Final report for SERDP WP-2209 Replacement melt-castable formulations for Composition B

DTIC Science & Technology

2017-05-19

Chemical reaction of the materials in the melt ............................................................... 5 Thermal degradation of materials...reasons other than the hazard of explosion, these include: • Chemical reaction of the materials in the melt • Thermal degradation at low...temperature • Sublimation and condensation of explosive material on equipment and exposure to workers Chemical reaction of the materials in the melt

Suitability of regulatory data to predict micropollutant degradation in rivers

NASA Astrophysics Data System (ADS)

Honti, Mark; Bischoff, Fabian; Moser, Andreas; Stamm, Christian; Fenner, Kathrin

2017-04-01

For many chemicals a certain loss to surface water bodies over their life-cycle is unavoidable. These include pesticides, human pharmaceuticals, biocides, industrial chemicals, and veterinary medicines. Since most of them possess an intentional biological activity, they bear the potential to harm non-target organisms in the environment. The actual exposure to a chemical in the environment after emission is determined by its persistence, i.e., by the rate at which it is removed by biological and chemical degradation processes. For surface water systems, major transformation processes include chemical hydrolysis, direct and indirect photo-transformation and microbial biotransformation. Laboratory-based test systems play an important role in evaluating chemical transformation for regulatory purposes due to their replicability, their lower costs compared to field tests, and the better representation of environmental systems compared to lower tier biodegradability and hydrolysis tests. The OECD 308 and 309 test systems are relevant for evaluation of microbial biotransformation of chemicals in surface waters. Degradation half-lives derived from these experiments are typically used in exposure modeling and persistence assessment. These "simulation" tests have been severely criticized for yielding results strongly specific to the experimental systems and for therefore being irrelevant for most environmental conditions. Our objective was to check the relation between degradation half-lives measured in regulatory tests and half-lives observed in actual surface water bodies. We used the Rhine river catchment and the results of a field campaign carried out in 2011 (Ruff et al. 2015, Water Research). 7 pharmaceuticals were selected, including a conservative benchmark substance. Laboratory degradation half-lives were extracted from OECD 308 data. A GIS model was set up to simulate the accumulation of chemicals from the wastewater treatment plants of the catchment and the behavior of the chemicals in the river Rhine. For substances with OECD 308 data, predictions using compartment-specific degradation half-lives were found to be in accordance with measured concentrations, but not much different from simulations assuming no degradation. This suggests that the usually fairly long water half-lives dominated the compounds' behavior in the river Rhine. Besides this, it highlighted that the shorter total system half-lives derived from OECD 308 are indeed irrelevant for assessing persistence in medium to large river systems. For two substances, it was not possible to tune modelled concentration patterns to be in agreement with observed data, even when assuming different extents of degradation. This underlined the influence of input uncertainty (e.g. consumption in different countries and regions). Finally, the model was used to investigate what kind of water half-lives would result in an observable degradation along the Rhine. Substances with half-lives shorter than 9 days would show spatial concentration patterns that are clearly different from those of a conservative benchmark chemical, given the typical measurement, model and input uncertainty. Besides learning the inadequacy of certain indicators from laboratory simulation studies for assessment of environmental persistence, our results suggest that emissions of many organic micropollutants showing observable degradation in the laboratory are transferred almost without loss to the sea, even from such a large river basin as the Rhine.

Survey of the Anaerobic Biodegradation Potential of Organic Chemicals in Digesting Sludge

PubMed Central

Battersby, Nigel S.; Wilson, Valerie

1989-01-01

The degradation potential of 77 organic chemicals under methanogenic conditions was examined with an anaerobic digesting sludge from the United Kingdom. Degradation was assessed in terms of net total gas (CH4 plus CO2) produced, expressed as a percentage of the theoretical production (ThGP). The compounds tested were selected from various chemical groups and included substituted phenols and benzoates, pesticides, phthalic acid esters, homocyclic and heterocyclic ring compounds, glycols, and monosubstituted benzenes. The results obtained were in good agreement with published surveys of biodegradability in U.S. digesting sludges and other methanogenic environments. In general, the presence of chloro or nitro groups inhibited anaerobic gas production, while carboxyl and hydroxyl groups facilitated biodegradation. The relationship between substituent position and susceptibility to methanogenic degradation was compound dependent. The following chemicals were completely degraded (≥80% ThGP) at a concentration of 50 mg of carbon per liter: phenol, 2-aminophenol, 4-cresol, catechol, sodium benzoate, 4-aminobenzoic acid, 3-chlorobenzoic acid, phthalic acid, ethylene glycol, diethylene glycol, triethylene glycol, sodium stearate, and quinoline. 3-Cresol, 4-chlorobenzoic acid, dimethyl phthalate, and pyridine were partially degraded. Although the remaining chemicals tested were either persistent or toxic, their behavior may differ at more environmentally realistic chemical-to-biomass ratios. Our findings suggest that biodegradability assessments made with sludge from one source can be extrapolated to sludge from another source with a reasonable degree of confidence and should help in predicting the fate of an organic chemical during the anaerobic digestion of sewage sludge. PMID:16347851

Evaporation and Degradation of a Sessile Droplet of VX on an Impermeable Surface

DTIC Science & Technology

2017-09-01

NOTES 14. ABSTRACT: This report highlights experimental studies into the combined physical and chemical processes that occur when a sessile droplet...resulting chemical change causes a corresponding change in the contact angle and evaporation rate of the sessile droplet on an impermeable surface...for phase separation. 15. SUBJECT TERMS Chemical degradation Phase separation Contact angle 2-(diisopropylamino)ethyl-O-ethyl

Desorption Electrospray Ionization Mass Spectrometry (DESI-MS) Analysis of Organophosphorus Chemical Warfare Agents: Rapid Acquisition of Time-Aligned Parallel (TAP) Fragmentation Data

DTIC Science & Technology

2010-06-01

phase microextraction. Anal. Chem., 69, 1866-72. [39] Sng , M.T. and Ng ,W.F. (1999). In-situ derivatisation of degradation products of chemical warfare...Chromatogr. A., 1141, 151-157. [46] Lee, H.S.N., Sng , M.T., Basheer, C., and Lee, H.K. (2007). Determination of degradation products of chemical

Effect of drying temperatures on structural performance and photocatalytic activity of BiOCl synthesized by a soft chemical method

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

Guang, Lu, E-mail: lu_g@163.com; Hui, Wang; Xuejun, Zou

2016-07-15

A group of BiOCl photocatalysts with different drying temperatures were prepared by a soft chemical method. The effects of drying temperatures on the crystalline phase, morphology, surface area and optical property of as-prepared samples were investigated in detail by XRD, SEM, N{sub 2} absorption–desorption and DRS. Moreover, their photocatalytic activities on the degradation of rhodamine B were evaluated under visible light irradiation. It was found that the sample dried at 120 °C had the best photocatalytic activity, which was mainly attributed to the highest exposing proportion of {001} facets correspond to BiOCl, largest BET and minimum bandgap. The degradation mechanismmore » was explored that superoxide radicals were mainly contributed to the degradation of chromophore, however, holes and hydroxyl were mainly contributed to the photo degradation. Moreover, holes and hydroxyl dominated the degradation of RhB. - Graphical abstract: Holes, hydroxyl and superoxide radicals can attribute to the degradation process but take different degradation pathways. Superoxide radicals mainly contribute to the degradation of chromophore, however, holes and hydroxyl mainly contribute to the photo degradation. Display Omitted - Highlights: • BiOCl nanosheets were prepared by a soft chemical method. • Effect of drying temperatures on as-prepared BiOCl samples was studied. • The highest removal efficiency of RhB was obtained over the sample dried at 120 °C.« less

Sorption and degradation of wastewater-associated pharmaceuticals and personal care products in agricultural soils and sediment.

