospheric ozone and ozone in the Antarctic ozone hole have been observed. The claimed detection of significant recovery, however, is still subject of debate. In this talk we will discuss first current uncertainties in the assessment of ozone recovery in the Antarctic ozone hole by using multi-variate regression methods, and, secondly present an alternative approach to identify ozone hole recovery unequivocally. Even though multi-variate regression methods help to reduce uncertainties in estimates of ozone recovery, great care has to be taken in their application due to the existence of uncertainties and degrees of freedom in the choice of independent variables. We show that taking all uncertainties into account in the regressions the formal recovery of ozone in the Antarctic ozone hole cannot be established yet, though is likely before the end of the decade (before 2020). Rather than focusing on time and area averages of total ozone columns or ozone profiles, we argue that the time evolution of the probability distribution of vertically resolved ozone in the Antarctic ozone hole contains a better fingerprint for the detection of ozone recovery in the Antarctic ozone hole. The advantages of this method over more tradition methods of trend analyses based on spatio-temporal average ozone are discussed. The 10-year record of MLS satellite measurements of ozone in the Antarctic ozone hole shows a

Effect of ozone on biopolymers in biofiltration and ultrafiltration processes.

PubMed

Siembida-Lösch, Barbara; Anderson, William B; Wang, Yulang Michael; Bonsteel, Jane; Huck, Peter M

2015-03-01

The focus of this full-scale study was to determine the effect of ozone on biopolymer concentrations in biofiltration and ultrafiltration (UF) processes treating surface water from Lake Ontario. Ozonation was out of service for maintenance for 9 months, hence, it was possible to investigate ozone's action on biologically active carbon contactors (BACCs) and UF, in terms of biopolymer removal. Given the importance of biopolymers for fouling, this fraction was quantified using a chromatographic technique. Ozone pre-treatment was observed to positively impact the active biomass in biofilters. However, since an increase of the active biomass did not result in higher biopolymer removal, active biomass concentration cannot be a surrogate for biofiltration performance. It was evident that increasing empty bed contact time (EBCT) from 4 to 19 min only had a positive effect on biopolymer removal through BACCs when ozone was out of service. However, as a mass balance experiment showed, ozone-free operation resulted in higher deposition of biopolymers on a UF membrane and slight deterioration in its performance. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ozone

MedlinePlus

Ozone is a gas. It can be good or bad, depending on where it is. "Good" ozone occurs naturally about 10 to 30 miles above ... the sun's ultraviolet rays. Part of the good ozone layer is gone. Man-made chemicals have destroyed ...

Removing PAHs from urban runoff water by combining ozonation and carbon nano-onions.

PubMed

Sakulthaew, Chainarong; Comfort, Steve D; Chokejaroenrat, Chanat; Li, Xu; Harris, Clifford E

2015-12-01

Ozone (O3) is a chemical oxidant capable of transforming polycyclic aromatic hydrocarbons (PAHs) in urban runoff within minutes but complete oxidation to CO2 can take days to weeks. We developed and tested a flow-through system that used ozone to quickly transform PAHs in a runoff stream and then removed the ozone-transformed PAHs via adsorption to carbon nano-onions (CNOs). To quantify the efficacy of this approach, (14)C-labeled phenanthrene and benzo(a)pyrene, as well as a mixture of 16 unlabeled PAHs were used as test compounds. These PAHs were pumped from a reservoir into a flow-through reactor that continuously ozonated the solution. Outflow from the reactor then went to a chamber that contained CNOs to adsorb the ozone-transformed PAHs and allowed clean water to pass. By adding a microbial consortium to the CNOs following adsorption, we observed that bacteria were able to degrade the adsorbed products and release more soluble, biodegradable products back into solution. Control treatments confirmed that parent PAH structures (i.e., non-ozonated) were not biologically degraded following CNO adsorption and that O3-transformed PAHs were not released from the CNOs in the absence of bacteria. These results support the combined use of ozone, carbon nano-onions with subsequent biological degradation as a means of removing PAHs from urban runoff or a commercial waste stream. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhanced ozone loss by active inorganic bromine chemistry in the tropical troposphere

NASA Astrophysics Data System (ADS)

Le Breton, Michael; Bannan, Thomas J.; Shallcross, Dudley E.; Khan, M. Anwar; Evans, Mathew J.; Lee, James; Lidster, Richard; Andrews, Stephen; Carpenter, Lucy J.; Schmidt, Johan; Jacob, Daniel; Harris, Neil R. P.; Bauguitte, Stephane; Gallagher, Martin; Bacak, Asan; Leather, Kimberley E.; Percival, Carl J.

2017-04-01

Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17-1.64 pptv BrO and 3.6-8 pptv total inorganic Br from these four species throughout the troposphere causes 10-20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br- and Cl-) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species.

Ozonation catalyzed by the raw bauxite for the degradation of 2,4,6-trichloroanisole in drinking water.

PubMed

Qi, Fei; Xu, Bingbing; Chen, Zhonglin; Ma, Jun; Sun, Dezhi; Zhang, Liqiu; Wu, Fengchang

2009-08-30

A kind of inexpensive and environmental friendly mineral, the raw bauxite has been used successfully as a catalyst combined with ozonation in the degradation of 2,4,6-trichloroanisole (TCA). The catalyst was characterized by using various analytical techniques. X-ray powder diffraction (XRD) characterization showed that the raw bauxite containing boehmite (gamma-AlOOH), kaolinite (Al(2)Si(2)O(5)(OH)(4)) and quartz (SiO(2)), and gamma-AlOOH was the major composition. The catalytic ozonation removal effectiveness of TCA was investigated under various physicochemical conditions. Both the adsorption and the single ozonation were not effective for the degradation of TCA, and the presence of the raw bauxite in ozonation enhanced the TCA removal effectiveness. Both the hydroxyl radicals (OH) scavenging experiment and R(ct) characterization confirmed that the generation of OH was accounted for the enhancement of the degradation of TCA. The generation of OH was inhibited faintly by the presence of both natural organic matters (NOMs) and alkalinity in the natural water during catalyzed ozonation with the raw bauxite. The increasing of both the bauxite dosage and the ozone dosage enhanced the removal effectiveness of TCA. The raw bauxite was an efficient green catalyst for TCA degradation in drinking water.

The usefulness of ozone treatment in spinal pain

PubMed Central

Bocci, Velio; Borrelli, Emma; Zanardi, Iacopo; Travagli, Valter

2015-01-01

Objective The aim of this review is to elucidate the biochemical, molecular, immunological, and pharmaceutical mechanisms of action of ozone dissolved in biological fluids. Studies performed during the last two decades allow the drawing of a comprehensive framework for understanding and recommending the integration of ozone therapy for spinal pain. Methods An in-depth screening of primary sources of information online – via SciFinder Scholar, Google Scholar, and Scopus databases as well as Embase, PubMed, and the Cochrane Database of Systemic Reviews – was performed. In this review, the most significant papers of the last 25 years are presented and their proposals critically evaluated, regardless of the bibliometric impact of the journals. Results The efficacy of standard treatments combined with the unique capacity of ozone therapy to reactivate the innate antioxidant system is the key to correcting the oxidative stress typical of chronic inflammatory diseases. Pain pathways and control systems of algesic signals after ozone administration are described. Conclusion This paper finds favors the full insertion of ozone therapy into pharmaceutical sciences, rather than as either an alternative or an esoteric approach. PMID:26028964

Liquid-phase study of ozone inactivation of Venezuelan equine encephalomyelitis virus.

PubMed Central

Akey, D H; Walton, T E

1985-01-01

Ozone, in a liquid-phase application, was evaluated as a residue-free viral inactivant that may be suitable for use in an arboviral research laboratory. Commonly used sterilizing agents may leave trace residues, be flammable or explosive, and require lengthy periods for gases or residues to dissipate after decontamination of equipment such as biological safety cabinets. Complete liquid-phase inactivation of Venezuelan equine encephalomyelitis virus was attained at 0.025 mg of ozone per liter within 45 min of exposure. The inactivation of 10(6.5) median cell culture infective doses (CCID50 of Venezuelan equine encephalomyelitis virus per milliliter represented a reduction of 99.99997% of the viral particles from the control levels of 10(7.25-7.5) CCID50/ml. A dose-response relationship was demonstrated. Analysis by polynomial regression of the logarithmic values for both ozone concentrations and percent reduction of viral titers had a highly significant r2 of 0.8 (F = 63.6; df = 1, 16). These results, together with those of Akey (J. Econ. Entomol. 75:387-392, 1982) on the use of ozone to kill a winged arboviral vector, indicate that ozone is a promising candidate as a sterilizing agent in some applications for biological safety cabinets and other equipment used in vector studies with arboviruses. PMID:4083884

16 CFR 260.11 - Ozone-safe and ozone-friendly claims.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 16 Commercial Practices 1 2013-01-01 2013-01-01 false Ozone-safe and ozone-friendly claims. 260.11... THE USE OF ENVIRONMENTAL MARKETING CLAIMS § 260.11 Ozone-safe and ozone-friendly claims. It is... friendly to, the ozone layer or the atmosphere. Example 1: A product is labeled “ozone-friendly.” The claim...

16 CFR 260.11 - Ozone-safe and ozone-friendly claims.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 16 Commercial Practices 1 2014-01-01 2014-01-01 false Ozone-safe and ozone-friendly claims. 260.11... THE USE OF ENVIRONMENTAL MARKETING CLAIMS § 260.11 Ozone-safe and ozone-friendly claims. It is... friendly to, the ozone layer or the atmosphere. Example 1: A product is labeled “ozone-friendly.” The claim...

Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor.

PubMed

Lucas, Marco S; Peres, José A; Lan, Bing Yan; Li Puma, Gianluca

2009-04-01

The degradation of organic substances present in winery wastewater was studied in a pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen demand (COD) was observed under the action of ozone at the natural pH of the wastewater (pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen peroxide (formed from natural organic matter in the wastewater) and ozone enhances the oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP), UV absorbance (254 nm), polyphenol content and ozone consumption was correlated with the oxidation of the organic species in the water. The ozonation of winery wastewater in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was determined that the ozonation reaction can develop both in and across different kinetic regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic change of the rate coefficient estimated by the model was correlated with changes in the water composition and oxidant species.

Antarctic Climate Variability: Covariance of Ozone and Sea Ice in Atmosphere - Ocean Coupled Model Simulations

NASA Astrophysics Data System (ADS)

Jrrar, Amna; Abraham, N. Luke; Pyle, John A.; Holland, David

2014-05-01

Changes in sea ice significantly modulate climate change because of its high reflective and insulating nature. While Arctic Sea Ice Extent (SIE) shows a negative trend. Antarctic SIE shows a weak but positive trend, estimated at 0.127 x 106 km2 per decade. The trend results from large regional cancellations, more ice in the Weddell and the Ross seas, and less ice in the Amundsen - Bellingshausen seas. A number of studies had demonstrated that stratospheric ozone depletion has had a major impact on the atmospheric circulation, causing a positive trend in the Southern Annular Mode (SAM), which has been linked to the observed positive trend in autumn sea ice in the Ross Sea. However, other modelling studies show that models forced with prescribed ozone hole simulate decreased sea ice in all regions comparative to a control run. A recent study has also shown that stratospheric ozone recovery will mitigate Antarctic sea ice loss. To verify this assumed relationship, it is important first to investigate the covariance between ozone's natural (dynamical) variability and Antarctic sea ice distribution in pre-industrial climate, to estimate the trend due to natural variability. We investigate the relationship between anomalous Antarctic ozone years and the subsequent changes in Antarctic sea ice distribution in a multidecadal control simulation using the AO-UMUKCA model. The model has a horizontal resolution of 3.75 X 2.5 degrees in longitude and latitude; and 60 hybrid height levels in the vertical, from the surface up to a height of 84 km. The ocean component is the NEMO ocean model on the ORCA2 tripolar grid, and the sea ice model is CICE. We evaluate the model's performance in terms of sea ice distribution, and we calculate sea ice extent trends for composites of anomalously low versus anomalously high SH polar ozone column. We apply EOF analysis to the seasonal anomalies of sea ice concentration, MSLP, and Z 500, and identify the leading climate modes controlling the

Measurements of upward turbulent ozone fluxes above a subalpine spruce-fir forest

Treesearch

Karl Zeller; Ted Hehn

1996-01-01

High rural concentrations of ozone (O3) are thought to be either stratospheric in origin, advected from upwind urban sources, or photochemically generated locally as a result of natural trace gas emissions. Ozone is known to be transported vertically downward from the above-canopy atmospheric surface layer and destroyed within stomata or on other biological and mineral...

Foreign and Domestic Contributions to Springtime Ozone Pollution over China

NASA Astrophysics Data System (ADS)

Ni, R.; Lin, J.; Yan, Y.; Lin, W.; Chen, H.

2017-12-01

Ozone is a critical air pollutant that damages human health and vegetation. Previous studies for the United States and Europe have shown large influences of foreign emissions on domestic ozone levels, whereas the relative contributions of foreign versus domestic emissions are much less clear for China. Here, we use a global-regional two-way coupled model system based on GEOS-Chem to quantify the contributions to springtime ozone over China from anthropogenic emissions in major source regions across the globe. Our results indicate considerable influences of foreign anthropogenic pollution on China's ozone pollution. Together, foreign anthropogenic emissions enhance springtime surface ozone over China by 3 12 ppb. Of all ozone over China produced by global anthropogenic emissions, foreign emissions contribute 40% near the surface, and the contribution increases with altitude until a value of 80% in the upper troposphere. Impact from Japan and Korea is 1 2 ppb over east coastal regions, and negligible in inland. Anthropogenic emissions of South and South-East Asia increase ozone over Tibet and the Yunnan-Guizhou Plateau by up to 5 ppb, and their contribution increases with height due to strong vertical transport. Pollution from North America and Europe mainly accompanies strong westerly winds and frequent cyclonic activities that are favorable to long-range transport. European anthropogenic pollution enhances surface ozone by 1 3 ppb over West and North China. Despite a much longer transport distance, the contribution from North America is greater than European contribution due to the nearly doubled amount of anthropogenic NMVOC emissions. The high percentage contribution of foreign anthropogenic emissions to China's ozone pollution can be partly explained by excessive domestic NOx emissions that suppress ozone production efficiency and even destroy ozone. Our study is relevant to Chinese ozone pollution control and global environmental protection collaboration.

Bimetallic catalysis for C–C and C–X coupling reactions

PubMed Central

Pye, Dominic R.

2017-01-01

Bimetallic catalysis represents an alternative paradigm for coupling chemistry that complements the more traditional single-site catalysis approach. In this perspective, recent advances in bimetallic systems for catalytic C–C and C–X coupling reactions are reviewed. Behavior which complements that of established single-site catalysts is highlighted. Two major reaction classes are covered. First, generation of catalytic amounts of organometallic species of e.g. Cu, Au, or Ni capable of transmetallation to a Pd co-catalyst (or other traditional cross-coupling catalyst) has allowed important new C–C coupling technologies to emerge. Second, catalytic transformations involving binuclear bond-breaking and/or bond-forming steps, in some cases involving metal–metal bonds, represent a frontier area for C–C and C–X coupling processes.

Ozone pretreatment of process waste water generated in course of fluoroquinolone production.