PubMed

Zhang, Ting; Wu, Bo; Sun, Na; Ye, Yong; Chen, Huaixia

2013-01-01

Pharmaceuticals and personal care products (PPCPs) have drawn popular concerns recently as an emerging class of aquatic contaminants. In this study, adsorption and degradation of four selected PPCPs, metronidazole, tinidazole, caffeine and chloramphenicol, have been investigated in the laboratory using two agricultural soils in China and sediment from Changjiang River. Adsorption tests using a batch equilibrium method demonstrated that adsorption of all tested chemicals in soils could be well described with Freundlich equation, and their adsorption affinity on soil followed the order of chloramphenicol > caffeine > tinidazole > metronidazole. Generally, higher Kf value was associated with soils which had higher organic matter contents (except for caffeine acid in this study). Degradation of selected PPCPs in soils generally followed first-order exponential decay kinetics, and half-lives ranging from 0.97 to 10.21 d. Sterilization generally decreased the degradation rates, indicating that microbial activity played a significant role in the degradation in soils. The degradation rate constant decreased with increasing initial chemical concentrations in soil, implying that the microbial activity was inhibited with high chemical loading levels.

A thermal and chemical degradation approach to decipher pristane and phytane precursors in sedimentary organic matter

USGS Publications Warehouse

Koopmans, M.P.; Rijpstra, W.I.C.; Klapwijk, M.M.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.

1999-01-01

A thermal and chemical degradation approach was followed to determine the precursors of pristane (Pr) and phytane (Ph) in samples from the Gessoso-solfifera, Ghareb and Green River Formations. Hydrous pyrolysis of these samples yields large amounts of Pr and Ph carbon skeletons, indicating that their precursors are predominantly sequestered in high-molecular-weight fractions. However, chemical degradation of the polar fraction and the kerogen of the unheated samples generally does not release large amounts of Pr and Ph. Additional information on the precursors of Pr and Ph is obtained from flash pyrolysis analyses of kerogens and residues after hydrous pyrolysis and after chemical degradation. Multiple precursors for Pr and Ph are recognised in these three samples. The main increase of the Pr/Ph ratio with increasing maturation temperature, which is associated with strongly increasing amounts of Pr and Ph, is probably due to the higher amount of precursors of Pr compared to Ph, and not to the different timing of generation of Pr and Ph.A thermal and chemical degradation approach was followed to determine the precursors of pristane (Pr) and phytane (Ph) in samples from the Gessoso-solfifera, Ghareb and Green River Formations. Hydrous pyrolysis of these samples yields large amounts of Pr and Ph carbon skeletons, indicating that their precursors are predominantly sequestered in high-molecular-weight fractions. However, chemical degradation of the polar fraction and the kerogen of the unheated samples generally does not release large amounts of Pr and Ph. Additional information on the precursors of Pr and Ph is obtained from flash pyrolysis analyses of kerogens and residues after hydrous pyrolysis and after chemical degradation. Multiple precursors for Pr and Ph are recognised in these three samples. The main increase of the Pr/Ph ratio with increasing maturation temperature, which is associated with strongly increasing amounts of Pr and Ph, is probably due to the higher amount of precursors of Pr compared to Ph, and not to the different timing of generation of Pr and Ph.

Detection of the spectroscopic signatures of explosives and their degradation products

NASA Astrophysics Data System (ADS)

Florian, Vivian; Cabanzo, Andrea; Baez, Bibiana; Correa, Sandra; Irrazabal, Maik; Briano, Julio G.; Castro, Miguel E.; Hernandez-Rivera, Samuel P.

2005-06-01

Detection and removal of antipersonnel and antitank landmines is a great challenge and a worldwide enviromental and humanitarian problem. Sensors tuned on the spectroscopic signature of the chemicals released from mines are a potential solution. Enviromental factors (temperature, relative humidity, rainfall precipitation, wind, sun irradiation, pressure, etc.) as well as soil characteristics (water content, compaction, porosity, chemical composition, particle size distribution, topography, vegetation, etc), have a direct impact on the fate and transport of the chemicals released from landmines. Chemicals such as TNT, DNT and their degradation products, are semi-volatile, and somewhat soluble in water. Also, they may adsorb strongly to soil particles, and are susceptible to degradation by microorganisms, light, or chemical agents. Here we show an experimental procedure to quantify the effect of the above variables on the spectroscopic signature. A number of soil tanks under controlled conditions are used to study the effect of temperature, water content, relative humidity and light radiation.

Biodegradation of Mycotoxins: Tales from Known and Unexplored Worlds

PubMed Central

Vanhoutte, Ilse; Audenaert, Kris; De Gelder, Leen

2016-01-01

Exposure to mycotoxins, secondary metabolites produced by fungi, may infer serious risks for animal and human health and lead to economic losses. Several approaches to reduce these mycotoxins have been investigated such as chemical removal, physical binding, or microbial degradation. This review focuses on the microbial degradation or transformation of mycotoxins, with specific attention to the actual detoxification mechanisms of the mother compound. Furthermore, based on the similarities in chemical structure between groups of mycotoxins and environmentally recalcitrant compounds, known biodegradation pathways and degrading organisms which hold promise for the degradation of mycotoxins are presented. PMID:27199907

Photo- and radiation chemical induced degradation of lignin model compounds.

PubMed

Lanzalunga; Bietti, M

2000-07-01

The basic mechanistic aspects of the photo- and radiation chemistry of lignin model compounds (LMCs) are discussed with respect to important processes related to lignin degradation. Several reactions occur after direct irradiation, photosensitized or radiation chemically induced oxidation of LMCs. Direct irradiation studies on LMCs have provided supportive evidence for the involvement of hydrogen abstraction reactions from phenols, beta-cleavage of substituted alpha-aryloxyacetophenones and cleavage of ketyl radicals (formed by photoreduction of aromatic ketones or hydrogen abstraction from arylglycerol beta-aryl ethers) in the photoyellowing of lignin rich pulps. Photosensitized and radiation chemically induced generation of reactive oxygen species and their reaction with LMCs are reviewed. The side-chain reactivity of LMC radical cations, generated by radiation chemical means, is also discussed in relation with the enzymatic degradation of lignin.

Enhanced atrazine degradation is widespread across the United States.

PubMed

Mueller, Thomas C; Parker, Ethan T; Steckel, Larry; Clay, Sharon A; Owen, Micheal Dk; Curran, William S; Currie, Randall; Scott, Robert; Sprague, Christy; Stephenson, Daniel O; Miller, Donnie K; Prostko, Eric P; Grichar, W James; Martin, James; Kruz, L Jason; Bradley, Kevin; Bernards, Mark L; Dotray, Peter; Knezevic, Stevan; Davis, Vince; Klein, Robert

2017-09-01

Atrazine (ATZ) has been a key herbicide for annual weed control in corn, with both a soil and post-emergence vegetation application period. Although enhanced ATZ degradation in soil with a history of ATZ use has been reported, the extent and rate of degradation in the US Corn Belt is uncertain. We show that enhanced ATZ degradation exists across much of the country. Soils from 15 of 16 surveyed states had enhanced ATZ degradation. The average ATZ half-life was only 2.3 days in ATZ history soils, compared with an average 14.5 days in soils with no previous ATZ use, meaning that ATZ degrades an average 6 times faster in soils with previous ATZ use. When ATZ is used for several years, enhanced degradation will undoubtedly change the way ATZ is used in agronomic crops and also its ultimate environmental fate. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

EVALUATING DEGRADATION RATES OF CHLORINATED ORGANICS IN GROUNDWATER USING ANALYTICAL MODELS

EPA Science Inventory

The persistence and fate of organic contaminants in the environment largely depends on their rate of degradation. Most studies of degradation rate are performed in the lab where chemical conditions can be controlled precisely. Unfortunately, literature values for lab degradation ...

Effects of species and season on chemical composition and ruminal crude protein and organic matter degradability of some multi-purpose tree species by West African dwarf rams.

PubMed

Arigbede, O M; Anele, U Y; Südekum, K-H; Hummel, J; Oni, A O; Olanite, J A; Isah, A O

2012-04-01

Seasonal chemical composition and ruminal organic matter (OM) and crude protein (CP) degradabilities were determined in four tropical multi-purpose tree species (MPTS) namely; Pterocarpus santalinoides, Grewia pubescens, Enterolobium cyclocarpum and Leucaena leucocephala. Three West African dwarf (WAD) rams fitted with permanent rumen cannula were used for the degradability trials. Foliage samples were collected four times to represent seasonal variations as follows: January--mid dry; April--late dry; July--mid rainy and October--late rainy seasons. Leaf samples were randomly collected from the trees for estimation of dry matter (DM) and chemical composition. Ruminal in sacco OM and CP degradabilities were estimated from residues in nylon bags. All samples had high CP (161-259 g/kg DM) and moderate fibre concentrations [neutral detergent fibre (without residual ash], 300-501 g/kg DM; acid detergent fibre (without residual ash), 225-409 g/kg DM and acid detergent lignin, 87-179 g/kg DM across seasons. Interaction effects of species and season on chemical composition were highly significant (p = 0.001) except for trypsin inhibitor (p = 0.614). The MPTS recorded more than 60% OM and CP degradability at 24 h, which implied that they were all highly degradable in the rumen. Their incorporation into ruminant feeding systems as dry season forage supplements is therefore recommended. © 2011 Blackwell Verlag GmbH.

Combined use of GIS and environmental indicators for assessment of chemical, physical and biological soil degradation in a Spanish Mediterranean region.

PubMed

de Paz, José-Miguel; Sánchez, Juan; Visconti, Fernando

2006-04-01

Soil is one of the main non-renewable natural resources in the world. In the Valencian Community (Mediterranean coast of Spain), it is especially important because agriculture and forest biomass exploitation are two of the main economic activities in the region. More than 44% of the total area is under agriculture and 52% is forested. The frequently arid or semi-arid climate with rainfall concentrated in few events, usually in the autumn and spring, scarcity of vegetation cover, and eroded and shallow soils in several areas lead to soil degradation processes. These processes, mainly water erosion and salinization, can be intense in many locations within the Valencian Community. Evaluation of soil degradation on a regional scale is important because degradation is incompatible with sustainable development. Policy makers involved in land use planning require tools to evaluate soil degradation so they can go on to develop measures aimed at protecting and conserving soils. In this study, a methodology to evaluate physical, chemical and biological soil degradation in a GIS-based approach was developed for the Valencian Community on a 1/200,000 scale. The information used in this study was obtained from two different sources: (i) a soil survey with more than 850 soil profiles sampled within the Valencian Community, and (ii) the environmental information implemented in the Geo-scientific map of the Valencian Community digitised on an Arc/Info GIS. Maps of physical, chemical and biological soil degradation in the Valencian Community on a 1/200,000 scale were obtained using the methodology devised. These maps can be used to make a cost-effective evaluation of soil degradation on a regional scale. Around 29% of the area corresponding to the Valencian Community is affected by high to very high physical soil degradation, 36% by high to very high biological degradation, and 6% by high to very high chemical degradation. It is, therefore, necessary to draw up legislation and to establish the policy framework for actions focused on preventing soil degradation and conserving its productive potential.

In Vivo Biological Evaluation of High Molecular Weight Multifunctional Acid-Degradable Polymeric Drug Carriers with Structurally Different Ketals.

PubMed

Shenoi, Rajesh A; Abbina, Srinivas; Kizhakkedathu, Jayachandran N

2016-11-14

Understanding the influence of degradable chemical moieties on in vivo degradation, tissue distribution, and excretion is critical for the design of novel biodegradable drug carriers. Polyketals have recently emerged as a promising therapeutic delivery platform due to their ability to degrade under mild acidic intracellular compartments and generation of nontoxic degradation products. However, the effect of chemical structure of the ketal groups on the in vivo degradation, biodistribution, and pharmacokinetics of water-soluble ketal-containing polymers has not been explored. In the present work, we synthesized high molecular weight, water-soluble biodegradable hyperbranched polyglycerols (BHPGs) through the incorporation of structurally different ketal groups into the main chain of highly biocompatible polyglycerols. BHPGs showed pH and ketal group structure dependent degradation in buffer solutions. When the polymers were intravenously administered in mice, a strong dependence of in vivo degradation, biodistribution, and clearance on the ketal group structure was observed. All the BHPGs demonstrated degradation and clearance in vivo, with minimal tissue accumulation. Interestingly, an unanticipated degradation behavior of BHPGs with structurally different ketal groups was observed in vivo in comparison to their degradation in buffer solutions. BHPGs with cyclohexyl ketal (CHK) and cyclopentyl ketal (CPK) groups degraded much faster and were cleared from circulation much rapidly, while BHPG with glycerol hydroxy butanone ketal (GHBK) group degraded at a much slower rate and exhibited similar plasma half-life as that of nondegradable HPG. BHPG-GHBK also showed significantly lower tissue accumulation than nondegradable HPG after 30 days of administration. The difference in in vivo degradation may be attributed to the difference in hydrophobic characteristics of different ketal containing polymers, which may change their interaction with proteins and cells in vivo. This is the first study that demonstrates the influence of chemical structure of ketal groups on in vivo degradation and circulation profile of polymers, and through proper surface modifications, these polymers would be useful as multifunctional drug carriers.

Effect of various gases and chemical catalysts on phenol degradation pathways by pulsed electrical discharges.

PubMed

Shen, Yongjun; Lei, Lecheng; Zhang, Xingwang; Zhou, Minghua; Zhang, Yi

2008-02-11

The processes of phenol degradation by pulsed electrical discharges were investigated under several kinds of discharge atmospheres (oxygen, argon, nitrogen and ozone) and chemical catalysts (ferrous ion and hydrogen peroxide). The temporal variations of the concentrations of phenol and the intermediate products were monitored by HPLC and GC-MS, respectively. It has been found that the effect of various gases bubbling on phenol degradation rate ranked in the following order: oxygen-containing ozone>oxygen>argon>nitrogen. The high gas bubbling flow rate was beneficial to the removal of phenol. It was found that the degradation proceeded differently when in the presence and absence of catalysts. The phenol removal rate was increased when ferrous ion was added. This considerable enhancement may be due to the Fenton's reaction. What's more, putting the chemical additives hydrogen peroxide into the reactor led to a dramatic increase in phenol degradation rate. The mechanism was due to the direct or indirect photolysis and pyrolysis destruction in plasma channel. Furthermore, the intermediate products were monitored by GC-MS under three degradation conditions. More THBs were generated under degradation conditions without gases bubbling or adding any catalyst, and more DHBs under the condition of adding ferrous ion, and more carboxylic acids under the condition of oxygen-containing ozone gas bubbling. Consequently, three distinct degradation pathways based on different conditions were proposed.

Fast degradation of dyes in water using manganese-oxide-coated diatomite for environmental remediation

NASA Astrophysics Data System (ADS)

Dang, Trung-Dung; Banerjee, Arghya Narayan; Tran, Quang-Tung; Roy, Sudipta

2016-11-01

By a simple wet-chemical procedure using a permanganate in the acidic medium, diatomite coated with amorphous manganese oxide nanoparticles was synthesized. The structural, microstructural and morphological characterizations of the as-synthesized catalysts confirmed the nanostructure of MnO2 and its stabilization on the support - diatomite. The highly efficient and rapid degradation of methylene blue and methyl orange over synthesized MnO2 coated Diatomite has been carried out. The results revealed considerably faster degradation of the dyes against the previously reported data. The proposed mechanism of the dye-degradation is considered to be a combinatorial effect of chemical, physicochemical and physical processes. Therefore, the fabricated catalysts have potential application in waste water treatment, and pollution degradation for environmental remediation.

Synergistic enzymatic and microbial lignin conversion

DOE PAGES

Zhao, Cheng; Xie, Shangxian; Pu, Yunqiao; ...