PubMed

Daoud, Fares; Pelzer, David; Zuehlke, Sebastian; Spiteller, Michael; Kayser, Oliver

2017-10-01

During production of active pharmaceutical ingredients, process waste water is generated at several stages of manufacturing. Whenever possible, the resulting waste water will be processed by conventional waste water treatment plants. Currently, incineration of the process waste water is the method to eliminate compounds with high biological activity. Thus, ozone treatment followed by biological waste water treatment was tested as an alternative method. Two prominent representatives of the large group of fluoroquinolone antibiotics (ciprofloxacin and moxifloxacin) were investigated, focussing on waste water of the bulk production. Elimination of the target compounds and generation of their main transformation products were determined by liquid chromatography - high resolution mass spectrometry (LC-HRMS). The obtained results demonstrated, that the concentration of moxifloxacin and its metabolites can be effectively reduced (>99.7%) prior entering the receiving water. On the contrary, the concentration of ciprofloxacin and its metabolites remained too high for safe discharge, necessitating application of prolonged ozonation for its further degradation. The required ozonation time can be estimated based on the determined kinetics. To assure a low biological activity the ecotoxicity of the ozonated waste water was investigated using three trophic levels. By means of multiple-stage mass spectrometry (MS n ) experiments several new transformation products of the fluoroquinolones were identified. Thus, previously published proposed structures could be corrected or confirmed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of calcium-ozone treatment on chemical and biological properties of polyethylene terephthalate.

PubMed

Rashid, Ahmed Nafis; Tsuru, Kanji; Ishikawa, Kunio

2015-05-01

Ozone (O3 ) treatment of polyethylene terephthalate (PET) in distilled water was performed in the presence and absence of calcium (Ca(2+) ). PET was oxidized and thus carboxylic and hydroxyl functional groups were introduced on its surface after O3 treatment, regardless of the presence or absence of Ca(2+) . In the case of O3 treatment with Ca(2+) , PET surface was modified with Ca(2+) . Ca(2+) immobilization was confirmed by X-ray photoelectron spectrometric analysis. Hydrophilicity was investigated by measuring contact angles (CA). CA of PET decreased significantly after ozonation. Surface topography of PET before and after ozone treatment was observed by scanning electron microscopy, and showed no morphological changes. In vitro studies showed enhanced rat bone marrow cell responses on the O3 -treated PET surface. Ca(2+) -O3 oxidation at 37°C for 6 h is expected to be an effective method to fabricate PET with good biocompatibility. © 2014 Wiley Periodicals, Inc.

Fate of return activated sludge after ozonation: an optimization study for sludge disintegration.

PubMed

Demir, Ozlem; Filibeli, Ayse

2012-09-01

The effects of ozonation on sludge disintegration should be investigated before the application of ozone during biological treatment, in order to minimize excess sludge production. In this study, changes in sludge and supernatant after ozonation of return activated sludge were investigated for seven different ozone doses. The optimum ozone dose to avoid inhibition of ozonation and high ozone cost was determined in terms of disintegration degree as 0.05 g O3/gTS. Suspended solid and volatile suspended solid concentrations of sludge decreased by 77.8% and 71.6%, respectively, at the optimum ozone dose. Ozonation significantly decomposed sludge flocs. The release of cell contents was proved by the increase of supernatant total nitrogen (TN) and phosphorus (TP). While TN increased from 7 mg/L to 151 mg/L, TP increased from 8.8 to 33 mg/L at the optimum ozone dose. The dewaterability and filterability characteristics of the ozonated sludge were also examined. Capillary suction time increased with increasing ozone dosage, but specific resistance to filtration increased to a specific value and then decreased dramatically. The particle size distribution changed significantly as a result of floc disruption at an optimum dose of 0.05 gO3/gTS.

Ozone-induced stomatal sluggishness changes carbon and water balance of temperate deciduous forests.

PubMed

Hoshika, Yasutomo; Katata, Genki; Deushi, Makoto; Watanabe, Makoto; Koike, Takayoshi; Paoletti, Elena

2015-05-06

Tropospheric ozone concentrations have increased by 60-100% in the Northern Hemisphere since the 19(th) century. The phytotoxic nature of ozone can impair forest productivity. In addition, ozone affects stomatal functions, by both favoring stomatal closure and impairing stomatal control. Ozone-induced stomatal sluggishness, i.e., a delay in stomatal responses to fluctuating stimuli, has the potential to change the carbon and water balance of forests. This effect has to be included in models for ozone risk assessment. Here we examine the effects of ozone-induced stomatal sluggishness on carbon assimilation and transpiration of temperate deciduous forests in the Northern Hemisphere in 2006-2009 by combining a detailed multi-layer land surface model and a global atmospheric chemistry model. An analysis of results by ozone FACE (Free-Air Controlled Exposure) experiments suggested that ozone-induced stomatal sluggishness can be incorporated into modelling based on a simple parameter (gmin, minimum stomatal conductance) which is used in the coupled photosynthesis-stomatal model. Our simulation showed that ozone can decrease water use efficiency, i.e., the ratio of net CO2 assimilation to transpiration, of temperate deciduous forests up to 20% when ozone-induced stomatal sluggishness is considered, and up to only 5% when the stomatal sluggishness is neglected.

A novel organic solvent-based coupling method for the preparation of covalently immobilized proteins on gold.

PubMed Central

Parker, M. C.; Patel, N.; Davies, M. C.; Roberts, C. J.; Tendler, S. J.; Williams, P. M.

1996-01-01

A novel organic solvent-based coupling method has been developed for the covalent immobilization of biological material to gold surfaces. The method employs the polar organic solvent anhydrous 2,2,2-trifluoroethanol as the reaction medium and involves dissolution of the protein (catalase) in the solvent allowing protein coupling to proceed under basic conditions in a dry organic environment. The advantage of this method is that protein attachment is favored over hydrolysis of the coupling reagent. We have shown qualitatively and quantitatively that following attachment to the gold surface a significant proportion of the enzyme catalase remains catalytically active (at least 20-31%). PMID:8931151

On the structural context and identification of enzyme catalytic residues.

PubMed

Chien, Yu-Tung; Huang, Shao-Wei

2013-01-01

Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

Microphysical Modelling of the 1999-2000 Arctic Winter. 2; Chlorine Activation and Ozone Depletion

NASA Technical Reports Server (NTRS)

Drdla, K.; Schoeberl, M. R.; Gore, Warren J. (Technical Monitor)

2001-01-01

The effect of a range of assumptions about polar stratospheric clouds (PSCs) on ozone depletion has been assessed using at couple microphysical/photochemical model. The composition of the PSCs was varied (ternary solutions, nitric acid trihydrate, nitric acid dehydrate, or ice), as were parameters that affected the levels of denitrification and dehydration. Ozone depletion was affected by assumptions about PSC freezing because of the variability in resultant nitrification chlorine activation in all scenarios was similar despite the range of assumed PSC compositions. Vortex-average ozone loss exceeded 40% in the lower stratosphere for simulations without nitrification an additional ozone loss of 15-20% was possible in scenarios where vortex-average nitrification reached 60%. Ozone loss intensifies non-linearly with enhanced nitrification in air parcels with 90% nitrification 40% ozone loss in mid-April can be attributed to nitrification alone. However, these effects are sensitive to the stability of the vortex in springtime: nitrification only began to influence ozone depletion in mid-March.

Dynamic evaluation of two decades of WRF-CMAQ ozone ...

EPA Pesticide Factsheets

Dynamic evaluation of the fully coupled Weather Research and Forecasting (WRF)– Community Multi-scale Air Quality (CMAQ) model ozone simulations over the contiguous United States (CONUS) using two decades of simulations covering the period from 1990 to 2010 is conducted to assess how well the changes in observed ozone air quality are simulated by the model. The changes induced by variations in meteorology and/or emissions are also evaluated during the same timeframe using spectral decomposition of observed and modeled ozone time series with the aim of identifying the underlying forcing mechanisms that control ozone exceedances and making informed recommendations for the optimal use of regional-scale air quality models. The evaluation is focused on the warm season's (i.e., May–September) daily maximum 8-hr (DM8HR) ozone concentrations, the 4th highest (4th) and average of top 10 DM8HR ozone values (top10), as well as the spectrally-decomposed components of the DM8HR ozone time series using the Kolmogorov-Zurbenko (KZ) filter. Results of the dynamic evaluation are presented for six regions in the U.S., consistent with the National Oceanic and Atmospheric Administration (NOAA) climatic regions. During the earlier 11-yr period (1990–2000), the simulated and observed trends are not statistically significant. During the more recent 2000–2010 period, all trends are statistically significant and WRF-CMAQ captures the observed trend in most regions. Given large n

Constraining global dry deposition of ozone: observations and modeling

NASA Astrophysics Data System (ADS)

Silva, S. J.; Heald, C. L.

2016-12-01

Ozone loss through dry deposition to vegetation is a critically important process for both air quality and ecosystem health. Current estimates are that nearly 25% of all surface ozone is destroyed through dry deposition, and billions of dollars are lost annually due to losses of ecosystem services and agricultural yield associated with ozone damage. However there are still substantial uncertainties regarding the spatial distribution and magnitude of the global depositional flux. As land cover change continues throughout this century, dry deposition of ozone will change in ways that are yet still poorly understood. Nearly every major atmospheric chemistry model uses a variation of the "resistor in series parameterization" for the calculation of dry deposition. By far the most commonly implemented parameterization is of the form presented in Wesely (1989), and is dependent on many variables, including land type look up tables, solar radiation, leaf area index, temperature, and more. The uncertainties contained within the various parts of this parameterization have to date not been fully explored. A lack of understanding of these uncertainties, coupled with a dearth of routine measurements of ozone deposition, ultimately challenges our ability to understand the impacts of land cover change on surface ozone. In this work, we use a suite of globally-distributed observations from the past two decades and the GEOS-Chem chemical transport model to constrain global dry deposition, improve our understanding of these uncertainties, and contextualize the impact of land cover change on ozone concentrations.

A kinetic study of enhancing effect by phenolic compounds on the hydroxyl radical generation during ozonation.

PubMed

Han, Y H; Ichikawa, K; Utsumi, H

2004-01-01

Ozone decomposition in aqueous solution proceeds through a radical type chain mechanism. These reactions involve the very reactive and catalytic intermediates O2- radical, OH radical, HO2 radical, OH-, H2O2, etc. OH radical is proposed as an important factor in the ozonation of water among them. In the present study, the enhancing effects of several phenolic compounds; phenol, 2-, 3-, 4-monochloro, 2,4-dichloro, 2,4,6-trichlorophenol on OH radical generation were mathematically evaluated using the electron spin resonance (ESR)/spin-trapping technique. OH radical was trapped with a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a stable adduct, DMPO-OH. The initial velocities of DMPO-OH generation in ozonated water containing phenolic compounds were quantitatively measured using a combined system of ESR spectroscopy with stopped-flow apparatus, which was controlled by homemade software. The initial velocities of DMPO-OH generation increased as a function of the ozone concentration. The relation among ozone concentration, amount of phenolic compounds and the initial velocity (v0) of DMPO-OH generation was mathematically analyzed and the following equation was obtained, v0 (10(-6) M/s) = (A' x [PhOHs (10(-9) M)] + 0.0005) exp (60 x [ozone (10(-9) M)]). The equation fitted very well with the experimental results, and the correlation coefficient was larger than 0.98.

When eyes drive hand: Influence of non-biological motion on visuo-motor coupling.

PubMed

Thoret, Etienne; Aramaki, Mitsuko; Bringoux, Lionel; Ystad, Sølvi; Kronland-Martinet, Richard

2016-01-26

Many studies stressed that the human movement execution but also the perception of motion are constrained by specific kinematics. For instance, it has been shown that the visuo-manual tracking of a spotlight was optimal when the spotlight motion complies with biological rules such as the so-called 1/3 power law, establishing the co-variation between the velocity and the trajectory curvature of the movement. The visual or kinesthetic perception of a geometry induced by motion has also been shown to be constrained by such biological rules. In the present study, we investigated whether the geometry induced by the visuo-motor coupling of biological movements was also constrained by the 1/3 power law under visual open loop control, i.e. without visual feedback of arm displacement. We showed that when someone was asked to synchronize a drawing movement with a visual spotlight following a circular shape, the geometry of the reproduced shape was fooled by visual kinematics that did not respect the 1/3 power law. In particular, elliptical shapes were reproduced when the circle is trailed with a kinematics corresponding to an ellipse. Moreover, the distortions observed here were larger than in the perceptual tasks stressing the role of motor attractors in such a visuo-motor coupling. Finally, by investigating the direct influence of visual kinematics on the motor reproduction, our result conciliates previous knowledge on sensorimotor coupling of biological motions with external stimuli and gives evidence to the amodal encoding of biological motion. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Seasonal Variability in Tropospheric Ozone Distribution Over Qatar

NASA Astrophysics Data System (ADS)

Ayoub, Mohammed; Ackermann, Luis

2015-04-01

We report on the vertical distribution and seasonal variability in tropospheric ozone over the Middle East through one year of weekly ozonesondes launched from Doha, Qatar during 2014. A total of 49 2Z-V7 DMT/EN-SCI Electrochemical Concentration Cell (ECC) ozonesondes employing a 1% buffered potassium iodide solution (KI), coupled with iMet-1-RS GPS radiosondes were launched around 1300 local time. The authors used the SkySonde telemetry software (developed by CIRES and NOAA/ESRL) and developed robust in-house data quality assurance and validation methodologies. The average height of the thermal tropopause is between 15-17.5 km (125-85 hPa). Monthly average relative humidity around the tropopause shows an enhancement during the months of June through the beginning of October. Monthly average temperature profiles show the development of the subtropical subsidence inversion around 5-6 km (450-520 hPa) between the months of April through October. The subsidence inversion is strongest during the months of June and July and is accompanied by a sharp drop in relative humidity over a 100-300 m in the vertical. The monthly average ozone background concentration between the Planetary Boundary Layer (PBL) height and the subsidence inversion increases from 50 ppb in the winter to almost 80 ppb in the summer months. An enhancement of up to 50% in the average ozone in the mid-to-upper troposphere (above the subsidence inversion) is strongest during the summer months (June through September) and results in average concentrations between 80-100 ppb. In the upper troposphere (above 13 km/200 hPa) ozone concentrations are highest during the spring and summer months. This is coupled with a drop in the average height of the tropopause. HYSPLIT back-trajectory analysis shows the enhancement in mid-to-upper tropospheric ozone in the summer is due to persistent high pressure over the Middle East between the months of June through September. Evidence of Stratosphere-Troposphere Exchange

Efficient enhancement of ozonation performance via ZVZ immobilized g-C3N4 towards superior oxidation of micropollutants.

PubMed

Yuan, Xiangjuan; Qin, Wenlei; Lei, Xiaoman; Sun, Lei; Li, Qiang; Li, Dongya; Xu, Haiming; Xia, Dongsheng

2018-08-01

A functional organic-metal composite material zero-valent zinc immobilized graphitic carbon nitride (ZVZ-g-C 3 N 4 ) was prepared by a fast and facile two-step synthetic approach with an optimal ZVZ content of 5.4 wt%. The structure, surface morphology and chemical composition of the as-synthesized ZVZ-g-C 3 N 4 were characterized by BET surface area, XRD, FT-IR, SEM, TEM, and XPS, respectively. ZVZ-g-C 3 N 4 composite exhibited superior catalytic ozonation activity with an improvement of 61.2% on atrazine (ATZ) degradation efficiency in 1.5 min reaction, more than 12 times of the pseudo-first-order rate constant, and almost 16-fold of the R ct value obtained in O 3 /ZVZ-g-C 3 N 4 process compared to O 3 alone. Meanwhile, the ATZ degradation efficiency was gradually enhanced with increasing ZVZ-g-C 3 N 4 dosage and initial solution pH in the range from 3.0 to 9.0, and a higher amount of ATZ was degraded when the initial concentration of ATZ rose from 1 to 10 mg L -1 . The enhanced catalytic ozonation activity of ZVZ-g-C 3 N 4 is attributed to the synergistic effects among ZVZ, ZnO and g-C 3 N 4 , as well as the improved dispersibility, increased surface area, and intensive electron-transfer ascribed to the electronic and surface properties modification. The radical scavengers experiments demonstrated that O 2 - , OH, and 1 O 2 were the dominant reactive radical species in the multifunctional processes. Moreover, an empirical kinetic model was proposed to predict ATZ degradation. The results indicated that the ZVZ-g-C 3 N 4 composite was a highly efficient, recoverable, and durable catalyst, which would provide a promising alternative in catalytic ozonation. Copyright © 2018 Elsevier Ltd. All rights reserved.