2015-10-02

We represent the utilization of lignin for fungible fuels and chemicals and it's one of the most imminent challenges in modern biorefineries. However, bioconversion of lignin is highly challenging due to its recalcitrant nature as a phenolic heteropolymer. This study addressed the challenges by revealing the chemical and biological mechanisms for synergistic lignin degradation by a bacterial and enzymatic system, which significantly improved lignin consumption, cell growth and lipid yield. The Rhodococcus opacus cell growth increased exponentially in response to the level of laccase treatment, indicating the synergy between laccase and bacterial cells in lignin degradation. Other treatments like ironmore » and hydrogen peroxide showed limited impact on cell growth. Chemical analysis of lignin under various treatments further confirmed the synergy between laccase and cells at the chemical level. 31P nuclear magnetic resonance (NMR) suggested that laccase, R. opacus cell and Fenton reaction reagents promoted the degradation of different types of lignin functional groups, elucidating the chemical basis for the synergistic effects. 31P NMR further revealed that laccase treatment had the most significant impact for degrading the abundant chemical groups. The results were further confirmed by the molecular weight analysis and lignin quantification by the Prussian blue assay. The cell–laccase fermentation led to a 17-fold increase of lipid production. Overall, the study indicated that laccase and R. opacus can synergize to degrade lignin efficiently, likely through rapid utilization of monomers generated by laccase to promote the reaction toward depolymerization. The study provided a potential path for more efficient lignin conversion and development of consolidated lignin conversion.« less

Synergistic enzymatic and microbial lignin conversion

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

Zhao, Cheng; Xie, Shangxian; Pu, Yunqiao

We represent the utilization of lignin for fungible fuels and chemicals and it's one of the most imminent challenges in modern biorefineries. However, bioconversion of lignin is highly challenging due to its recalcitrant nature as a phenolic heteropolymer. This study addressed the challenges by revealing the chemical and biological mechanisms for synergistic lignin degradation by a bacterial and enzymatic system, which significantly improved lignin consumption, cell growth and lipid yield. The Rhodococcus opacus cell growth increased exponentially in response to the level of laccase treatment, indicating the synergy between laccase and bacterial cells in lignin degradation. Other treatments like ironmore » and hydrogen peroxide showed limited impact on cell growth. Chemical analysis of lignin under various treatments further confirmed the synergy between laccase and cells at the chemical level. 31P nuclear magnetic resonance (NMR) suggested that laccase, R. opacus cell and Fenton reaction reagents promoted the degradation of different types of lignin functional groups, elucidating the chemical basis for the synergistic effects. 31P NMR further revealed that laccase treatment had the most significant impact for degrading the abundant chemical groups. The results were further confirmed by the molecular weight analysis and lignin quantification by the Prussian blue assay. The cell–laccase fermentation led to a 17-fold increase of lipid production. Overall, the study indicated that laccase and R. opacus can synergize to degrade lignin efficiently, likely through rapid utilization of monomers generated by laccase to promote the reaction toward depolymerization. The study provided a potential path for more efficient lignin conversion and development of consolidated lignin conversion.« less

Fracture Fluid Additive and Formation Degradations

EPA Pesticide Factsheets

This presentation is on reactions that describe the degradation of fracturing fluids & formations during the hydraulic fracturing process & the clean‐up period. It contains a description of primary chemical reaction controls, & common degradation reactions

Open circuit voltage durability study and model of catalyst coated membranes at different humidification levels

NASA Astrophysics Data System (ADS)

Kundu, Sumit; Fowler, Michael W.; Simon, Leonardo C.; Abouatallah, Rami; Beydokhti, Natasha

Fuel cell material durability is an area of extensive research today. Chemical degradation of the ionomer membrane is one important degradation mechanism leading to overall failure of fuel cells. This study examined the effects of relative humidity on the chemical degradation of the membrane during open circuit voltage testing. Five Gore™ PRIMEA ® series 5510 catalyst coated membranes were degraded at 100%, 75%, 50%, and 20% RH. Open circuit potential and cumulative fluoride release were monitored over time. Additionally scanning electron microscopy images were taken at end of the test. The results showed that with decreasing RH fluoride release rate increased as did performance degradation. This was attributed to an increase in gas crossover with a decrease in RH. Further, it is also shown that interruptions in testing may heavily influence cumulative fluoride release measurements where frequent stoppages in testing will cause fluoride release to be underestimated. SEM analysis shows that degradation occurred in the ionomer layer close to the cathode catalyst. A chemical degradation model of the ionomer membrane was used to model the results. The model was able to predict fluoride release trends, including the effects of interruptions, showing that changes in gas crossover with RH could explain the experimental results.

Effect of ultrasonic frequency on degradation of methylene blue in the presence of particle

NASA Astrophysics Data System (ADS)

Kobayashi, Daisuke; Suzuki, Atsushi; Takahashi, Tomoki; Matsumoto, Hideyuki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

2012-05-01

Techniques for the degradation of hazardous organic compounds have been investigated such as solvent extraction, incineration, chemical dehalogenation and biodegradation, etc. Ultrasound has been found to be an attractive advanced technology for the degradation of hazardous organic compounds in water. In addition, the sonochemical reaction is enhanced by particle addition. However, the enhancement mechanism of particle addition has not been investigated well, because ultrasound enhances not only chemical reaction but also mass transfer. In this study, the degradation process of methylene blue as the model hazardous organic compound by ultrasonic irradiation was investigated. The effects of ultrasonic irradiation condition on degradation rate were investigated. The effect of ultrasonic frequency on improvement of degradation reaction by particle addition was also investigated. In addition, the effects of ultrasonic frequency on ultrasonic power and chemical efficiency were investigated by calorimetry and SE value. The degradation rate constants were estimated from the results of temporal change of the concentration of methylene blue assuming first order kinetics for the decomposition. There was a linear relation in the degradation rate and the ultrasonic power. In addition, the degradation rates at 127 kHz and 490 kHz were much larger than that at 22.8 kHz. The effect of ultrasonic frequency on sonochemical efficiency has been investigated, and the sonochemical effects in the range of frequency of 200 - 500 kHz are 10 times larger than those in the lower or higher frequency regions. Therefore, the degradation rate of methylene blue was considered to estimate using sonochemical efficiency. The degradation process of methylene blue was intensified by particle addition, and the degradation rate increased with increasing amount of particle. On the other hand, the enhancement of degradation rate by particle addition was influenced by both ultrasonic frequency and species of particle. The relationship between particle size and resonance diameter of ultrasound is considered to influence the enhancement of ultrasonic degradation process.

Adaptation of the Conditions of US EPA Method 538 for the ...

EPA Pesticide Factsheets

Report The objective of this study was to evaluate U.S. EPA’s Method 538 for the assessment of drinking water exposure to the nerve agent degradation product, EA2192, the most toxic degradation product of nerve agent VX. As a result of the similarities in sample preparation and analysis that Method 538 uses for nonvolatile chemicals, this method is applicable to the nonvolatile Chemical Warfare Agent (CWA) degradation product, EA2192, in drinking water. The method may be applicable to other nonvolatile CWAs and their respective degradation products as well, but the method will need extensive testing to verify compatibility. Gaps associated with the need for analysis methods capable of analyzing such analytes were addressed by adapting the EPA 538 method for this CWA degradation product. Many laboratories have the experience and capability to run the already rigorous method for nonvolatile compounds in drinking water. Increasing the number of laboratories capable of carrying out these methods serves to significantly increase the surge laboratory capacity to address sample throughput during a large exposure event. The approach desired for this study was to start with a proven high performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) method for nonvolatile chemicals in drinking water and assess the inclusion of a similar nonvolatile chemical, EA2192.

Analysis of the Precursors, Simulants and Degradation Products of Chemical Warfare Agents.

PubMed

Witkiewicz, Zygfryd; Neffe, Slawomir; Sliwka, Ewa; Quagliano, Javier

2018-09-03

Recent advances in analysis of precursors, simulants and degradation products of chemical warfare agents (CWA) are reviewed. Fast and reliable analysis of precursors, simulants and CWA degradation products is extremely important at a time, when more and more terrorist groups and radical non-state organizations use or plan to use chemical weapons to achieve their own psychological, political and military goals. The review covers the open source literature analysis after the time, when the chemical weapons convention had come into force (1997). The authors stated that during last 15 years increased number of laboratories are focused not only on trace analysis of CWA (mostly nerve and blister agents) in environmental and biological samples, but the growing number of research are devoted to instrumental analysis of precursors and degradation products of these substances. The identification of low-level concentration of CWA degradation products is often more important and difficult than the original CWA, because of lower level of concentration and a very large number of compounds present in environmental and biological samples. Many of them are hydrolysis products and are present in samples in the ionic form. For this reason, two or three instrumental methods are used to perform a reliable analysis of these substances.

Chemical structure-based predictive model for methanogenic anaerobic biodegradation potential.