LUNG INJURY AFTER OZONE EXPOSURE IS IRON-DEPENDENT

EPA Science Inventory

We tested the hypothesis that oxidative stress and biological effect after ozone (O3) exposure are dependent on changes in iron homeostasis. After O3 exposure, healthy volunteers demonstrated increased lavage concentrations of iron, transferrin, lactoferrin, and ferritin. In norm...

Ozone Layer Protection

MedlinePlus

... Offices Labs and Research Centers Contact Us Share Ozone Layer Protection The stratospheric ozone layer is Earth’s “ ... to ozone-depleting substances, and sun safety. Stratospheric Ozone Layer Basic Ozone Layer Science Health and Environmental ...

Meteorology-induced variations in the spatial behavior of summer ozone pollution in Central California

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

Jin, Ling; Harley, Robert A.; Brown, Nancy J.

Cluster analysis was applied to daily 8 h ozone maxima modeled for a summer season to characterize meteorology-induced variations in the spatial distribution of ozone. Principal component analysis is employed to form a reduced dimension set to describe and interpret ozone spatial patterns. The first three principal components (PCs) capture {approx}85% of total variance, with PC1 describing a general spatial trend, and PC2 and PC3 each describing a spatial contrast. Six clusters were identified for California's San Joaquin Valley (SJV) with two low, three moderate, and one high-ozone cluster. The moderate ozone clusters are distinguished by elevated ozone levels inmore » different parts of the valley: northern, western, and eastern, respectively. The SJV ozone clusters have stronger coupling with the San Francisco Bay area (SFB) than with the Sacramento Valley (SV). Variations in ozone spatial distributions induced by anthropogenic emission changes are small relative to the overall variations in ozone amomalies observed for the whole summer. Ozone regimes identified here are mostly determined by the direct and indirect meteorological effects. Existing measurement sites are sufficiently representative to capture ozone spatial patterns in the SFB and SV, but the western side of the SJV is under-sampled.« less

Impact of chemical plant start-up emissions on ambient ozone concentration

NASA Astrophysics Data System (ADS)

Ge, Sijie; Wang, Sujing; Xu, Qiang; Ho, Thomas

2017-09-01

Flare emissions, especially start-up flare emissions, during chemical plant operations generate large amounts of ozone precursors that may cause highly localized and transient ground-level ozone increment. Such an adverse ozone impact could be aggravated by the synergies of multiple plant start-ups in an industrial zone. In this paper, a systematic study on ozone increment superposition due to chemical plant start-up emissions has been performed. It employs dynamic flaring profiles of two olefin plants' start-ups to investigate the superposition of the regional 1-hr ozone increment. It also summaries the superposition trend by manipulating the starting time (00:00-10:00) of plant start-up operations and the plant distance (4-32 km). The study indicates that the ozone increment induced by simultaneous start-up emissions from multiple chemical plants generally does not follow the linear superposition of the ozone increment induced by individual plant start-ups. Meanwhile, the trend of such nonlinear superposition related to the temporal (starting time and operating hours of plant start-ups) and spatial (plant distance) factors is also disclosed. This paper couples dynamic simulations of chemical plant start-up operations with air-quality modeling and statistical methods to examine the regional ozone impact. It could be helpful for technical decision support for cost-effective air-quality and industrial flare emission controls.

Occurrence and fate of amisulpride, sulpiride, and lamotrigine in municipal wastewater treatment plants with biological treatment and ozonation.

PubMed

Bollmann, Anna Franka; Seitz, Wolfram; Prasse, Carsten; Lucke, Thomas; Schulz, Wolfgang; Ternes, Thomas

2016-12-15

This study examines the transformation and removal of the atypical antipsychotics amisulpride and sulpiride and the anticonvulsant lamotrigine in municipal wastewater treatment plants (WWTPs). Amisulpride, sulpiride and lamotrigine were selected using a tailored non-target screening approach. In WWTPs, lamotrigine concentrations increased from 1.1 to 1.6μg/L while sulpiride and amisulpride exhibited similar concentrations, up to 1.1μg/L and 1.3μg/L, respectively. It was found that N2-glucuronide conjugates of lamotrigine were cleaved to form lamotrigine. Both lamotrigine and amisulpride were detected in groundwater with a concentration of 0.07μg/L. Sulpiride was identified but not quantified. This demonstrates that amisulpride, sulpiride and lamotrigine might be used as indicators for treated wastewater in raw waters used for drinking water production. Furthermore, it could be shown that all three pharmaceutical compounds are efficiently oxidized by ozonation, leading mainly to N-oxide oxidation products. No significant removal of the N-oxides of amisulpride, sulpiride and lamotrigine was observed in the bench-scale biodegradation experiments with activated sludge. This indicated their high biological persistence. Therefore, N-oxides might be appropriate as indicators for post-ozonation as a major technology for the advanced treatment of secondary effluent. Copyright © 2016 Elsevier B.V. All rights reserved.

Uncertainties in models of tropospheric ozone based on Monte Carlo analysis: Tropospheric ozone burdens, atmospheric lifetimes and surface distributions

NASA Astrophysics Data System (ADS)

Derwent, Richard G.; Parrish, David D.; Galbally, Ian E.; Stevenson, David S.; Doherty, Ruth M.; Naik, Vaishali; Young, Paul J.

2018-05-01

Recognising that global tropospheric ozone models have many uncertain input parameters, an attempt has been made to employ Monte Carlo sampling to quantify the uncertainties in model output that arise from global tropospheric ozone precursor emissions and from ozone production and destruction in a global Lagrangian chemistry-transport model. Ninety eight quasi-randomly Monte Carlo sampled model runs were completed and the uncertainties were quantified in tropospheric burdens and lifetimes of ozone, carbon monoxide and methane, together with the surface distribution and seasonal cycle in ozone. The results have shown a satisfactory degree of convergence and provide a first estimate of the likely uncertainties in tropospheric ozone model outputs. There are likely to be diminishing returns in carrying out many more Monte Carlo runs in order to refine further these outputs. Uncertainties due to model formulation were separately addressed using the results from 14 Atmospheric Chemistry Coupled Climate Model Intercomparison Project (ACCMIP) chemistry-climate models. The 95% confidence ranges surrounding the ACCMIP model burdens and lifetimes for ozone, carbon monoxide and methane were somewhat smaller than for the Monte Carlo estimates. This reflected the situation where the ACCMIP models used harmonised emissions data and differed only in their meteorological data and model formulations whereas a conscious effort was made to describe the uncertainties in the ozone precursor emissions and in the kinetic and photochemical data in the Monte Carlo runs. Attention was focussed on the model predictions of the ozone seasonal cycles at three marine boundary layer stations: Mace Head, Ireland, Trinidad Head, California and Cape Grim, Tasmania. Despite comprehensively addressing the uncertainties due to global emissions and ozone sources and sinks, none of the Monte Carlo runs were able to generate seasonal cycles that matched the observations at all three MBL stations. Although

IVF, same-sex couples and the value of biological ties.

PubMed

Di Nucci, Ezio

2016-12-01

Ought parents, in general, to value being biologically tied to their children? Is it important, in particular, that both parents be biologically tied to their children? I will address these fundamental questions by looking at a fairly new practice within IVF treatments, so-called IVF-with-ROPA (Reception of Oocytes from Partner), which allows lesbian couples to 'share motherhood', with one partner providing the eggs while the other becomes pregnant. I believe that IVF-with-ROPA is, just like other IVF treatments, morally permissible, but here I argue that the increased biological ties which IVF-with-ROPA allows for do not have any particular value beside the satisfaction of a legitimate wish, because there is no intrinsic value in a biological tie between parents and children; further, I argue that equality within parental projects cannot be achieved by redistributing biological ties. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Structural determinants of APOBEC3B non-catalytic domain for molecular assembly and catalytic regulation

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

Xiao, Xiao; Yang, Hanjing; Arutiunian, Vagan

The catalytic activity of human cytidine deaminase APOBEC3B (A3B) has been correlated with kataegic mutational patterns within multiple cancer types. The molecular basis of how the N-terminal non-catalytic CD1 regulates the catalytic activity and consequently, biological function of A3B remains relatively unknown. Here, we report the crystal structure of a soluble human A3B-CD1 variant and delineate several structural elements of CD1 involved in molecular assembly, nucleic acid interactions and catalytic regulation of A3B. We show that (i) A3B expressed in human cells exists in hypoactive high-molecular-weight (HMW) complexes, which can be activated without apparent dissociation into low-molecular-weight (LMW) species aftermore » RNase A treatment. (ii) Multiple surface hydrophobic residues of CD1 mediate the HMW complex assembly and affect the catalytic activity, including one tryptophan residue W127 that likely acts through regulating nucleic acid binding. (iii) One of the highly positively charged surfaces on CD1 is involved in RNA-dependent attenuation of A3B catalysis. (iv) Surface hydrophobic residues of CD1 are involved in heterogeneous nuclear ribonucleoproteins (hnRNPs) binding to A3B. The structural and biochemical insights described here suggest that unique structural features on CD1 regulate the molecular assembly and catalytic activity of A3B through distinct mechanisms.« less

A method for retrieving vertical ozone profiles from limb scattered measurements

NASA Astrophysics Data System (ADS)

Wang, Zijun; Chen, Shengbo; Yang, Chunyan; Jin, Lihua

2011-10-01

A two-step method is employed in this study to retrieve vertical ozone profiles using scattered measurements from the limb of the atmosphere. The combination of the Differential Optical Absorption Spectroscopy (DOAS) and the Multiplicative Algebraic Reconstruction Technique (MART) is proposed. First, the limb radiance, measured over a range of tangent heights, is processed using the DOAS technique to recover the effective column densities of atmospheric ozone. Second, these effective column densities along the lines of sight (LOSs) are inverted using the MART coupled with a forward model SCIATRAN (radiative transfer model for SCIAMACHY) to derive the ozone profiles. This method is applied to Optical Spectrograph and Infra Red Imager System (OSIRIS) radiance, using the wavelength windows 571-617 nm. Vertical ozone profiles between 10 and 48 km are derived with a vertical resolution of 1 km. The results illustrate a good agreement with the cloud-free coincident SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) ozone measurements, with deviations less than ±10% (±5% for altitudes from 17 to 47 km). Furthermore, sensitivities of retrieved ozone to aerosol, cloud parameters and NO2 concentration are also investigated.

Evaluation of the persistence of transformation products from ozonation of trace organic compounds - a critical review.

PubMed

Hübner, Uwe; von Gunten, Urs; Jekel, Martin

2015-01-01

Ozonation is an efficient treatment system to reduce the concentration of trace organic compounds (TrOCs) from technical aquatic systems such as drinking water, wastewater and industrial water, etc. Although it is well established that ozonation generally improves the removal of organic matter in biological post-treatment, little is known about the biodegradability of individual transformation products resulting from ozonation of TrOCs. This publication provides a qualified assessment of the persistence of ozone-induced transformation products based on a review of published product studies and an evaluation of the biodegradability of transformation products with the biodegradability probability program (BIOWIN) and the University of Minnesota Pathway Prediction System (UM-PPS). The oxidation of TrOCs containing the four major ozone-reactive sites (olefins, amines, aromatics and sulfur-containing compounds) follows well described reaction pathways leading to characteristic transformation products. Assessment of biodegradability revealed a high sensitivity to the formed products and hence the ozone-reactive site present in the target compound. Based on BIOWIN, efficient removal can be expected for products from cleavage of olefin groups and aromatic rings. In contrast, estimations and literature indicate that hydroxylamines and N-oxides, the major products from ozonation of secondary and tertiary amines are not necessarily better removed in biological post-treatment. According to UM-PPS, degradation of these products might even occur via reformation of the corresponding amine. Some product studies with sulfide-containing TrOCs showed a stoichiometric formation of sulfoxides from oxygen transfer reactions. However, conclusions on the fate of transformation products in biological post-treatment cannot be drawn based on BIOWIN and UM-PPS.

Antarctic ozone loss in 1989-2010: evidence for ozone recovery?

NASA Astrophysics Data System (ADS)

Kuttippurath, J.; Lefèvre, F.; Pommereau, J.-P.; Roscoe, H. K.; Goutail, F.; Pazmiño, A.; Shanklin, J. D.

2012-04-01

We present a detailed estimation of chemical ozone loss in the Antarctic polar vortex from 1989 to 2010. The analyses include ozone loss estimates for 12 Antarctic ground-based (GB) stations. All GB observations show minimum ozone in the late September-early October period. Among the stations, the lowest minimum ozone values are observed at South Pole and the highest at Dumont d'Urville. The ozone loss starts by mid-June at the vortex edge and then progresses towards the vortex core with time. The loss intensifies in August-September, peaks by the end of September-early October, and recovers thereafter. The average ozone loss in the Antarctic is revealed to be about 33-50% in 1989-1992 in agreement with the increase in halogens during this period, and then stayed at around 48% due to saturation of the loss. The ozone loss in the warmer winters (e.g. 2002, and 2004) is lower (37-46%) and in the colder winters (e.g. 2003, and 2006) is higher (52-55%). Because of small inter-annual variability, the correlation between ozone loss and the volume of polar stratospheric clouds yields ~0.51. The GB ozone and ozone loss values are in good agreement with those found from the space-based observations of the Total Ozone Mapping Spectrometer/Ozone Monitoring Instrument (TOMS/OMI), the Global Ozone Monitoring Experiment (GOME), the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY), and the Aura Microwave Limb Sounder (MLS), where the differences are within ±5% and are mostly within the error bars of the measurements. The piece-wise linear trends computed from the September-November vortex average GB and TOMS/OMI ozone show about -4 to -5.6 DU (Dobson Unit) yr-1 in 1989-1996 and about +1 DU yr-1 in 1997-2010. The trend during the former period is significant at 95% confidence intervals, but the trend in 1997-2010 is significant only at 85% confidence intervals. Our analyses suggest a period of about 9-10 yr to get the first detectable ozone

Boulder Ozone Sonde Data Analyses for Multiple Tropopause Origins

NASA Astrophysics Data System (ADS)

Petropavlovskikh, I. V.; Manney, G. L.; Johnson, B.; Minschwaner, K.; Torres, L.; Lawrence, Z. D.

2014-12-01

Boulder ozone profile measurements tend to feature structures with multiple layers in the troposphere, so called laminae. These have been shown to be related to several phenomena, including stratospheric air intrusions that are transported to the location of measurements and local gravity wave perturbations (Boulder is located near the Rocky Mountain range where gravity waves are prevalent). In addition, observations indicate that air from the tropical tropopause layer can be transported into regions with multiple tropopauses over the middle latitudes in the vicinity of the subtropical jets. We use GMAO's GEOS-5 data assimilation system products, including Modern-Era Retrospective analysis for Research and Applications (MERRA), interpolated to Boulder, Colorado, USA (40N, 105W) to assess incidence of upper tropospheric jets that influence UTLS ozone distribution. The proximity of the subtropical jet to Boulder results in frequent observations of multiple tropopauses. We analyze ozonesonde data launched in June-July 2014 to determine the origins of laminae observed in the upper troposphere/lower stratosphere (UTLS). Our tools include back trajectory analysis coupled with 4D satellite ozone profile data, including those from NASA's Aura Microwave Limb Sounder instrument. Filaments causing laminae in ozone profiles observed at Boulder will be tracked to origins in either stratospheric or tropospheric intrusions using reverse domain-filling (RDF) trajectory methods. Detailed studies of several ozone profiles collected over Boulder in June/July 2014 will help determine techniques for future analysis of a larger dataset that goes back to 1978. Ozone variability in the UTLS over Boulder is of importance for studies of local climatological ozone conditions, their causes/attribution, and with regard to EPA ozone regulations at the mountain sites across the USA.

Low temperature ozone oxidation of solid waste surrogates

NASA Astrophysics Data System (ADS)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

PubMed

Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

2016-04-04

Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98% isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polar ozone

NASA Technical Reports Server (NTRS)

Solomon, S.; Grose, W. L.; Jones, R. L.; Mccormick, M. P.; Molina, Mario J.; Oneill, A.; Poole, L. R.; Shine, K. P.; Plumb, R. A.; Pope, V.

1990-01-01

The observation and interpretation of a large, unexpected ozone depletion over Antarctica has changed the international scientific view of stratospheric chemistry. The observations which show the veracity, seasonal nature, and vertical structure of the Antarctic ozone hole are presented. Evidence for Arctic and midlatitude ozone loss is also discussed. The chemical theory for Antarctic ozone depletion centers around the occurrence of polar stratospheric clouds (PSCs) in Antarctic winter and spring; the climatology and radiative properties of these clouds are presented. Lab studies of the physical properties of PSCs and the chemical processes that subsequently influence ozone depletion are discussed. Observations and interpretation of the chemical composition of the Antarctic stratosphere are described. It is shown that the observed, greatly enhanced abundances of chlorine monoxide in the lower stratosphere are sufficient to explain much if not all of the ozone decrease. The dynamic meteorology of both polar regions is given, interannual and interhemispheric variations in dynamical processes are outlined, and their likely roles in ozone loss are discussed.

From globally coupled maps to complex-systems biology

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

Kaneko, Kunihiko, E-mail: kaneko@complex.c.u-tokyo.ac.jp

Studies of globally coupled maps, introduced as a network of chaotic dynamics, are briefly reviewed with an emphasis on novel concepts therein, which are universal in high-dimensional dynamical systems. They include clustering of synchronized oscillations, hierarchical clustering, chimera of synchronization and desynchronization, partition complexity, prevalence of Milnor attractors, chaotic itinerancy, and collective chaos. The degrees of freedom necessary for high dimensionality are proposed to equal the number in which the combinatorial exceeds the exponential. Future analysis of high-dimensional dynamical systems with regard to complex-systems biology is briefly discussed.

Influence of ozonation and biodegradation on toxicity of industrial textile wastewater.

PubMed

Paździor, Katarzyna; Wrębiak, Julita; Klepacz-Smółka, Anna; Gmurek, Marta; Bilińska, Lucyna; Kos, Lech; Sójka-Ledakowicz, Jadwiga; Ledakowicz, Stanisław

2017-06-15

The textile industry demands huge volumes of high quality water which converts into wastewater contaminated by wide spectrum of chemicals. Estimation of textile wastewater influence on the aquatic systems is a very important issue. Therefore, closing of the water cycle within the factories is a promising method of decreasing its environmental impact as well as operational costs. Taking both reasons into account, the aim of this work was to establish the acute toxicity of the textile wastewater before and after separate chemical, biological as well as combined chemical-biological treatment. For the first time the effects of three different combinations of chemical and biological methods were investigated. The acute toxicity analysis were evaluated using the Microtox ® toxicity test. Ozonation in two reactors of working volume 1 dm 3 (stirred cell) and 20 dm 3 (bubble column) were tested as chemical process, while biodegradation was conducted in two, different systems - Sequence Batch Reactors (SBR; working volume 1.5 dm 3 ) and Horizontal Continuous Flow Bioreactor (HCFB; working volume 12 dm 3 ). The untreated wastewater had the highest toxicity (EC50 value in range: 3-6%). Ozonation caused lower reduction of the toxicity than biodegradation. In the system with SBR the best results were obtained for the biodegradation followed by the ozonation and additional biodegradation - 96% of the toxicity removal. In the second system (with HCFB) two-stage treatment (biodegradation followed by the ozonation) led to the highest toxicity reduction (98%). Copyright © 2016 Elsevier Ltd. All rights reserved.

Long-term Ozone Changes and Associated Climate Impacts in CMIP5 Simulations

NASA Technical Reports Server (NTRS)

Eyring, V.; Arblaster, J. M.; Cionni, I.; Sedlacek, J.; Perlwitz, J.; Young, P. J.; Bekki, S.; Bergmann, D.; Cameron-Smith, P.; Collins, W. J.;

Catalytic and transport cycles of ABC exporters.

PubMed

Al-Shawi, Marwan K

2011-09-07

ABC (ATP-binding cassette) transporters are arguably the most important family of ATP-driven transporters in biology. Despite considerable effort and advances in determining the structures and physiology of these transporters, their fundamental molecular mechanisms remain elusive and highly controversial. How does ATP hydrolysis by ABC transporters drive their transport function? Part of the problem in answering this question appears to be a perceived need to formulate a universal mechanism. Although it has been generally hoped and assumed that the whole superfamily of ABC transporters would exhibit similar conserved mechanisms, this is proving not to be the case. Structural considerations alone suggest that there are three overall types of coupling mechanisms related to ABC exporters, small ABC importers and large ABC importers. Biochemical and biophysical characterization leads us to the conclusion that, even within these three classes, the catalytic and transport mechanisms are not fully conserved, but continue to evolve. ABC transporters also exhibit unusual characteristics not observed in other primary transporters, such as uncoupled basal ATPase activity, that severely complicate mechanistic studies by established methods. In this chapter, I review these issues as related to ABC exporters in particular. A consensus view has emerged that ABC exporters follow alternating-access switch transport mechanisms. However, some biochemical data suggest that alternating catalytic site transport mechanisms are more appropriate for fully symmetrical ABC exporters. Heterodimeric and asymmetrical ABC exporters appear to conform to simple alternating-access-type mechanisms.

Photoinduced catalytic synthesis of biologically important metabolites from formaldehyde and ammonia under plausible "prebiotic" conditions

NASA Astrophysics Data System (ADS)

Delidovich, I. V.; Taran, O. P.; Simonov, A. N.; Matvienko, L. G.; Parmon, V. N.

2011-08-01

The article analyzes new and previously reported data on several catalytic and photochemical processes yielding biologically important molecules. UV-irradiation of formaldehyde aqueous solution yields acetaldehyde, glyoxal, glycolaldehyde and glyceraldehyde, which can serve as precursors of more complex biochemically relevant compounds. Photolysis of aqueous solution of acetaldehyde and ammonium nitrate results in formation of alanine and pyruvic acid. Dehydration of glyceraldehyde catalyzed by zeolite HZSM-5-17 yields pyruvaldehyde. Monosaccharides are formed in the course of the phosphate-catalyzed aldol condensation reactions of glycolaldehyde, glyceraldehyde and formaldehyde. The possibility of the direct synthesis of tetroses, keto- and aldo-pentoses from pure formaldehyde due to the combination of the photochemical production of glycolahyde and phosphate-catalyzed carbohydrate chain growth is demonstrated. Erythrulose and 3-pentulose are the main products of such combined synthesis with selectivity up to 10%. Biologically relevant aldotetroses, aldo- and ketopentoses are more resistant to the photochemical destruction owing to the stabilization in hemiacetal cyclic forms. They are formed as products of isomerization of erythrulose and 3-pentulose. The conjugation of the concerned reactions results in a plausible route to the formation of sugars, amino and organic acids from formaldehyde and ammonia under presumed 'prebiotic' conditions.

Ozone reaction characteristics of indoor floor dust examined in the emission cell "FLEC".

PubMed

Vibenholt, Anni; Clausen, Per Axel; Wolkoff, Peder

2014-07-01

Ozone reacts with C-C double bonds in common indoor VOCs and SVOCs contained in indoor dust and may be catalytically degraded on dust surfaces. The reaction between floor dust and ozone was investigated in the FLEC emission cell at different ozone concentrations and relative humidities (0%, 25%, and 50% RH). One gram of dust was spread on a clean stainless steel plate which was placed in the FLEC. Steady state reaction rate (kDust) at 2.2 ppm ozone was determined for four different floor dust samples collected in Danish homes and offices. This high concentration was necessary in order to measure and determine the consumption in the outlet air from the FLEC. Measurements were corrected for FLEC wall effects by subtraction of the steady state reaction rate between ozone and a FLEC on a stainless steel plate without dust (kFLEC). The composition of organic compounds in the dust was analyzed by pressurized liquid extraction and thermal desorption GC-MS before and after ozone exposure. kFLEC was independent of the ozone concentration and the reaction was treated as first order. The same was indicated for kDust since it remained unchanged at 2.2 and 1.6 ppm ozone for one dust sample. However, the measured kDust in the FLEC should be considered an average rate constant due to the FLEC geometry. kDust was in the range 0.039-0.14s(-1) pr. g dust at 50% RH. kDust was 3 times higher at 25% RH than at 50% RH and 6 times higher than at 0% RH. The inhomogeneity of the dust was assessed by experiments in triplicate with a new portion of dust each time. The relative standard deviation of kDust at 50% RH was 6-20%. The major identified compounds before and after ozone exposure included aldehydes, saturated and unsaturated linear alkanoic acids, benzoic acid and their methyl esters, dimethyl esters, phthalates and traces of α-pinene and limonene. Substantial increase of C7-C9 aldehydes was observed after ozone exposure. Copyright © 2014 Elsevier Ltd. All rights reserved.

Stratospheric ozone depletion from future nitrous oxide increases

NASA Astrophysics Data System (ADS)

Wang, W.; Tian, W.; Dhomse, S.; Xie, F.; Shu, J.; Austin, J.

2014-12-01

We have investigated the impact of the assumed nitrous oxide (N2O) increases on stratospheric chemistry and dynamics using a series of idealized simulations with a coupled chemistry-climate model (CCM). In a future cooler stratosphere the net yield of NOy from N2O is shown to decrease in a reference run following the IPCC A1B scenario, but NOy can still be significantly increased by extra increases of N2O over 2001-2050. Over the last decade of simulations, 50% increases in N2O result in a maximal 6% reduction in ozone mixing ratios in the middle stratosphere at around 10 hPa and an average 2% decrease in the total ozone column (TCO) compared with the control run. This enhanced destruction could cause an ozone decline in the first half of this century in the middle stratosphere around 10 hPa, while global TCO still shows an increase at the same time. The results from a multiple linear regression analysis and sensitivity simulations with different forcings show that the chemical effect of N2O increases dominates the N2O-induced ozone depletion in the stratosphere, while the dynamical and radiative effects of N2O increases are overall insignificant. The analysis of the results reveals that the ozone depleting potential of N2O varies with the time period and is influenced by the environmental conditions. For example, carbon dioxide (CO2) increases can strongly offset the ozone depletion effect of N2O.

On the role of ozone feedback in the ENSO amplitude response under global warming.

PubMed

Nowack, Peer J; Braesicke, Peter; Luke Abraham, N; Pyle, John A

2017-04-28

The El Niño-Southern Oscillation (ENSO) in the tropical Pacific Ocean is of key importance to global climate and weather. However, state-of-the-art climate models still disagree on the ENSO's response under climate change. The potential role of atmospheric ozone changes in this context has not been explored before. Here we show that differences between typical model representations of ozone can have a first-order impact on ENSO amplitude projections in climate sensitivity simulations. The vertical temperature gradient of the tropical middle-to-upper troposphere adjusts to ozone changes in the upper troposphere and lower stratosphere, modifying the Walker circulation and consequently tropical Pacific surface temperature gradients. We show that neglecting ozone changes thus results in a significant increase in the number of extreme ENSO events in our model. Climate modeling studies of the ENSO often neglect changes in ozone. We therefore highlight the need to understand better the coupling between ozone, the tropospheric circulation, and climate variability.

What would have happened to the ozone layer if chlorofluorocarbons (CFCs) had not been regulated?

NASA Astrophysics Data System (ADS)

Oman, L.; Newman, P. A.; Douglass, A. R.; Fleming, E. L.; Frith, S. M.; Hurwitz, M.; Kawa, S. R.; Jackman, C. H.; Krotkov, N. A.; Nash, E. R.; Nielsen, J. E.; Pawson, S.; Stolarski, R. S.; Velders, G. J.

2010-12-01

The Montreal Protocol on Substances that Deplete the Ozone Layer was negotiated in 1987 and by 2010 had been signed by all of the nations of the world. In this presentation we use a fully coupled radiation-chemical-dynamical model to simulate a future world where ozone depletion substances (ODSs) were never regulated. In this “world avoided” simulation, ODS levels increase by 3% per year. From 1980 to 2020 we find that 17% of the globally average column ozone is destroyed, and from 1980 to 2065 67% is destroyed. Severe polar depletions (e.g., the Antarctic ozone hole) become year-round rather than just seasonal. Ozone levels in the tropical lower stratosphere remain constant until about 2053 and then collapse to near zero by 2058 as a result of heterogeneous chemical processes (as currently observed in the Antarctic ozone hole). The tropical cooling that triggers the ozone collapse is caused by an increase of the tropical lower stratospheric upwelling. In response to ozone changes, ultraviolet (UV) radiation increases, tripling the erythemal (sunburn) radiation in the northern summer mid-latitudes by 2065.

Techno-economic evaluation of the application of ozone-oxidation in a full-scale aerobic digestion plant.

PubMed

Chiavola, Agostina; D'Amato, Emilio; Gori, Riccardo; Lubello, Claudio; Sirini, Piero

2013-04-01

This paper deals with the application of the ozone-oxidation in a full scale aerobic sludge digester. Ozonation was applied continuously to a fraction of the biological sludge extracted from the digestion unit; the ozonated sludge was then recirculated to the same digester. Three different ozone flow rates were tested (60,500 and 670g O3 h(-1)) and their effects evaluated in terms of variation of the total and soluble fractions of COD, nitrogen and phosphorous, of total and volatile suspended solids concentrations and Sludge Volume Index in the aerobic digestion unit. During the 7-month operation of the ozonation process, it was observed an appreciable improvement of the aerobic digestion efficiency (up to about 20% under the optimal conditions) and of the sludge settleability properties. These results determined an average reduction of about 60% in the biological sludge extracted from the plant and delivered to final disposal. A thorough economic analysis showed that this reduction allowed to achieve a significant cost saving for the plant with respect to the previous years operated without ozonation. Furthermore, it was determined the threshold disposal cost above which implementation of the ozone oxidation in the aerobic digestion units of similar WWTPs becomes economically convenient (about 60€t(-1) of sludge). Copyright © 2013 Elsevier Ltd. All rights reserved.

Theoretical study of catalytic efficiency of a Diels-Alderase catalytic antibody: an indirect effect produced during the maturation process.

PubMed

Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan

2008-01-01

The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate.