PubMed

Meylan, William; Boethling, Robert; Aronson, Dallas; Howard, Philip; Tunkel, Jay

2007-09-01

Many screening-level models exist for predicting aerobic biodegradation potential from chemical structure, but anaerobic biodegradation generally has been ignored by modelers. We used a fragment contribution approach to develop a model for predicting biodegradation potential under methanogenic anaerobic conditions. The new model has 37 fragments (substructures) and classifies a substance as either fast or slow, relative to the potential to be biodegraded in the "serum bottle" anaerobic biodegradation screening test (Organization for Economic Cooperation and Development Guideline 311). The model correctly classified 90, 77, and 91% of the chemicals in the training set (n = 169) and two independent validation sets (n = 35 and 23), respectively. Accuracy of predictions of fast and slow degradation was equal for training-set chemicals, but fast-degradation predictions were less accurate than slow-degradation predictions for the validation sets. Analysis of the signs of the fragment coefficients for this and the other (aerobic) Biowin models suggests that in the context of simple group contribution models, the majority of positive and negative structural influences on ultimate degradation are the same for aerobic and methanogenic anaerobic biodegradation.

Chemical approaches to targeted protein degradation through modulation of the ubiquitin-proteasome pathway.

PubMed

Collins, Ian; Wang, Hannah; Caldwell, John J; Chopra, Raj

2017-03-15

Manipulation of the ubiquitin-proteasome system to achieve targeted degradation of proteins within cells using chemical tools and drugs has the potential to transform pharmacological and therapeutic approaches in cancer and other diseases. An increased understanding of the molecular mechanism of thalidomide and its analogues following their clinical use has unlocked small-molecule modulation of the substrate specificity of the E3 ligase cereblon (CRBN), which in turn has resulted in the advancement of new immunomodulatory drugs (IMiDs) into the clinic. The degradation of multiple context-specific proteins by these pleiotropic small molecules provides a means to uncover new cell biology and to generate future drug molecules against currently undruggable targets. In parallel, the development of larger bifunctional molecules that bring together highly specific protein targets in complexes with CRBN, von Hippel-Lindau, or other E3 ligases to promote ubiquitin-dependent degradation has progressed to generate selective chemical compounds with potent effects in cells and in vivo models, providing valuable tools for biological target validation and with future potential for therapeutic use. In this review, we survey recent breakthroughs achieved in these two complementary methods and the discovery of new modes of direct and indirect engagement of target proteins with the proteasome. We discuss the experimental characterisation that validates the use of molecules that promote protein degradation as chemical tools, the preclinical and clinical examples disclosed to date, and the future prospects for this exciting area of chemical biology. © 2017 The Author(s).

Chemical dispersants enhance the activity of oil- and gas condensate-degrading marine bacteria.

PubMed

Tremblay, Julien; Yergeau, Etienne; Fortin, Nathalie; Cobanli, Susan; Elias, Miria; King, Thomas L; Lee, Kenneth; Greer, Charles W

2017-12-01

Application of chemical dispersants to oil spills in the marine environment is a common practice to disperse oil into the water column and stimulate oil biodegradation by increasing its bioavailability to indigenous bacteria capable of naturally metabolizing hydrocarbons. In the context of a spill event, the biodegradation of crude oil and gas condensate off eastern Canada is an essential component of a response strategy. In laboratory experiments, we simulated conditions similar to an oil spill with and without the addition of chemical dispersant under both winter and summer conditions and evaluated the natural attenuation potential for hydrocarbons in near-surface sea water from the vicinity of crude oil and natural gas production facilities off eastern Canada. Chemical analyses were performed to determine hydrocarbon degradation rates, and metagenome binning combined with metatranscriptomics was used to reconstruct abundant bacterial genomes and estimate their oil degradation gene abundance and activity. Our results show important and rapid structural shifts in microbial populations in all three different oil production sites examined following exposure to oil, oil with dispersant and dispersant alone. We found that the addition of dispersant to crude oil enhanced oil degradation rates and favored the abundance and expression of oil-degrading genes from a Thalassolituus sp. (that is, metagenome bin) that harbors multiple alkane hydroxylase (alkB) gene copies. We propose that this member of the Oceanospirillales group would be an important oil degrader when oil spills are treated with dispersant.

Backbone-Degradable Polymers Prepared by Chemical Vapor Deposition.

PubMed

Xie, Fan; Deng, Xiaopei; Kratzer, Domenic; Cheng, Kenneth C K; Friedmann, Christian; Qi, Shuhua; Solorio, Luis; Lahann, Joerg

2017-01-02

Polymers prepared by chemical vapor deposition (CVD) polymerization have found broad acceptance in research and industrial applications. However, their intrinsic lack of degradability has limited wider applicability in many areas, such as biomedical devices or regenerative medicine. Herein, we demonstrate, for the first time, a backbone-degradable polymer directly synthesized via CVD. The CVD co-polymerization of [2.2]para-cyclophanes with cyclic ketene acetals, specifically 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), results in well-defined, hydrolytically degradable polymers, as confirmed by FTIR spectroscopy and ellipsometry. The degradation kinetics are dependent on the ratio of ketene acetals to [2.2]para-cyclophanes as well as the hydrophobicity of the films. These coatings address an unmet need in the biomedical polymer field, as they provide access to a wide range of reactive polymer coatings that combine interfacial multifunctionality with degradability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gibberellic acid promoting phytic acid degradation in germinating soybean under calcium lactate treatment.

PubMed

Hui, Qianru; Wang, Mian; Wang, Pei; Ma, Ya; Gu, Zhenxin; Yang, Runqiang

2018-01-01

Phytic acid as a phosphorus storage vault provides phosphorus for plant development. It is an anti-nutritional factor for humans and some animals. However, its degradation products lower inositol phosphates have positive effects on human health. In this study, the effect of gibberellic acid (GA) on phytic acid degradation under calcium lactate (Ca) existence was investigated. The results showed that Ca + GA treatment promoted the growth status, hormone metabolism and phytic acid degradation in germinating soybean. At the same time, the availability of phosphorus, the activity of phytic acid degradation-associated enzyme and phosphoinositide-specific phospholipase C (PI-PLC) increased. However, the relative genes expression of phytic acid degradation-associated enzymes did not vary in accordance with their enzymes activity. The results revealed that GA could mediate the transport and function of calcium and a series of physiological and biochemical changes to regulate phytic acid degradation of soybean sprouts. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Chemical Degradation of the Cathodic Electrical Contact Between Carbon and Cast Iron in Aluminum Production Cells

NASA Astrophysics Data System (ADS)

Brassard, Martin; Désilets, Martin; Soucy, Gervais; Bilodeau, Jean-François; Forté, Martin

2017-06-01

The cathodic carbon to cast iron electrical contact degradation is one of the factors to consider in the cathode voltage drop (CVD) increase over the lifetime of aluminum production cells. Lab-scale experiments were carried out to study the cast iron to carbon interface chemical degradation and the impact of important cell parameters like temperature and bath chemistry. Laboratory degradation results were compared with industrial samples. A thermoelectric Ansys numerical model was then used to predict the effect of cast iron surface degradation over CVD. Results show that the aluminum formation on the cast iron surface and its subsequent diffusion creates an immiscible mixture of Fe-Al metal alloy and electrolytic bath. Disparities were also observed between industrial samples taken from two different technologies, suggesting that the degradation can be slowed down. Thermoelectric calculations finally revealed that the impact of the contact resistance augmentation is by far greater than the cast iron degradation.

Assessment of potential soil degradation on agricultural land in the czech republic.