Impact of parameterization choices on the restitution of ozone deposition over vegetation

NASA Astrophysics Data System (ADS)

Le Morvan-Quéméner, Aurélie; Coll, Isabelle; Kammer, Julien; Lamaud, Eric; Loubet, Benjamin; Personne, Erwan; Stella, Patrick

2018-04-01

Ozone is a potentially phyto-toxic air pollutant, which can cause leaf damage and drastically alter crop yields, causing serious economic losses around the world. The VULNOZ (VULNerability to OZone in Anthropised Ecosystems) project is a biology and modeling project that aims to understand how plants respond to the stress of high ozone concentrations, then use a set of models to (i) predict the impact of ozone on plant growth, (ii) represent ozone deposition fluxes to vegetation, and finally (iii) estimate the economic consequences of an increasing ozone background the future. In this work, as part of the VULNOZ project, an innovative representation of ozone deposition to vegetation was developed and implemented in the CHIMERE regional chemistry-transport model. This type of model calculates the average amount of ozone deposited on a parcel each hour, as well as the integrated amount of ozone deposited to the surface at the regional or country level. Our new approach was based on a refinement of the representation of crop types in the model and the use of empirical parameters specific to each crop category. The results obtained were compared with a conventional ozone deposition modeling approach, and evaluated against observations from several agricultural areas in France. They showed that a better representation of the distribution between stomatal and non-stomatal ozone fluxes was obtained in the empirical approach, and they allowed us to produce a new estimate of the total amount of ozone deposited on the subtypes of vegetation at the national level.

Topological entropy of catalytic sets: Hypercycles revisited

NASA Astrophysics Data System (ADS)

Sardanyés, Josep; Duarte, Jorge; Januário, Cristina; Martins, Nuno

2012-02-01

The dynamics of catalytic networks have been widely studied over the last decades because of their implications in several fields like prebiotic evolution, virology, neural networks, immunology or ecology. One of the most studied mathematical bodies for catalytic networks was initially formulated in the context of prebiotic evolution, by means of the hypercycle theory. The hypercycle is a set of self-replicating species able to catalyze other replicator species within a cyclic architecture. Hypercyclic organization might arise from a quasispecies as a way to increase the informational containt surpassing the so-called error threshold. The catalytic coupling between replicators makes all the species to behave like a single and coherent evolutionary multimolecular unit. The inherent nonlinearities of catalytic interactions are responsible for the emergence of several types of dynamics, among them, chaos. In this article we begin with a brief review of the hypercycle theory focusing on its evolutionary implications as well as on different dynamics associated to different types of small catalytic networks. Then we study the properties of chaotic hypercycles with error-prone replication with symbolic dynamics theory, characterizing, by means of the theory of topological Markov chains, the topological entropy and the periods of the orbits of unimodal-like iterated maps obtained from the strange attractor. We will focus our study on some key parameters responsible for the structure of the catalytic network: mutation rates, autocatalytic and cross-catalytic interactions.

Ozonation strategies to reduce sludge production of a seafood industry WWTP.

PubMed

Campos, J L; Otero, L; Franco, A; Mosquera-Corral, A; Roca, E

2009-02-01

In this work, several alternatives related to the application of ozone in different streams of a seafood industry WWTP were evaluated to minimize the production of waste sludge. The WWTP was composed of two coagulation-flocculation units and a biological unit and generated around of 6550 kg/d of sludge. Ozone was applied to sludge coming from flotation units (110 g TSS/L) at doses up to 0.03 g O(3)/g TSS during batch tests, no solids solubilization being observed. Ozone doses ranging from 0.007 to 0.02 g O(3)/g TSS were also applied to the raw wastewater in a bubble column reaching a 6.8% of TSS removal for the highest ozone dose. Finally, the effect of the pre-ozonation (0.05 g O(3)/g TSS) of wastewater coming from the first flotation unit was tested in two activated sludge systems during 70 days. Ozonation caused a reduction of the observed yield coefficient of biomass from 0.14 to 0.07g TSS/g COD(Tremoved) and a slight improvement of COD removal efficiencies. On the basis of the capacity for ozone production available in the industry, a maximum reduction of sludge generated by the WWTP of 7.5% could be expected.

Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2017-04-01

In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

Dobson total ozone series of Oxford: Reevaluation and applications

NASA Astrophysics Data System (ADS)

Vogler, C.; BröNnimann, S.; Staehelin, J.; Griffin, R. E. M.

2007-10-01

We have reevaluated the original total ozone measurements made in Oxford between 1924 and 1957, with a view to extending backward in time the existing total ozone series from 1957 to 1975. The Oxford measurements are the oldest Dobson observations in the world. Their prime importance, when coupled with the series from Arosa (since 1926) and Tromsø (since 1935), is for increasing basic understanding of stratospheric ozone and dynamics, while in relation to studies of the recent ozone depletion they constitute a baseline of considerable (and unique) significance and value. However, the reevaluation was made difficult on account of changes to the instruments and wavelengths as the early data collection methods evolved, while unknowns due to the influence of aerosols and the possible presence of dioxides of sulphur and nitrogen created additional problems. Our reevaluation was based on statistical procedures (comparisons with meteorological upper air data and ozone series from Arosa) and also on corrections suggested by Dobson himself. The comparisons demonstrate that the data are internally consistent and of good quality. Nevertheless, as post-1957 data were not assessed in this study, the series cannot be recommended at present for trend analysis, though the series can be used for climatological studies. By supplementing the Oxford data with other existing series, we present a European total ozone climatology for 1924-1939, 1950-1965, and 1988-2000 and analyze the data with respect to variables measuring the strength and the temperature of the polar vortex.

Dissolved organic nitrogen and its biodegradable portion in a water treatment plant with ozone oxidation.

PubMed

Wadhawan, Tanush; Simsek, Halis; Kasi, Murthy; Knutson, Kristofer; Prüβ, Birgit; McEvoy, John; Khan, Eakalak

2014-05-01

Biodegradability of dissolved organic nitrogen (DON) has been studied in wastewater, freshwater and marine water but not in drinking water. Presence of biodegradable DON (BDON) in water prior to and after chlorination may promote formation of nitrogenous disinfectant by-products and growth of microorganisms in the distribution system. In this study, an existing bioassay to determine BDON in wastewater was adapted and optimized, and its application was tested on samples from four treatment stages of a water treatment plant including ozonation and biologically active filtration. The optimized bioassay was able to detect BDON in 50 μg L(-1) as N of glycine and glutamic solutions. BDON in raw (144-275 μg L(-1) as N), softened (59-226 μg L(-1) as N), ozonated (190-254 μg L(-1) as N), and biologically filtered (17-103 μg L(-1) as N) water samples varied over a sampling period of 2 years. The plant on average removed 30% of DON and 68% of BDON. Ozonation played a major role in increasing the amount of BDON (31%) and biologically active filtration removed 71% of BDON in ozonated water. Copyright © 2014 Elsevier Ltd. All rights reserved.

The total ozone and UV solar radiation over Stara Zagora, Bulgaria

NASA Astrophysics Data System (ADS)

Mendeva, B.; Gogosheva, Ts.; Petkov, B.; Krastev, D.

Direct ground-based UV measurements and the total ozone content (TOC) over Stara Zagora, Bulgaria are presented. The observations are conducted by a scanning spectrophotometer, which measures the direct solar radiation in the range 290 - 360 nm with 1 nm resolution. For the time period 1998 -- 2003 the TOC data show seasonal variations, typical for the middle latitudes -- maximum in the spring and minimum in the autumn. The comparison of these TOC ground-based data to TOC satellite-borne data from the Global Ozone Monitoring Experiment (GOME) shows a seasonal dependence of the differences between the ground-based and satellite data. The relation between the UV radiation and TOC is investigated. Clear negative relationship is recognized between the total ozone and the irradiance of the wavelength 305 nm. The opposition of the two variables is significant ( r = - 0,62 ± 0,18) at 98 % confidence level. Yet, for 325 nm it is almost independent with the total ozone. The dependence of the UV-B radiation on the solar zenith angle at given TOC is also analyzed. A decrease of all wavelengths intensities with increase of the solar zenith angle is obtained but with different rate for each of them. The direct sun UV doses for some specific biological effects (erythema and eyes) are obtained as the integral in the wavelength interval 290-330 nm of the measured UV solar spectrum, weighted with an action spectrum, typical for each effect. The estimation of the radiation amplification factor RAF shows that the ozone reduction by 1% increases the erythemal dose by 2,3 %.The eye-damaging doses are more influenced by the TOC changes and in this case RAF=-2,7%. The amount of these biological doses is in a direct ratio with the solar altitude over the horizon. This dependence is more markedly expressed at lower total ozone content in the atmosphere.

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Exploration of two-enzyme coupled catalysis system using scanning electrochemical microscopy.

PubMed

Wu, Zeng-Qiang; Jia, Wen-Zhi; Wang, Kang; Xu, Jing-Juan; Chen, Hong-Yuan; Xia, Xing-Hua

2012-12-18

In biological metabolism, a given metabolic process usually occurs via a group of enzymes working together in sequential pathways. To explore the metabolism mechanism requires the understanding of the multienzyme coupled catalysis systems. In this paper, an approach has been proposed to study the kinetics of a two-enzyme coupled reaction using SECM combining numerical simulations. Acetylcholine esterase and choline oxidase are immobilized on cysteamine self-assembled monolayers on tip and substrate gold electrodes of SECM via electrostatic interactions, respectively. The reaction kinetics of this two-enzyme coupled system upon various separation distance precisely regulated by SECM are measured. An overall apparent Michaelis-Menten constant of this enzyme cascade is thus measured as 2.97 mM at an optimal tip-substrate gap distance of 18 μm. Then, a kinetic model of this enzyme cascade is established for evaluating the kinetic parameters of individual enzyme by using the finite element method. The simulated results demonstrate the choline oxidase catalytic reaction is the rate determining step of this enzyme cascade. The Michaelis-Menten constant of acetylcholine esterase is evaluated as 1.8 mM. This study offers a promising approach to exploring mechanism of other two-enzyme coupled reactions in biological system and would promote the development of biosensors and enzyme-based logic systems.

Control of Oscillation Patterns in a Symmetric Coupled Biological Oscillator System

NASA Astrophysics Data System (ADS)

Takamatsu, Atsuko; Tanaka, Reiko; Yamamoto, Takatoki; Fujii, Teruo

2003-08-01

A chain of three-oscillator system was constructed with living biological oscillators of phasmodial slime mold, Physarum polycehalum and the oscillation patterns were analyzed by the symmetric Hopf bifurcation theory using group theory. Multi-stability of oscillation patterns was observed, even when the coupling strength was fixed. This suggests that the coupling strength is not an effective parameter to obtain a desired oscillation pattern among the multiple patterns. Here we propose a method to control oscillation patterns using resonance to external stimulus and demonstrate pattern switching induced by frequency resonance given to only one of oscillators in the system.

Model-based analysis of avoidance of ozone stress by stomatal closure in Siebold's beech (Fagus crenata)

PubMed Central

Hoshika, Yasutomo; Watanabe, Makoto; Inada, Naoki; Koike, Takayoshi

2013-01-01

Background and Aims Resistance of plants to ozone stress can be classified as either avoidance or tolerance. Avoidance of ozone stress may be explained by decreased stomatal conductance during ozone exposure because stomata are the principal interface for entry of ozone into plants. In this study, a coupled photosynthesis–stomatal model was modified to test whether the presence of ozone can induce avoidance of ozone stress by stomatal closure. Methods The response of Siebold's beech (Fagus crenata), a representative deciduous tree species, to ozone was studied in a free-air ozone exposure experiment in Japan. Photosynthesis and stomatal conductance were measured under ambient and elevated ozone. An optimization model of stomata involving water, CO2 and ozone flux was tested using the leaf gas exchange data. Key Results The data suggest that there are two phases in the avoidance of ozone stress via stomatal closure for Siebold's beech: (1) in early summer ozone influx is efficiently limited by a reduction in stomatal conductance, without any clear effect on photosynthetic capacity; and (2) in late summer and autumn the efficiency of ozone stress avoidance was decreased because the decrease in stomatal conductance was small and accompanied by an ozone-induced decline of photosynthetic capacity. Conclusions Ozone-induced stomatal closure in Siebold's beech during early summer reduces ozone influx and allows the maximum photosynthetic capacity to be reached, but is not sufficient in older leaves to protect the photosynthetic system. PMID:23904447

Geostatistics as a validation tool for setting ozone standards for durum wheat.

PubMed

De Marco, Alessandra; Screpanti, Augusto; Paoletti, Elena

2010-02-01

Which is the best standard for protecting plants from ozone? To answer this question, we must validate the standards by testing biological responses vs. ambient data in the field. A validation is missing for European and USA standards, because the networks for ozone, meteorology and plant responses are spatially independent. We proposed geostatistics as validation tool, and used durum wheat in central Italy as a test. The standards summarized ozone impact on yield better than hourly averages. Although USA criteria explained ozone-induced yield losses better than European criteria, USA legal level (75 ppb) protected only 39% of sites. European exposure-based standards protected > or =90%. Reducing the USA level to the Canadian 65 ppb or using W126 protected 91% and 97%, respectively. For a no-threshold accumulated stomatal flux, 22 mmol m(-2) was suggested to protect 97% of sites. In a multiple regression, precipitation explained 22% and ozone explained <0.9% of yield variability. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

N-nitrosodimethylamine (NDMA) formation during ozonation of wastewater and water treatment polymers.

PubMed

Sgroi, Massimiliano; Roccaro, Paolo; Oelker, Gregg; Snyder, Shane A

2016-02-01

N-Nitrosodimethylamine (NDMA) formation by ozonation was investigated in the effluents of four different wastewater treatment plants destined for alternative reuse. Very high levels of NDMA formation were observed in wastewaters from treatment plants non operating with biological nitrogen removal. Selected experiments showed that hydroxyl radical did not have a significant role in NDMA formation during ozonation of wastewater. Furthermore, ozonation of three different polymers used for water treatment, including polyDADMAC, anionic polyacrylamide, and cationic polyacrylamide, spiked in wastewater did not increase the NDMA formation. Effluent organic matter (EfOM) likely reduced the availability of ozone in water able to react with polymers and quenched the produced ·OH radicals which limited polymer degradation and subsequent NDMA production. Excellent correlations were observed between NDMA formation, UV absorbance at 254 nm, and total fluorescence reduction. These data provide evidence that UV and fluorescence surrogates could be used for monitoring and/or controlling NDMA formation during ozonation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of acute ozone exposure on the lung metabolomes of obese and lean mice.

PubMed

Mathews, Joel Andrew; Kasahara, David Itiro; Cho, Youngji; Bell, Lauren Nicole; Gunst, Philip Ross; Karoly, Edward D; Shore, Stephanie Ann

2017-01-01

Pulmonary responses to the air pollutant, ozone, are increased in obesity. Both obesity and ozone cause changes in systemic metabolism. Consequently, we examined the impact of ozone on the lung metabolomes of obese and lean mice. Lean wildtype and obese db/db mice were exposed to acute ozone (2 ppm for 3 h) or air. 24 hours later, the lungs were excised, flushed with PBS to remove blood and analyzed via liquid-chromatography or gas-chromatography coupled to mass spectrometry for metabolites. Both obesity and ozone caused changes in the lung metabolome. Of 321 compounds identified, 101 were significantly impacted by obesity in air-exposed mice. These included biochemicals related to carbohydrate and lipid metabolism, which were each increased in lungs of obese versus lean mice. These metabolite changes may be of functional importance given the signaling capacity of these moieties. Ozone differentially affected the lung metabolome in obese versus lean mice. For example, almost all phosphocholine-containing lysolipids were significantly reduced in lean mice, but this effect was attenuated in obese mice. Glutathione metabolism was also differentially affected by ozone in obese and lean mice. Finally, the lung metabolome indicated a role for the microbiome in the effects of both obesity and ozone: all measured bacterial/mammalian co-metabolites were significantly affected by obesity and/or ozone. Thus, metabolic derangements in obesity appear to impact the response to ozone.

In vitro evaluation of wound healing and antimicrobial potential of ozone therapy.

PubMed

Borges, Gabriel Álvares; Elias, Silvia Taveira; da Silva, Sandra Márcia Mazutti; Magalhães, Pérola Oliveira; Macedo, Sergio Bruzadelli; Ribeiro, Ana Paula Dias; Guerra, Eliete Neves Silva

2017-03-01

Although ozone therapy is extensively applied when wound repair and antimicrobial effect are necessary, little is known about cellular mechanisms regarding this process. Thus, this study aimed to evaluate ozone cytotoxicity in fibroblasts (L929) and keratinocytes (HaCaT) cell lines, its effects on cell migration and its antimicrobial activity. Cells were treated with ozonated phosphate-buffered saline (8, 4, 2, 1, 0.5 and 0.25 μg/mL ozone), chlorhexidine 0.2% or buffered-solution, and cell viability was determined through MTT assay. The effect of ozone on cell migration was evaluated through scratch wound healing and transwell migration assays. The minimum inhibitory concentrations for Candida albicans and Staphylococcus aureus were determined. Ozone showed no cytotoxicity for the cell lines, while chlorhexidine markedly reduced cell viability. Although no significant difference between control and ozone-treated cells was observed in the scratch assay, a considerable increase in fibroblasts migration was noticed on cells treated with 8 μg/mL ozonated solution. Ozone alone did not inhibit growth of microorganisms; however, its association with chlorhexidine resulted in antimicrobial activity. This study confirms the wound healing and antimicrobial potential of ozone therapy and presents the need for studies to elucidate the molecular mechanisms through which it exerts such biological effects. Copyright © 2017 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

NASA Technical Reports Server (NTRS)

Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

2014-01-01

The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

Evaluation of neural reflex activation as a mode of action for the acute respiratory effects of ozone.

PubMed

Prueitt, Robyn L; Goodman, Julie E

2016-09-01

Exposure to elevated levels of ozone has been associated with a variety of respiratory-related health endpoints in both epidemiology and controlled human exposure studies, including lung function decrements and airway inflammation. A mode of action (MoA) for these effects has not been established, but it has been proposed that they may occur through ozone-induced activation of neural reflexes. We critically reviewed experimental studies of ozone exposure and neural reflex activation and applied the International Programme on Chemical Safety (IPCS) mode-of-action/human relevance framework to evaluate the biological plausibility and human relevance of this proposed MoA. Based on the currently available experimental data, we found that the proposed MoA of neural reflex activation is biologically plausible for the endpoint of ozone-induced lung function decrements at high ozone exposures, but further studies are needed to fill important data gaps regarding the relevance of this MoA at lower exposures. A role for the proposed MoA in ozone-induced airway inflammation is less plausible, as the evidence is conflicting and is also of unclear relevance given the lack of studies conducted at lower exposures. The evidence suggests a different MoA for ozone-induced inflammation that may still be linked to the key events in the proposed MoA, such that neural reflex activation may have some degree of involvement in modulating ozone-induced neutrophil influx, even if it is not a direct role.

Effects of stratospheric ozone recovery on photochemistry and ozone air quality in the troposphere

NASA Astrophysics Data System (ADS)

Zhang, H.; Wu, S.; Huang, Y.; Wang, Y.

2014-04-01

There has been significant stratospheric ozone depletion since the late 1970s due to ozone-depleting substances (ODSs). With the implementation of the Montreal Protocol and its amendments and adjustments, stratospheric ozone is expected to recover towards its pre-1980 level in the coming decades. In this study, we examine the implications of stratospheric ozone recovery for the tropospheric chemistry and ozone air quality with a global chemical transport model (GEOS-Chem). With a full recovery of the stratospheric ozone, the projected increases in ozone column range from 1% over the low latitudes to more than 10% over the polar regions. The sensitivity factor of troposphere ozone photolysis rate, defined as the percentage changes in surface ozone photolysis rate for 1% increase in stratospheric ozone column, shows significant seasonal variation but is always negative with absolute value larger than one. The expected stratospheric ozone recovery is found to affect the tropospheric ozone destruction rates much more than the ozone production rates. Significant decreases in surface ozone photolysis rates due to stratospheric ozone recovery are simulated. The global average tropospheric OH decreases by 1.7%, and the global average lifetime of tropospheric ozone increases by 1.5%. The perturbations to tropospheric ozone and surface ozone show large seasonal and spatial variations. General increases in surface ozone are calculated for each season, with increases by up to 0.8 ppbv in the remote areas. Increases in ozone lifetime by up to 13% are found in the troposphere. The increased lifetimes of tropospheric ozone in response to stratospheric ozone recovery enhance the intercontinental transport of ozone and global pollution, in particular for the summertime. The global background ozone attributable to Asian emissions is calculated to increase by up to 15% or 0.3 ppbv in the Northern Hemisphere in response to the projected stratospheric ozone recovery.

Coupling Processes Between Atmospheric Chemistry and Climate

NASA Technical Reports Server (NTRS)

Ko, Malcolm K. W.; Weisenstein, Debra; Rodriguez, Jose; Danilin, Michael; Scott, Courtney; Shia, Run-Lie; Eluszkiewicz, Junusz; Sze, Nien-Dak

1999-01-01

This is the final report. The overall objective of this project is to improve the understanding of coupling processes among atmospheric chemistry, aerosol and climate, all important for quantitative assessments of global change. Among our priority are changes in ozone and stratospheric sulfate aerosol, with emphasis on how ozone in the lower stratosphere would respond to natural or anthropogenic changes. The work emphasizes two important aspects: (1) AER's continued participation in preparation of, and providing scientific input for, various scientific reports connected with assessment of stratospheric ozone and climate. These include participation in various model intercomparison exercises as well as preparation of national and international reports. and (2) Continued development of the AER three-wave interactive model to address how the transport circulation will change as ozone and the thermal properties of the atmosphere change, and assess how these new findings will affect our confidence in the ozone assessment results.

Required ozone doses for removing pharmaceuticals from wastewater effluents.

PubMed

Antoniou, Maria G; Hey, Gerly; Rodríguez Vega, Sergio; Spiliotopoulou, Aikaterini; Fick, Jerker; Tysklind, Mats; la Cour Jansen, Jes; Andersen, Henrik Rasmus

2013-07-01

The aim of the this study was to investigate the ozone dosage required to remove active pharmaceutical ingredients (APIs) from biologically treated wastewater of varying quality, originated from different raw wastewater and wastewater treatment processes. Secondary effluents from six Swedish wastewater treatment plants (WWTP) were spiked with 42 APIs (nominal concentration μg/L) and treated with different O₃ doses (0.5-12.0 mg/L ozone) in bench-scale experiments. In order to compare the sensitivity of APIs in each matrix, the specific dose of ozone required to achieve reduction by one decade of each investigated API (DDO₃) was determined for each effluent by fitting a first order equation to the remaining concentration of API at each applied ozone dose. Ozone dose requirements were found to vary significantly between effluents depending on their matrix characteristics. The specific ozone dose was then normalized to the dissolved organic carbon (DOC) of each effluent. The DDO₃/DOC ratios were comparable for each API between the effluents. 15 of the 42 investigated APIs could be classified as easily degradable (DDO₃/DOC ≤ 0.7), while 19 were moderately degradable (0.7 < DDO₃/DOC ≤ 1.4), and 8 were recalcitrant towards O₃-treatment (DDO₃/DOC >1.4). Furthermore, we predict that a reasonable estimate of the ozone dose required to remove any of the investigated APIs may be attained by multiplying the experimental average DDO₃/DOC obtained with the actual DOC of any effluent. Copyright © 2013 Elsevier B.V. All rights reserved.

Measurements of Unexpected Ozone Loss in a Nighttime Space Shuttle Exhaust Plume: Implications for Geo-Engineering Projects

NASA Astrophysics Data System (ADS)

Avallone, L. M.; Kalnajs, L. E.; Toohey, D. W.; Ross, M. N.

2008-12-01

Measurements of ozone, carbon dioxide and particulate water were made in the nighttime exhaust plume of the Space Shuttle (STS-116) on 9 December 2006 as part of the PUMA/WAVE campaign (Plume Ultrafast Measurements Acquisition/WB-57F Ascent Video Experiment). The launch took place from Kennedy Space Center at 8:47 pm (local time) on a moonless night and the WB-57F aircraft penetrated the shuttle plume approximately 25 minutes after launch in the lowermost stratosphere. Ozone loss is not predicted to occur in a nighttime Space Shuttle plume since it has long been assumed that the main ozone loss mechanism associated with rocket emissions requires solar photolysis to drive several chlorine-based catalytic cycles. However, the nighttime in situ observations show an unexpected loss of ozone of approximately 250 ppb in the evolving exhaust plume, inconsistent with model predictions. We will present the observations of the shuttle exhaust plume composition and the results of photochemical models of the Space Shuttle plume. We will show that models constrained by known rocket emission kinetics, including afterburning, and reasonable plume dispersion rates, based on the CO2 observations, cannot explain the observed ozone loss. We will propose potential explanations for the lack of agreement between models and the observations, and will discuss the implications of these explanations for our understanding of the composition of rocket emissions. We will describe the potential consequences of the observed ozone loss for long-term damage to the stratospheric ozone layer should geo-engineering projects based on rocket launches be employed.

The Extrapolar SWIFT model (version 1.0): fast stratospheric ozone chemistry for global climate models

NASA Astrophysics Data System (ADS)

Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

2018-03-01

The Extrapolar SWIFT model is a fast ozone chemistry scheme for interactive calculation of the extrapolar stratospheric ozone layer in coupled general circulation models (GCMs). In contrast to the widely used prescribed ozone, the SWIFT ozone layer interacts with the model dynamics and can respond to atmospheric variability or climatological trends.The Extrapolar SWIFT model employs a repro-modelling approach, in which algebraic functions are used to approximate the numerical output of a full stratospheric chemistry and transport model (ATLAS). The full model solves a coupled chemical differential equation system with 55 initial and boundary conditions (mixing ratio of various chemical species and atmospheric parameters). Hence the rate of change of ozone over 24 h is a function of 55 variables. Using covariances between these variables, we can find linear combinations in order to reduce the parameter space to the following nine basic variables: latitude, pressure altitude, temperature, overhead ozone column and the mixing ratio of ozone and of the ozone-depleting families (Cly, Bry, NOy and HOy). We will show that these nine variables are sufficient to characterize the rate of change of ozone. An automated procedure fits a polynomial function of fourth degree to the rate of change of ozone obtained from several simulations with the ATLAS model. One polynomial function is determined per month, which yields the rate of change of ozone over 24 h. A key aspect for the robustness of the Extrapolar SWIFT model is to include a wide range of stratospheric variability in the numerical output of the ATLAS model, also covering atmospheric states that will occur in a future climate (e.g. temperature and meridional circulation changes or reduction of stratospheric chlorine loading).For validation purposes, the Extrapolar SWIFT model has been integrated into the ATLAS model, replacing the full stratospheric chemistry scheme. Simulations with SWIFT in ATLAS have proven that the

Biomedical consequences of ozone depletion

NASA Astrophysics Data System (ADS)

Coohill, Thomas P.

1994-07-01

It is widely agreed that a portion of the earth's protective stratospheric ozone layer is being depleted. The major effect of this ozone loss will be an increase in the amount of ultraviolet radiation (UV reaching the biosphere. This increase will be completely contained within the UVB (290nm - 320nm). It is imperative that assessments be made of the effects of this additional UVB on living organisms. This requires a detailed knowledge of the UVB photobiology of these life forms. One analytical technique to aid in the approximations is the construction of UV action spectra for such important biological end-points as human skin cancer, cataracts, immune suppression; plant photosynthesis and crop yields; and aquatic organism responses to UVB, especially the phytoplankton. Combining these action spectra with the known solar spectrum (and estimates for various ozone depletion scenarios) can give rise to a series of effectiveness spectra for these parameters. This manuscript gives a first approximation, rough estimate, for the effectiveness spectra for some of these bioresponses, and a series of crude temporary values for how a 10% ozone loss would affect the above end-points. These are not intended to masquerade as final answers, but rather, to serve as beginning attempts for a process which should be continually refined. It is hoped that these estimates will be of some limited use to agencies, such as government and industry, that have to plan now for changes in human activities that might alter future atmospheric chemistry in a beneficial manner.

Spectroscopic, thermal, catalytic and biological studies of Cu(II) azo dye complexes

NASA Astrophysics Data System (ADS)

El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Shoair, A. F.; Hussein, M. A.; El-Boz, R. A.

2017-08-01

New complexes of copper(II) with azo compounds of 5-amino-2-(aryl diazenyl)phenol (HLn) are prepared and investigated by elemental analyses, molar conductance, IR, 1H NMR, UV-Visible, mass, ESR spectra, magnetic susceptibility measurements and thermal analyses. The complexes have a square planar structure and general formula [Cu(Ln)(OAc)]H2O. Study the catalytic activities of Cu(II) complexes toward oxidation of benzyl alcohol derivatives to carbonyl compounds were tested using H2O2 as the oxidant. The intrinsic binding constants (Kb) of the ligands (HLn) and Cu(II) complexes (1-4) with CT-DNA are determined. The formed compounds have been tested for biological activity of antioxidants, antibacterial against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and yeast Candida albicans. Antibiotic (Ampicillin) and antifungal against (Colitrimazole) and cytotoxic compounds HL1, HL2, HL3 and complex (1) showed moderate to good activity against S. aureus, E. coli and Candida albicans, and also to be moderate on antioxidants and toxic substances. Molecular docking is used to predict the binding between the ligands with the receptor of breast cancer (2a91).

Regulation of Catalytic and Non-catalytic Functions of the Drosophila Ste20 Kinase Slik by Activation Segment Phosphorylation.

PubMed

Panneton, Vincent; Nath, Apurba; Sader, Fadi; Delaunay, Nathalie; Pelletier, Ariane; Maier, Dominic; Oh, Karen; Hipfner, David R

2015-08-21

Protein kinases carry out important functions in cells both by phosphorylating substrates and by means of regulated non-catalytic activities. Such non-catalytic functions have been ascribed to many kinases, including some members of the Ste20 family. The Drosophila Ste20 kinase Slik phosphorylates and activates Moesin in developing epithelial tissues to promote epithelial tissue integrity. It also functions non-catalytically to promote epithelial cell proliferation and tissue growth. We carried out a structure-function analysis to determine how these two distinct activities of Slik are controlled. We find that the conserved C-terminal coiled-coil domain of Slik, which is necessary and sufficient for apical localization of the kinase in epithelial cells, is not required for Moesin phosphorylation but is critical for the growth-promoting function of Slik. Slik is auto- and trans-phosphorylated in vivo. Phosphorylation of at least two of three conserved sites in the activation segment is required for both efficient catalytic activity and non-catalytic signaling. Slik function is thus dependent upon proper localization of the kinase via the C-terminal coiled-coil domain and activation via activation segment phosphorylation, which enhances both phosphorylation of substrates like Moesin and engagement of effectors of its non-catalytic growth-promoting activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Mars Ozone Absorption Line Shapes from Infrared Heterodyne Spectra Applied to GCM-Predicted Ozone Profiles and to MEX/SPICAM Column Retrievals

NASA Technical Reports Server (NTRS)

Fast, Kelly E.; Kostiuk, T.; Annen, J.; Hewagama, T.; Delgado, J.; Livengood, T. A.; Lefevre, F.