PubMed

Šarapatka, Bořivoj; Bednář, Marek

2015-01-01

Many attempts have been made worldwide to develop methods to identify the areas most threatened by soil degradation. Some soils in afflicted areas may be irreversibly degraded and thus have very little resilience (the ability to restore themselves). For the purpose of assessing the current state of soil degradation in the Czech Republic (CZ) we have developed an overall indicator of land vulnerability to the threat of soil degradation on the basis of individual factors that contribute to soil degradation and are monitored on a long-term basis in various research worksites in the CZ. Individual degradation factors were divided into two groups: chemical and physical degradation. On the basis of principal component analysis, individual degradation factors were assigned a specific weight of influence. With the use of a GIS, the input factors of degradation were combined to create maps of chemical and physical soil degradation, and consequently a map of overall degradation-threatened soils for the CZ, along with a map of areas differentiated according to the prevailing type of degradation. Results showed that, at present, the most important degradation factor in the CZ is water erosion, followed by loss of organic matter. Statistical analysis showed that approximately 51% of agricultural land is moderately threatened in the CZ. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Modelling of chemical degradation of blended cement-based materials by leaching cycles with Callovo-Oxfordian porewater

NASA Astrophysics Data System (ADS)

Olmeda, Javier; Henocq, Pierre; Giffaut, Eric; Grivé, Mireia

2017-06-01

The present work describes a thermodynamic model based on pore water replacement cycles to simulate the chemical evolution of blended cement (BFS + FA) by interaction with external Callovo-Oxfordian (COx) pore water. In the framework of the radioactive waste management, the characterization of the radionuclide behaviour (solubility/speciation, adsorption) in cementitious materials needs to be done for several chemical degradation states (I to IV). In particular, in the context of the deep geological radioactive waste disposal project (Cigéo), cement-based materials will be chemically evolved with time in contact with the host-rock (COx formation). The objective of this study is to provide an equilibrium solution composition for each degradation state for a CEM-V cement-based material to support the adsorption and diffusion experiments reproducing any state of degradation. Calculations have been performed at 25 °C using the geochemical code PhreeqC and an up-to-date thermodynamic database (ThermoChimie v.9.0.b) coupled to SIT approach for ionic strength correction. The model replicates experimental data with accuracy. The approach followed in this study eases the analysis of the chemical evolution in both aqueous and solid phase to obtain a fast assessment of the geochemical effects associated to an external water intrusion of variable composition on concrete structures.

Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses.

PubMed

Kumpiene, Jurate; Robinson, Ryan; Brännvall, Evelina; Nordmark, Désirée; Bjurström, Henrik; Andreas, Lale; Lagerkvist, Anders; Ecke, Holger

2011-01-01

Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

EPA Science Inventory

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

Finding Hidden Chemistry in Ancient Egyptian Artifacts: Pigment Degradation Taught in a Chemical Engineering Course

ERIC Educational Resources Information Center

Gime´nez, Javier

2015-01-01

The main objective of this work was to show the application of the study of ancient technology and science on teaching (and learning) chemistry in Chemical Engineering Undergraduate studies. Degradation patterns of pigments used in Ancient Egypt were incorporated in the syllabus of the course entitled "Technological and Scientific…

Enhancing the effectiveness of polyoxyethylene in the filtration of flotation concentrate. [With polyoxyethylene

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

Baichenko, A.A.; Kaminskii, V.S.; Sokolova, V.S.

1977-01-01

Laboratory data are presented on the degradation of polyoxyethylene during storage and under mechanical and chemical action. Provided the physico-chemical properties of the polymer are considered and conditions are adjusted to minimize its degradation during solution preparation, POE can be used as a highly effective flocculant for the commercial filtration of flotation concentrate.

Report: More Information Is Needed On Toxaphene Degradation Products

EPA Pesticide Factsheets

Report #2006-P-00007, Dec 16, 2005. Toxaphene in the environment changes, or degrades. The degradation products are different from the original toxaphene in chemical composition and how they appear to testing instruments, so they could go unreported.

Soil Degradation: A North American perspective

USDA-ARS?s Scientific Manuscript database

Soil can be degraded through erosion and formation of undesirable physical, chemical, or biological properties due to industrialization or use of inappropriate farming practices that supersede natural regeneration. Soil degradation reflects unsustainable resource management that is global in scope a...

Modelling chemical degradation of concrete during leaching with rain and soil water types

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

Jacques, D., E-mail: djacques@sckcen.b; Wang, L.; Martens, E.

2010-08-15

Percolation of external water through concrete results in the degradation of cement and changes the concrete pore water and solid phase composition. The assessment of long-term degradation of concrete is possible by means of model simulation. This paper describes simulations of chemical degradation of cement for different types of rain and soil water at an ambient earth surface temperature (10 {sup o}C). Rain and soil water types were derived using generic equations and measurement of atmospheric boundary conditions representative for North-Belgium. An up-to-date and consistent thermodynamic model is used to calculate the geochemical changes during chemical degradation of the concrete.more » A general pattern of four degradation stages was simulated with the third stage being the geochemically most complex stage involving reactions with calcium-silicate hydrates, AFm and AFt phases. Whereas the sequence of the dissolution reactions was relatively insensitive to the composition of the percolating water, the duration of the different reactions depends strongly on the percolating water composition. Major identified factors influencing the velocity of cement degradation are the effect of dry deposition and biological activity increasing the partial pressure of CO{sub 2(g)} in the soil air phase (and thus increasing the inorganic carbon content in the percolating water). Soil weathering processes have only a minor impact, at least for the relatively inert sandy material considered in this study.« less

Shining light on the differences in molecular structural chemical makeup and the cause of distinct degradation behavior between malting- and feed-type barley using synchrotron FTIR microspectroscopy: a novel approach.

PubMed

Yu, Peiqiang; Doiron, Kevin; Liu, Dasen

2008-05-14

The objective of this study was to use advanced synchrotron-sourced FTIR microspectroscopy (SFTIRM) as a novel approach to identify the differences in protein and carbohydrate molecular structure (chemical makeup) between these two varieties of barley and illustrate the exact causes for their significantly different degradation kinetics. Items assessed included (1) molecular structural differences in protein amide I to amide II intensities and their ratio within cellular dimensions, (2) molecular structural differences in protein secondary structure profile and their ratios, and (3) molecular structural differences in carbohydrate component peak profile. Our hypothesis was that molecular structure (chemical makeup) affects barley quality, fermentation, and degradation behavior in both humans and animals. Using SFTIRM, the protein and carbohydrate molecular structural chemical makeup of barley was revealed and identified. The protein molecular structural chemical makeup differed significantly between the two varieties of barleys. No difference in carbohydrate molecular structural chemical makeup was detected. Harrington was lower than Valier in protein amide I, amide II, and protein amide I to amide II ratio, while Harrington was relatively higher in model-fitted protein alpha-helix and beta-sheet, but lower in the others (beta-turn and random coil). These results indicated that it is the molecular structure of protein (chemical makeup) that may play a major role in the different degradation kinetics between the two varieties of barleys (not the molecular structure of carbohydrate). It is believed that use of the advanced synchrotron technology will make a significant step and an important contribution to research in examining the molecular structure (chemical makeup) of plant, feed, and seeds.

Influence of the hydrophilic head size and hydrophobic tail length of surfactants on the ability of micelles to stabilize citral.

PubMed

Hong, Chi Rac; Park, Sung Joon; Choi, Seung Jun

2016-07-01

Surfactant-made micelles can control the rate of chemical degradation of poorly water-soluble food flavors. To evaluate how the molecular structure of surfactant has an influence on the chemical decomposition rate of citral, micelles were prepared with polyoxyethylene alkyl ether-type surfactants that had similar molecular structures but various hydrophilic head sizes and hydrophobic tail lengths. At a critical 20× micelle concentration of surfactant, there was no significant difference in the chemical degradation rate of citral in micelles in neutral pH, regardless of the hydrophilic head size or hydrophobic tail length. In an acidic environment, the degradation rate constant of citral generally increased proportionally with increasing hydrophilic head size of surfactant (0.1563 and 0.2217 for surfactants with 23 and 100 oxyethylene units, respectively) but the length of hydrophobic tail did not affect the citral stability. Also, little difference (0.2217 and 0.2265 for surfactant having 100 oxyethylene units with and without Fe(3+) ) in degradation rate constant of citral between simple micellar solution and micellar solution containing iron suggested that iron ions could not accelerate citral degradation in micelles, regardless of the form of iron (Fe(2+) and Fe(3+) ). This work concludes that although the concentration of surfactant could be relevant, if its concentration could be controlled in the same manner as the critical micelle concentration, then a polyethylene alkyl ether-type surfactant with a small hydrophilic head could more efficiently stabilize citral at an acidic pH. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Influence of organic matter, nutrients, and cyclodextrin on microbial and chemical herbicide and degradate dissipation in subsurface sediment slurries.