2008-01-01

We present the application of infrared heterodyne line shapes of ozone on Mars to those produced by radiative transfer modeling of ozone profiles predicted by general circulation models (GCM), and to contemporaneous column abundances measured by Mars Express SPICAM. Ozone is an important tracer of photochemistry Mars' atmosphere, serving as an observable with which to test predictions of photochemistry-coupled GCMs. Infrared heterodyne spectroscopy at 9.5 microns with spectral resolving power >1,000,000 is the only technique that can directly measure fully-resolved line shapes of Martian ozone features from the surface of the Earth. Measurements were made with Goddard Space Flight Center's Heterodyne instrument for Planetary Wind And Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii on February 21-24 2008 UT at Ls=35deg on or near the MEX orbital path. The HIPWAC observations were used to test GCM predictions. For example, a GCM-generated ozone profile for 60degN 112degW was scaled so that a radiative transfer calculation of its absorption line shape matched an observed HIPWAC absorption feature at the same areographic position, local time, and season. The RMS deviation of the model from the data was slightly smaller for the GCM-generated profile than for a line shape produced by a constant-with-height profile, even though the total column abundances were the same, showing potential for testing and constraining GCM ozone-profiles. The resulting ozone column abundance from matching the model to the HIPWAC line shape was 60% higher than that observed by SPICAM at the same areographic position one day earlier and 2.5 hours earlier in local time. This could be due to day-to-day, diurnal, or north polar region variability, or to measurement sensitivity to the ozone column and its distribution, and these possibilities will be explored. This work was supported by NASA's Planetary Astronomy Program.

Bio-Monitoring of Ozone by Young Students

ERIC Educational Resources Information Center

Lorenzini, Giacomo; Nali, Cristina

2004-01-01

An educational pilot project on the bio-monitoring of air quality was carried out in the Umbria Region of Central Italy. It involved about 1000 young students (ages 4 to 16) from 42 schools of 16 municipalities in active biomonitoring of tropospheric ozone with bio-indicator sensitive tobacco seedlings. Some 6500 raw biological readings were used…

CONTRIBUTION TO INDOOR OZONE LEVELS OF AN OZONE GENERATOR

EPA Science Inventory

This report gives results of a study of a commonly used commercially available ozone generator, undertaken to determine its impact on indoor ozone levels. xperiment were conducted in a typical mechanically ventilated office and in a test house. he generated ozone and the in-room ...

Impacts of Atmosphere-Ocean Coupling on Southern Hemisphere Climate Change

NASA Technical Reports Server (NTRS)

Li, Feng; Newman, Paul; Pawson, Steven

2013-01-01

Climate in the Southern Hemisphere (SH) has undergone significant changes in recent decades. These changes are closely linked to the shift of the Southern Annular Mode (SAM) towards its positive polarity, which is driven primarily by Antarctic ozone depletion. There is growing evidence that Antarctic ozone depletion has significant impacts on Southern Ocean circulation change. However, it is poorly understood whether and how ocean feedback might impact the SAM and climate change in the SH atmosphere. This outstanding science question is investigated using the Goddard Earth Observing System Coupled Atmosphere-Ocean-Chemistry Climate Model(GEOS-AOCCM).We perform ensemble simulations of the recent past (1960-2010) with and without the interactive ocean. For simulations without the interactive ocean, we use sea surface temperatures and sea ice concentrations produced by the interactive ocean simulations. The differences between these two ensemble simulations quantify the effects of atmosphere-ocean coupling. We will investigate the impacts of atmosphere-ocean coupling on stratospheric processes such as Antarctic ozone depletion and Antarctic polar vortex breakup. We will address whether ocean feedback affects Rossby wave generation in the troposphere and wave propagation into the stratosphere. Another focuson this study is to assess how ocean feedback might affect the tropospheric SAM response to Antarctic ozone depletion

Antarctic Ozone Hole, 2000

NASA Technical Reports Server (NTRS)

2002-01-01

Each spring the ozone layer over Antarctica nearly disappears, forming a 'hole' over the entire continent. The hole is created by the interaction of some man-made chemicals-freon, for example-with Antarctica's unique weather patterns and extremely cold temperatures. Ozone in the stratosphere absorbs ultraviolet radiation from the sun, thereby protecting living things. Since the ozone hole was discovered many of the chemicals that destroy ozone have been banned, but they will remain in the atmosphere for decades. In 2000, the ozone hole grew quicker than usual and exceptionally large. By the first week in September the hole was the largest ever-11.4 million square miles. The top image shows the average total column ozone values over Antarctica for September 2000. (Total column ozone is the amount of ozone from the ground to the top of the atmosphere. A relatively typical measurement of 300 Dobson Units is equivalent to a layer of ozone 0.12 inches thick on the Earth's surface. Levels below 220 Dobson Units are considered to be significant ozone depletion.) The record-breaking hole is likely the result of lower than average ozone levels during the Antarctic fall and winter, and exceptionally cold temperatures. In October, however (bottom image), the hole shrank dramatically, much more quickly than usual. By the end of October, the hole was only one-third of it's previous size. In a typical year, the ozone hole does not collapse until the end of November. NASA scientists were surprised by this early shrinking and speculate it is related to the region's weather. Global ozone levels are measured by the Total Ozone Mapping Spectrometer (TOMS). For more information about ozone, read the Earth Observatory's ozone fact sheet, view global ozone data and see these ozone images. Images by Greg Shirah, NASA GSFC Scientific Visualization Studio.

Development of Compact Ozonizer with High Ozone Output by Pulsed Power

NASA Astrophysics Data System (ADS)

Tanaka, Fumiaki; Ueda, Satoru; Kouno, Kanako; Sakugawa, Takashi; Akiyama, Hidenori; Kinoshita, Youhei

Conventional ozonizer with a high ozone output using silent or surface discharges needs a cooling system and a dielectric barrier, and therefore becomes a large machine. A compact ozonizer without the cooling system and the dielectric barrier has been developed by using a pulsed power generated discharge. The wire to plane electrodes made of metal have been used. However, the ozone output was low. Here, a compact and high repetition rate pulsed power generator is used as an electric source of a compact ozonizer. The ozone output of 6.1 g/h and the ozone yield of 86 g/kWh are achieved at 500 pulses per second, input average power of 280 W and an air flow rate of 20 L/min.

Analysis of ozone precursor data from Baton Rouge, Houston, El Paso, and Dallas

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

Sather, M.E.; Kemp, M.G.

1998-12-31

Ongoing analyses of ozone precursor data continue to be performed for Baton Rouge, Louisiana, and Houston, El Paso, and Dallas, Texas. All four areas have collected ambient monitoring data for ozone, nitrogen oxides (NO{sub x}), and over 50 volatile organic compound (VOC) species in accordance with the Photochemical Assessment Monitoring Stations (PAMS) requirements. The PAMS program was initiated to provide more detailed VOC, NO{sub x}, and meteorological data for scientists, modelers, and managers working toward eliminating violations of the ozone National Ambient Air Quality Standards (NAAQS). This paper will focus on several useful analyses of PAMS data for the fourmore » study areas including: (1) a trends analysis of Total Non-Methane Organic Compounds (TNMOC), NO{sub x}, and ozone data from two Baton Rouge sites, (2) results of TNMOC/NO{sub x} ratio analyses for the three Baton Rouge PAMS sites which can provide a starting point for evaluating specific site sensitivity to changes in VOC or NO{sub x} ambient concentrations, (3) results of benzene/toluene ratio analyses which supply information on aged/fresh air masses, and (4) results of ethylene/acetylene ratio analyses which are useful in determining the impacts of catalytic/noncatalytic vehicles. This paper will also discuss the continuing maturation of the PAMS program in Baton Rouge, Houston, and El Paso. The Dallas area is expected to formally begin implementing a PAMS program in 1998 after the area is reclassified to a serious status for ozone pollution. In addition, the Beaumont, Texas area is currently scheduled to be reclassified to a serious status for ozone pollution in the 1998/1999 time period, and thus would also need to begin implementing a PAMS program.« less

Attempts to probe the ozone layer and the ultraviolet-B levels of the past.

PubMed

Björn, Lars Olof; McKenzie, Richard L

2007-07-01

To get a proper perspective on the current status of atmospheric ozone, which protects the biosphere from ultraviolet-B (UV-B; 280-315 nm) radiation, it would be of value to know how ozone and UV-B radiation have varied in the past. The record of worldwide ozone monitoring goes back only a few decades, and the record of reliable UV-B measurements is even shorter. Here we review indirect methods to assess their status further back in time. These include variations in the Sun's emission and how these affect the atmosphere, changes in the Earth's orbit, geologic imprints of atmospheric ozone, effects of catastrophic events such as volcanic eruptions, biological proxies of UV-B radiation, the spectral signature of terrestrial ozone in old recordings of star spectra, and the modeling of UV-B irradiance from ozone data and meteorological recordings. Although reliable reconstructions do not yet extend far into the past, there is some hope for future progress.

A decontamination study of simulated chemical and biological agents

NASA Astrophysics Data System (ADS)

Uhm, Han S.; Lee, Han Y.; Hong, Yong C.; Shin, Dong H.; Park, Yun H.; Hong, Yi F.; Lee, Chong K.

2007-07-01

A comprehensive decontamination scheme of the chemical and biological agents, including airborne agents and surface contaminating agents, is presented. When a chemical and biological attack occurs, it is critical to decontaminate facilities or equipments to an acceptable level in a very short time. The plasma flame presented here may provide a rapid and effective elimination of toxic substances in the interior air in isolated spaces. As an example, a reaction chamber, with the dimensions of a 22cm diameter and 30cm length, purifies air with an airflow rate of 5000l/min contaminated with toluene, the simulated chemical agent, and soot from a diesel engine, the simulated aerosol for biological agents. Although the airborne agents in an isolated space are eliminated to an acceptable level by the plasma flame, the decontamination of the chemical and biological agents cannot be completed without cleaning surfaces of the facilities. A simulated sterilization study of micro-organisms was carried out using the electrolyzed ozone water. The electrolyzed ozone water very effectively kills endospores of Bacillus atrophaeus (ATCC 9372) within 3min. The electrolyzed ozone water also kills the vegetative micro-organisms, fungi, and virus. The electrolyzed ozone water, after the decontamination process, disintegrates into ordinary water and oxygen without any trace of harmful materials to the environment.

Dynamic coupling between the LID and NMP domain motions in the catalytic conversion of ATP and AMP to ADP by adenylate kinase

NASA Astrophysics Data System (ADS)

Jana, Biman; Adkar, Bharat V.; Biswas, Rajib; Bagchi, Biman

2011-01-01

The catalytic conversion of adenosine triphosphate (ATP) and adenosine monophosphate (AMP) to adenosine diphosphate (ADP) by adenylate kinase (ADK) involves large amplitude, ligand induced domain motions, involving the opening and the closing of ATP binding domain (LID) and AMP binding domain (NMP) domains, during the repeated catalytic cycle. We discover and analyze an interesting dynamical coupling between the motion of the two domains during the opening, using large scale atomistic molecular dynamics trajectory analysis, covariance analysis, and multidimensional free energy calculations with explicit water. Initially, the LID domain must open by a certain amount before the NMP domain can begin to open. Dynamical correlation map shows interesting cross-peak between LID and NMP domain which suggests the presence of correlated motion between them. This is also reflected in our calculated two-dimensional free energy surface contour diagram which has an interesting elliptic shape, revealing a strong correlation between the opening of the LID domain and that of the NMP domain. Our free energy surface of the LID domain motion is rugged due to interaction with water and the signature of ruggedness is evident in the observed root mean square deviation variation and its fluctuation time correlation functions. We develop a correlated dynamical disorder-type theoretical model to explain the observed dynamic coupling between the motion of the two domains in ADK. Our model correctly reproduces several features of the cross-correlation observed in simulations.

Geometric tuning of self-propulsion for Janus catalytic particles

NASA Astrophysics Data System (ADS)

Michelin, Sébastien; Lauga, Eric

2017-02-01

Catalytic swimmers have attracted much attention as alternatives to biological systems for examining collective microscopic dynamics and the response to physico-chemical signals. Yet, understanding and predicting even the most fundamental characteristics of their individual propulsion still raises important challenges. While chemical asymmetry is widely recognized as the cornerstone of catalytic propulsion, different experimental studies have reported that particles with identical chemical properties may propel in opposite directions. Here, we show that, beyond its chemical properties, the detailed shape of a catalytic swimmer plays an essential role in determining its direction of motion, demonstrating the compatibility of the classical theoretical framework with experimental observations.

Geometric tuning of self-propulsion for Janus catalytic particles

PubMed Central

Michelin, Sébastien; Lauga, Eric

2017-01-01

Catalytic swimmers have attracted much attention as alternatives to biological systems for examining collective microscopic dynamics and the response to physico-chemical signals. Yet, understanding and predicting even the most fundamental characteristics of their individual propulsion still raises important challenges. While chemical asymmetry is widely recognized as the cornerstone of catalytic propulsion, different experimental studies have reported that particles with identical chemical properties may propel in opposite directions. Here, we show that, beyond its chemical properties, the detailed shape of a catalytic swimmer plays an essential role in determining its direction of motion, demonstrating the compatibility of the classical theoretical framework with experimental observations. PMID:28205563

Geometric tuning of self-propulsion for Janus catalytic particles.

PubMed

Michelin, Sébastien; Lauga, Eric

2017-02-13

Catalytic swimmers have attracted much attention as alternatives to biological systems for examining collective microscopic dynamics and the response to physico-chemical signals. Yet, understanding and predicting even the most fundamental characteristics of their individual propulsion still raises important challenges. While chemical asymmetry is widely recognized as the cornerstone of catalytic propulsion, different experimental studies have reported that particles with identical chemical properties may propel in opposite directions. Here, we show that, beyond its chemical properties, the detailed shape of a catalytic swimmer plays an essential role in determining its direction of motion, demonstrating the compatibility of the classical theoretical framework with experimental observations.

Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

PubMed

Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

2014-05-21

Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

Mesospheric effects of solar ultraviolet variations - Further analysis of SME IR ozone and Nimbus 7 SAMS temperature data

NASA Astrophysics Data System (ADS)

Hood, L. L.; Huang, Z.; Bougher, S. W.

1991-07-01

In order to improve the constraints on models of the mesospheric response to solar UV variations, an analysis is conducted of the Solar Mesosphere Explorer (SME) IR ozone data and Nimbus 7 stratosphere and mesosphere sounder (SAMS) temperature data. Maximum low-altitude ozone and temperature-response amplitudes occur at about the same altitude, where a strong coupling between photochemical and thermal components of the mesospheric response is suggested by the simultaneous positive temperature and negative ozone response maxima. Increased Lyman-alpha dissociation of water vapor and temperature feedback are theorized to account for the negative ozone response. HO(x) chemical heating can increase as ozone destruction increases, and can therefore account for the positive temperature response.

Mesospheric effects of solar ultraviolet variations - Further analysis of SME IR ozone and Nimbus 7 SAMS temperature data

NASA Technical Reports Server (NTRS)

Hood, L. L.; Huang, Z.; Bougher, S. W.