PubMed

Kerminen, Kaisa; Le Moël, Romain; Harju, Vilhelmiina; Kontro, Merja H

2018-03-15

Pesticides leaching from soil to surface and groundwater are a global threat for drinking water safety, as no cleaning methods occur for groundwater environment. We examined whether peat, compost-peat-sand (CPS) mixture, NH 4 NO 3 , NH 4 NO 3 with sodium citrate (Na-citrate), and the surfactant methyl-β-cyclodextrin additions enhance atrazine, simazine, hexazinone, dichlobenil, and the degradate 2,6-dichlorobenzamide (BAM) dissipations in sediment slurries under aerobic and anaerobic conditions, with sterilized controls. The vadose zone sediment cores were drilled from a depth of 11.3-14.6m in an herbicide-contaminated groundwater area. The peat and CPS enhanced chemical atrazine and simazine dissipation, and the peat enhanced chemical hexazinone dissipation, all oxygen-independently. Dichlobenil dissipated under all conditions, while BAM dissipation was fairly slow and half-lives could not be calculated. The chemical dissipation rates could be associated with the chemical structures and properties of the herbicides, and additive compositions, not with pH. Microbial atrazine degradation was only observed in the Pseudomonas sp. ADP amended slurries, although the sediment slurries were known to contain atrazine-degrading microorganisms. The bioavailability of atrazine in the water phase seemed to be limited, which could be due to complex formation with organic and inorganic colloids. Atrazine degradation by indigenous microbes could not be stimulated by the surfactant methyl-β-cyclodextrin, or by the additives NH 4 NO 3 and NH 4 NO 3 with Na-citrate, although the nitrogen additives increased microbial growth. Copyright © 2017 Elsevier B.V. All rights reserved.

Biochemical stabilization of glucagon at alkaline pH.

PubMed

Caputo, Nicholas; Jackson, Melanie A; Castle, Jessica R; El Youssef, Joseph; Bakhtiani, Parkash A; Bergstrom, Colin P; Carroll, Julie M; Breen, Matthew E; Leonard, Gerald L; David, Larry L; Roberts, Charles T; Ward, W Kenneth

2014-11-01

For patients with type 1 diabetes mellitus, a bihormonal artificial endocrine pancreas system utilizing glucagon and insulin has been found to stabilize glycemic control. However, commercially available formulations of glucagon cannot currently be used in such systems because of physical instability characterized by aggregation and chemical degradation. Storing glucagon at pH 10 blocks protein aggregation but results in chemical degradation. Reductions in pH minimize chemical degradation, but even small reductions increase protein aggregation. We hypothesized that common pharmaceutical excipients accompanied by a new excipient would inhibit glucagon aggregation at an alkaline pH. As measured by tryptophan intrinsic fluorescence shift and optical density at 630 nm, protein aggregation was indeed minimized when glucagon was formulated with curcumin and albumin. This formulation also reduced chemical degradation, measured by liquid chromatography with mass spectrometry. Biological activity was retained after aging for 7 days in an in vitro cell-based bioassay and also in Yorkshire swine. Based on these findings, a formulation of glucagon stabilized with curcumin, polysorbate-80, l-methionine, and albumin at alkaline pH in glycine buffer may be suitable for extended use in a portable pump in the setting of a bihormonal artificial endocrine pancreas.

Biochemical Stabilization of Glucagon at Alkaline pH

PubMed Central

Jackson, Melanie A.; Castle, Jessica R.; El Youssef, Joseph; Bakhtiani, Parkash A.; Bergstrom, Colin P.; Carroll, Julie M.; Breen, Matthew E.; Leonard, Gerald L.; David, Larry L.; Roberts, Charles T.; Ward, W. Kenneth

2014-01-01

Abstract Background: For patients with type 1 diabetes mellitus, a bihormonal artificial endocrine pancreas system utilizing glucagon and insulin has been found to stabilize glycemic control. However, commercially available formulations of glucagon cannot currently be used in such systems because of physical instability characterized by aggregation and chemical degradation. Storing glucagon at pH 10 blocks protein aggregation but results in chemical degradation. Reductions in pH minimize chemical degradation, but even small reductions increase protein aggregation. We hypothesized that common pharmaceutical excipients accompanied by a new excipient would inhibit glucagon aggregation at an alkaline pH. Methods and Results: As measured by tryptophan intrinsic fluorescence shift and optical density at 630 nm, protein aggregation was indeed minimized when glucagon was formulated with curcumin and albumin. This formulation also reduced chemical degradation, measured by liquid chromatography with mass spectrometry. Biological activity was retained after aging for 7 days in an in vitro cell-based bioassay and also in Yorkshire swine. Conclusions: Based on these findings, a formulation of glucagon stabilized with curcumin, polysorbate-80, l-methionine, and albumin at alkaline pH in glycine buffer may be suitable for extended use in a portable pump in the setting of a bihormonal artificial endocrine pancreas. PMID:24968220

[Analysis of the character of film decomposition of methyl methacrylate (MMA) coated urea by infrared spectrum].

PubMed

Li, Dong-po; Wu, Zhi-jie; Liang, Cheng-hua; Chen, Li-jun; Zhang, Yu-lan; Nie, Yan-xi

2012-03-01

The degradability characteristics of film with 4 kinds of methyl methacrylate coated urea amended with inhibitors were analyzed by FITR, which was purposed to supply theoretical basis for applying the FITR analysis method to film decomposition and methyl methacrylate coated urea fertilizers on farming. The result showed that the chemical component, molecule structure and material form of the membrane were not changed because of adding different inhibitors to urea. the main peaks of expressing film degradation process were brought by the -C-H of CH3 & CH2, -OH, C-O, C-C, C-O-C, C=O, C=C flexing vibrancy in asymmetry and symmetry in 3 479-3 195, 2 993--2 873, 1 741-1 564, 1 461-925 and 850-650 cm(-1). The peak value changed from smooth to tip, and from width to narrow caused by chemical structural transform of film The infrared spectrum of 4 kinds of fertilizers was not different remarkably before 60 days, and the film was slowly degraded. But degradation of the film was expedited after 60 days, it was most quickened at 120 day, and the decomposition rate of film was decreased at 310 day. The substantiality change of film in main molecule structure of 4 kinds of fertilizers didn't happen in 310 days. The main component of film materials was degraded most slowly in brown soil. The speed of film degradation wasn't heavily impacted by different inhibitors. The characteristic of film degradation may be monitored entirely by infrared spectrum. The degradation dynamic, chemical structure change, degradation speed difference of the film could be represented through infrared spectrum.

Molecular building blocks and their architecture in biologically/environmentally compatible soft matter chemical machinery.

PubMed

Toyota, Taro; Banno, Taisuke; Nitta, Sachiko; Takinoue, Masahiro; Nomoto, Tomonori; Natsume, Yuno; Matsumura, Shuichi; Fujinami, Masanori

2014-01-01

This review briefly summarizes recent developments in the construction of biologically/environmentally compatible chemical machinery composed of soft matter. Since environmental and living systems are open systems, chemical machinery must continuously fulfill its functions not only through the influx and generation of molecules but also via the degradation and dissipation of molecules. If the degradation or dissipation of soft matter molecular building blocks and biomaterial molecules/polymers can be achieved, soft matter particles composed of them can be used to realize chemical machinery such as selfpropelled droplets, drug delivery carriers, tissue regeneration scaffolds, protocell models, cell-/tissuemarkers, and molecular computing systems.

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

NASA Astrophysics Data System (ADS)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

Analyzing the Limitations and the Applicability Domain of Water-Sediment Transformation Tests like OECD 308.

PubMed

Ter Horst, Mechteld M S; Koelmans, Albert A

2016-10-04

The assessment of chemical degradation rates from water-sediment experiments like for instance OECD 308 is challenging due to parallel occurrence of processes like degradation, sorption and diffusive transport, at different rates in water and sediment or at their interface. To systematically and quantitatively analyze this limitation, we generated artificial experiment data sets using model simulations and then used these data sets in an inverse modeling exercise to estimate degradation half-lives in water and sediment (DegT50 wat and DegT50 sed ), which then were evaluated against their true values. Results were visualized by chemical space diagrams that identified those substance property combinations for which the OECD 308 test is fundamentally inappropriate. We show that the uncertainty in estimated degradation half-lives in water increases as the process of diffusion to the sediment becomes dominant over degradation in the water. We show that in theory the uncertainty in the estimated DegT50 sed is smaller than the uncertainty in the DegT50 wat . The predictive value of our chemical space diagrams was validated using literature transformation rates and their uncertainties that were inferred from real water-sediment experiments.