1991-01-01

In order to improve the constraints on models of the mesospheric response to solar UV variations, an analysis is conducted of the Solar Mesosphere Explorer (SME) IR ozone data and Nimbus 7 stratosphere and mesosphere sounder (SAMS) temperature data. Maximum low-altitude ozone and temperature-response amplitudes occur at about the same altitude, where a strong coupling between photochemical and thermal components of the mesospheric response is suggested by the simultaneous positive temperature and negative ozone response maxima. Increased Lyman-alpha dissociation of water vapor and temperature feedback are theorized to account for the negative ozone response. HO(x) chemical heating can increase as ozone destruction increases, and can therefore account for the positive temperature response.

Simulated sensitivity of seasonal ozone exposure in the Great Lakes region to changes in anthropogenic emissions in the presence of interannual variability

Treesearch

Jerome D. Fast; Warren E. Heilman

2005-01-01

A coupled meteorological and chemical modeling system with a 12-km horizontal grid spacing was used to simulate the evolution of ozone over the Great Lakes region between May and September of 1999 and 2001. The overall temporal and spatial variations in hourly ozone concentrations and ozone exposure from control simulations agreed reasonably well with the observations...

Impact of biogenic very short-lived bromine on the Antarctic ozone hole during the 21st century

NASA Astrophysics Data System (ADS)

Fernandez, Rafael Pedro; Kinnison, Douglas E.; Lamarque, Jean-Francois; Tilmes, Simone; Saiz-Lopez, Alfonso

2017-04-01

Active bromine released from the photochemical decomposition of biogenic very short-lived bromocarbons (VSLBr) enhances stratospheric ozone depletion. Based on a dual set of 1960-2100 coupled chemistry-climate simulations (i.e. with and without VSLBr), we show that the maximum Antarctic ozone hole depletion increases by up to 14% when natural VSLBr are considered, in better agreement with ozone observations. The impact of the additional 5 pptv VSLBr on Antarctic ozone is most evident in the periphery of the ozone hole, producing an expansion of the ozone hole area of 5 million km2, which is equivalent in magnitude to the recently estimated Antarctic ozone healing due to the implementation of the Montreal Protocol. We find that the inclusion of VSLBr in CAM-Chem does not introduce a significant delay of the modelled ozone return date to 1980 October levels, but instead affect the depth and duration of the simulated ozone hole. Our analysis further shows that total bromine-catalysed ozone destruction in the lower stratosphere surpasses that of chlorine by year 2070, and indicates that natural VSLBr chemistry would dominate Antarctic ozone seasonality before the end of the 21st century. This work suggests a large influence of biogenic bromine on the future Antarctic ozone layer.

Variability of total ozone at Arosa, Switzerland, since 1931 related to atmospheric circulation indices

NASA Astrophysics Data System (ADS)

Brönnimann, S.; Luterbacher, J.; Schmutz, C.; Wanner, H.; Staehelin, J.

2000-08-01

Atmospheric circulation determines to a considerable extent the variability of lower stratospheric ozone and can modulate its long-term trends in Europe and the North Atlantic Region. Due to dynamical stratosphere-troposphere coupling, important features of the variability of the surface pressure field are reflected in the long-term total ozone record from Arosa, Switzerland. Significant (p<0.01) correlations between total ozone and different atmospheric circulation indices (NAOI, AOI, EU1, EU2) are found in all months except for April, June, July, and November for the period 1931 to 1997. An analysis of geopotential heights for the period 1958 to 1997 shows that these circulation anomaly patterns have upper tropospheric features over the North Atlantic-European sector that are consistent with a dynamical influence on total ozone.

Complex Wall Boundary Conditions for Modeling Combustion in Catalytic Channels

NASA Astrophysics Data System (ADS)

Zhu, Huayang; Jackson, Gregory

2000-11-01

Monolith catalytic reactors for exothermic oxidation are being used in automobile exhaust clean-up and ultra-low emissions combustion systems. The reactors present a unique coupling between mass, heat, and momentum transport in a channel flow configuration. The use of porous catalytic coatings along the channel wall presents a complex boundary condition when modeled with the two-dimensional channel flow. This current work presents a 2-D transient model for predicting the performance of catalytic combustion systems for methane oxidation on Pd catalysts. The model solves the 2-D compressible transport equations for momentum, species, and energy, which are solved with a porous washcoat model for the wall boundary conditions. A time-splitting algorithm is used to separate the stiff chemical reactions from the convective/diffusive equations for the channel flow. A detailed surface chemistry mechanism is incorporated for the catalytic wall model and is used to predict transient ignition and steady-state conversion of CH4-air flows in the catalytic reactor.

Dynamic Evaluation of Two Decades of WRF-CMAQ Ozone Simulations over the Contiguous United States (2017 MAC-MAQ Conference Presentation)

EPA Science Inventory

Dynamic evaluation of two decades of ozone simulations performed with the fully coupled Weather Research and Forecasting (WRF)–Community Multi-scale Air Quality (CMAQ) model over the contiguous United States is conducted to assess how well the changes in observed ozone air ...

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

2016-11-01

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

PubMed

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

Communication: Biological applications of coupled-cluster frozen-density embedding

NASA Astrophysics Data System (ADS)

Heuser, Johannes; Höfener, Sebastian

2018-04-01

We report the implementation of the Laplace-transform scaled opposite-spin (LT-SOS) resolution-of-the-identity second-order approximate coupled-cluster singles and doubles (RICC2) combined with frozen-density embedding for excitation energies and molecular properties. In the present work, we furthermore employ the Hartree-Fock density for the interaction energy leading to a simplified Lagrangian which is linear in the Lagrangian multipliers. This approximation has the key advantage of a decoupling of the coupled-cluster amplitude and multipliers, leading also to a significant reduction in computation time. Using the new simplified Lagrangian in combination with efficient wavefunction models such as RICC2 or LT-SOS-RICC2 and density-functional theory (DFT) for the environment molecules (CC2-in-DFT) enables the efficient study of biological applications such as the rhodopsin and visual cone pigments using ab initio methods as routine applications.

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds.

PubMed

Bijan, Leila; Mohseni, Madjid

2005-10-01

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD5, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O3/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD5 enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.

Catalytic Properties and Biomedical Applications of Cerium Oxide Nanoparticles

PubMed Central

Walkey, Carl; Das, Soumen; Seal, Sudipta; Erlichman, Joseph; Heckman, Karin; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William T.

2014-01-01

Cerium oxide nanoparticles (Nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of Nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of Nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of Nanoceria in animal studies? 2) What are the considerations to develop Nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials? PMID:26207185

Methods of increasing secretion of polypeptides having biological activity

DOEpatents

Merino, Sandra

2014-05-27

The present invention relates to methods for producing a secreted polypeptide having biological activity, comprising: (a) transforming a fungal host cell with a fusion protein construct encoding a fusion protein, which comprises: (i) a first polynucleotide encoding a signal peptide; (ii) a second polynucleotide encoding at least a catalytic domain of an endoglucanase or a portion thereof; and (iii) a third polynucleotide encoding at least a catalytic domain of a polypeptide having biological activity; wherein the signal peptide and at least the catalytic domain of the endoglucanase increases secretion of the polypeptide having biological activity compared to the absence of at least the catalytic domain of the endoglucanase; (b) cultivating the transformed fungal host cell under conditions suitable for production of the fusion protein; and (c) recovering the fusion protein, a component thereof, or a combination thereof, having biological activity, from the cultivation medium.

Methods of increasing secretion of polypeptides having biological activity

DOEpatents

Merino, Sandra

2014-10-28

The present invention relates to methods for producing a secreted polypeptide having biological activity, comprising: (a) transforming a fungal host cell with a fusion protein construct encoding a fusion protein, which comprises: (i) a first polynucleotide encoding a signal peptide; (ii) a second polynucleotide encoding at least a catalytic domain of an endoglucanase or a portion thereof; and (iii) a third polynucleotide encoding at least a catalytic domain of a polypeptide having biological activity; wherein the signal peptide and at least the catalytic domain of the endoglucanase increases secretion of the polypeptide having biological activity compared to the absence of at least the catalytic domain of the endoglucanase; (b) cultivating the transformed fungal host cell under conditions suitable for production of the fusion protein; and (c) recovering the fusion protein, a component thereof, or a combination thereof, having biological activity, from the cultivation medium.

Methods of increasing secretion of polypeptides having biological activity

DOEpatents

Merino, Sandra

2015-04-14

The present invention relates to methods for producing a secreted polypeptide having biological activity, comprising: (a) transforming a fungal host cell with a fusion protein construct encoding a fusion protein, which comprises: (i) a first polynucleotide encoding a signal peptide; (ii) a second polynucleotide encoding at least a catalytic domain of an endoglucanase or a portion thereof; and (iii) a third polynucleotide encoding at least a catalytic domain of a polypeptide having biological activity; wherein the signal peptide and at least the catalytic domain of the endoglucanase increases secretion of the polypeptide having biological activity compared to the absence of at least the catalytic domain of the endoglucanase; (b) cultivating the transformed fungal host cell under conditions suitable for production of the fusion protein; and (c) recovering the fusion protein, a component thereof, or a combination thereof, having biological activity, from the cultivation medium.

Methods of increasing secretion of polypeptides having biological activity

DOEpatents

Merino, Sandra

2013-10-01

The present invention relates to methods for producing a secreted polypeptide having biological activity, comprising: (a) transforming a fungal host cell with a fusion protein construct encoding a fusion protein, which comprises: (i) a first polynucleotide encoding a signal peptide; (ii) a second polynucleotide encoding at least a catalytic domain of an endoglucanase or a portion thereof; and (iii) a third polynucleotide encoding at least a catalytic domain of a polypeptide having biological activity; wherein the signal peptide and at least the catalytic domain of the endoglucanase increases secretion of the polypeptide having biological activity compared to the absence of at least the catalytic domain of the endoglucanase; (b) cultivating the transformed fungal host cell under conditions suitable for production of the fusion protein; and (c) recovering the fusion protein, a component thereof, or a combination thereof, having biological activity, from the cultivation medium.

Projections of Future Summertime Ozone over the U.S.

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

Pfister, G. G.; Walters, Stacy; Lamarque, J. F.

This study uses a regional fully coupled chemistry-transport model to assess changes in surface ozone over the summertime U.S. between present and a 2050 future time period at high spatial resolution (12 km grid spacing) under the SRES A2 climate and RCP8.5 anthropogenic pre-cursor emission scenario. The impact of predicted changes in climate and global background ozone is estimated to increase surface ozone over most of the U.S; the 5th - 95th percentile range for daily 8-hour maximum surface ozone increases from 31-79 ppbV to 30-87 ppbV between the present and future time periods. The analysis of a set ofmore » meteorological drivers suggests that these mostly will add to increasing ozone, but the set of simulations conducted does not allow to separate this effect from that through enhanced global background ozone. Statistically the most robust positive feedbacks are through increased temperature, biogenic emissions and solar radiation. Stringent emission controls can counteract these feedbacks and if considered, we estimate large reductions in surface ozone with the 5th-95th percentile reduced to 27-55 ppbV. A comparison of the high-resolution projections to global model projections shows that even though the global model is biased high in surface ozone compared to the regional model and compared to observations, both the global and the regional model predict similar changes in ozone between the present and future time periods. However, on smaller spatial scales, the regional predictions show more pronounced changes between urban and rural regimes that cannot be resolved at the coarse resolution of global model. In addition, the sign of the changes in overall ozone mixing ratios can be different between the global and the regional predictions in certain regions, such as the Western U.S. This study confirms the key role of emission control strategies in future air quality predictions and demonstrates the need for considering degradation of air quality with

Coupling Processes Between Atmospheric Chemistry and Climate

NASA Technical Reports Server (NTRS)

Ko, Malcolm; Weisenstein, Debra; Rodriquez, Jose; Danilin, Michael; Scott, Courtney; Shia, Run-Lie; Eluszkiewicz, Janusz; Sze, Nien-Dak; Stewart, Richard W. (Technical Monitor)

1999-01-01

This is the final report for NAS5-97039 for work performed between December 1996 and November 1999. The overall objective of this project is to improve the understanding of coupling processes among atmospheric chemistry, aerosol and climate, all important for quantitative assessments of global change. Among our priority are changes in ozone and stratospheric sulfate aerosol, with emphasis on how ozone in the lower stratosphere would respond to natural or anthropogenic changes. The work emphasizes two important aspects: (1) AER's continued participation in preparation of, and providing scientific input for, various scientific reports connected with assessment of stratospheric ozone and climate. These include participation in various model intercomparison exercises as well as preparation of national and international reports. (2) Continued development of the AER three-wave interactive model to address how the transport circulation will change as ozone and the thermal properties of the atmosphere change, and assess how these new findings will affect our confidence in the ozone assessment results.

2009 Antarctic Ozone Hole

NASA Image and Video Library

2009-09-16

The annual ozone hole has started developing over the South Pole, and it appears that it will be comparable to ozone depletions over the past decade. This composite image from September 10 depicts ozone concentrations in Dobson units, with purple and blues depicting severe deficits of ozone. "We have observed the ozone hole again in 2009, and it appears to be pretty average so far," said ozone researcher Paul Newman of NASA's Goddard Space Flight Center in Greenbelt, Md. "However, we won't know for another four weeks how this year's ozone hole will fully develop." Scientists are tracking the size and depth of the ozone hole with observations from the Ozone Monitoring Instrument on NASA's Aura spacecraft, the Global Ozone Monitoring Experiment on the European Space Agency's ERS-2 spacecraft, and the Solar Backscatter Ultraviolet instrument on the National Oceanic and Atmospheric Administration's NOAA-16 satellite. The depth and area of the ozone hole are governed by the amount of chlorine and bromine in the Antarctic stratosphere. Over the southern winter, polar stratospheric clouds (PSCs) form in the extreme cold of the atmosphere, and chlorine gases react on the cloud particles to release chlorine into a form that can easily destroy ozone. When the sun rises in August after months of seasonal polar darkness, the sunlight heats the clouds and catalyzes the chemical reactions that deplete the ozone layer. The ozone hole begins to grow in August and reaches its largest area in late September to early October. Recent observations and several studies have shown that the size of the annual ozone hole has stabilized and the level of ozone-depleting substances has decreased by 4 percent since 2001. But since chlorine and bromine compounds have long lifetimes in the atmosphere, a recovery of atmospheric ozone is not likely to be noticeable until 2020 or later. Visit NASA's Ozone Watch page for current imagery and data: ozonewatch.gsfc.nasa.gov/index.html

The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations

NASA Technical Reports Server (NTRS)

Brasseur, G.; Derudder, A.

1987-01-01

The response of the atmosphere to emissions of chlorofluorocarbons (CFCs) and other chlorocarbons, and to increasing concentrations of other radiatively active trace gases such as CO2, CH4, and N2O is calculated by a coupled chemical-radiative transport one-dimensional model. It is shown that significant reductions in the ozone concentration and in the temperature are expected in the upper stratosphere as a result of increasing concentrations of active chlorine produced by photodecomposition of the CFCs. The ozone content is expected to increase in the troposphere, as a consequence of increasing concentrations of methane and nitrogen oxides. Due to enhanced greenhouse effects, the Earth's surface should warm up by several degrees. The amplitude and even the sign of future changes in the ozone column are difficult to predict as they are strongly scenario-dependent. An early detection system to prevent noticeable ozone changes as a result of increasing concentrations of source gases should thus be based on a continuous monitoring of the ozone amount in the upper stratosphere rather than on measurements of the ozone column only. Measurements of NOx, Clx, and HOx are also required for unambiguous trend detection and interpretation.