Biodegradation of the chitin-protein complex in crustacean cuticle

USGS Publications Warehouse

Artur, Stankiewicz B.; Mastalerz, Maria; Hof, C.H.J.; Bierstedt, A.; Flannery, M.B.; Briggs, D.E.G.; Evershed, R.P.

1998-01-01

Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative analysis of amino acids (by HPLC) and chitin showed that the major loss of proteins and chitin occurred between weeks 1 and 2. After 8 weeks tyrosine, tryptophan and valine are the most prominent amino acid moieties, showing their resistance to degradation. The presence of cyclic ketones in the pyrolysates indicates that mucopolysaccharides or other bound non-chitinous carbohydrates are also resistant to decay. There is no evidence of structural degradation of chitin prior to 8 weeks when FTIR revealed a reduction in chitin-specific bands. The chemical changes are paralleled by structural changes in the cuticle, which becomes an increasingly open structure consisting of loose chitinous fibres. The rapid rate of decay in the experiments suggests that where chitin and protein are preserved in fossil cuticles degradation must have been inhibited.Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative analysis of amino acids (by HPLC) and chitin showed that the major loss of proteins and chitin occurred between weeks 1 and 2. After 8 weeks tyrosine, tryptophan and valine are the most prominent amino acid moieties, showing their resistance to degradation. The presence of cyclic ketones in the pyrolysates indicates that mucopolysaccharides or other bound non-chitinous carbohydrates are also resistant to decay. There is no evidence of structural degradation of chitin prior to 8 weeks when FTIR revealed a reduction in chitin-specific bands. The chemical changes are paralleled by structural changes in the cuticle, which becomes an increasingly open structure consisting of loose chitinous fibres. The rapid rate of decay in the experiments suggests, that where chitin and protein are preserved in fossil cuticles degradation must have been inhibited.

Development of Bioorthogonally Degradable Linkers and Polymers Using alpha-Azidoethers

NASA Astrophysics Data System (ADS)

Rajagopalan, Chandrasekhar Ramasubramanian

Degradable polymers have gained a lot of attention in recent years for applications in biotechnology and medicine. External control over polymer degradation can be obtained by incorporating functional groups that cleave in the presence of triggers that would normally be absent in biological environments, i.e. are bioorthogonal. This thesis explores the use of chemically cleavable alpha-azidoethers as a new method to obtain external control over the degradation behavior of polymers. My first goal is to illustrate the potential of alpha-azidoethers toward developing cleavable linkers. We have studied the relationship between alpha-azidoether structure and hydrolytic stability, to prepare linkers that withstand background hydrolytic cleavage until they are exposed to the cleaving trigger. The cleavage kinetics of the alpha-azidoether functional group was quantified. In addition to the conventionally used tris(2-carboxyethyl)phosphine (TCEP), dihydrolipoic acid (DHLA), a previously unexplored, biocompatible reducing agent, was also evaluated as a cleaving trigger. Based on these results, we have proposed design rules for utilizing alpha-azidoethers as cleavable linkers in applications that require bioorthogonal control over linker cleavage. Secondly, the alpha-azidoether cleavable linker chemistry was implemented into the development of polymeric materials. Two different types of polymers were developed. Polyamides incorporating alpha-azidoethers along the backbone were synthesized, and their physical properties and chemically triggered degradation behavior were characterized. The degradation timescale of these polymers can be tuned simply by manipulating the concentration of the externally applied chemical trigger. The alpha-azidoether functional group was then utilized to develop a unique triggered-release polymeric adhesive for potential applications in dental adhesive formulations. A methacrylamide-phosphonate adhesive monomer incorporating an alpha-azidoether group was designed and synthesized. The monomer was polymerized to adhere polymer-composite substrates. Adhesion strength was quantified, and on-demand release of bonded substrates was demonstrated using DHLA as a trigger. The results presented here shed some light on the scope, advantages and drawbacks of utilizing alpha-azidoethers to develop new types of cleavable linkers and degradable polymers. In principle, the triggered degradation method described here could be incorporated into polymers with different chemical structures, to develop a variety of materials that offer an external control over degradation.

ANALYTICAL METHOD DEVELOPMENT FOR ALACHLOR ESA AND OTHER ACETANILIDE HERBICIDE DEGRADATION PRODUCTS

EPA Science Inventory

In 1998, USEPA published a Drinking Water Contaminant Candidate List (CCL) of 50 chemicals and 10 microorganisms. "Alachlor ESA and other acetanilide herbicide degradation products" is listed on the the 1998 CCL. Acetanilide degradation products are generally more water soluble...

Degradation of isoproturon and bentazone in peat- and compost-based biomixtures.

PubMed

Coppola, Laura; Pilar Castillo, Maria Del; Vischetti, Costantino

2011-01-01

The composition and properties of a biomixture used in a biobed are decisive for pesticide sorption and degradation. This study was performed to investigate the capability of compost-based substrates in mixtures with citrus peel and vine branch straw and peat-based substrates in mixtures with soil and vine branch straw at different levels in order to degrade isoproturon and bentazone. Dissipation and mineralisation rates of both pesticides were determined, and metabolic activity was followed as respiration. Compost-based substrates showed faster pesticide dissipation in the presence of lignocellulosic materials, as in garden compost and vine branch straw. The increasing content of vine branch straw in peat-based substrates does not seem to affect dissipation of the parent compounds. Low mineralisation rate was observed in all treatments. Higher pesticide degradation was observed in the lignocellulosic substrates, probably because of the development of lignin-degrading microorganisms which have shown to be robust and are able to degrade recalcitrant pesticides. Copyright © 2010 Society of Chemical Industry. Copyright © 2010 Society of Chemical Industry.

Effect of Chemical and Physical Properties on the In Vitro Degradation of 3D Printed High Resolution Poly(propylene fumarate) Scaffolds.

PubMed

Walker, Jason M; Bodamer, Emily; Krebs, Olivia; Luo, Yuanyuan; Kleinfehn, Alex; Becker, Matthew L; Dean, David

2017-04-10

Two distinct molecular masses of poly(propylene fumarate) (PPF) are combined with an additive manufacturing process to fabricate highly complex scaffolds possessing controlled chemical properties and porous architecture. Scaffolds were manufactured with two polymer molecular masses and two architecture styles. Degradation was assessed in an accelerated in vitro environment. The purpose of the degradation study is not to model or mimic in vivo degradation, but to efficiently compare the effect of modulating scaffold properties. This is the first study addressing degradation of chain-growth synthesized PPF, a process that allows for considerably more control over molecular mass distribution. It demonstrates that, with greater process control, not only is scaffold fabrication reproducible, but the mechanical properties and degradation kinetics can be tailored by altering the physical properties of the scaffold. This is a clear step forward in using PPF to address unmet medical needs while meeting regulatory demands and ultimately obtaining clinical relevancy.

Degradation and adsorption of selected pharmaceuticals and personal care products (PPCPs) in agricultural soils.

PubMed

Xu, Jian; Wu, Laosheng; Chang, Andrew C

2009-11-01

Pharmaceuticals and personal care products (PPCPs) are emerging contaminants in the environment, which have drawn popular concerns recently. Most studies on the environmental fate of PPCPs have focused on their behaviors during wastewater treatment processes, in aquatic environments, and in the sludge, however, little is known about their behavior in agricultural soils. In this study, adsorption and degradation of six selected PPCPs, including clofibric acid, ibuprofen, naproxen, triclosan, diclofenac and bisphenol A have been investigated in the laboratory using four US agricultural soils associated with reclaimed wastewater reuse. Adsorption test using a batch equilibrium method demonstrated that adsorption of all tested chemicals in soils could be well described with Freundlich equation, and their adsorption affinity on soil followed the order of triclosan>bisphenol A>clofibric acid>naproxen>diclofenac>ibuprofen. Retardation factor (R(F)) suggested that ibuprofen had potential to move downward with percolating water, while triclosan and bisphenol A were readily retarded in soils. Degradation of selected PPCPs in soils generally followed first-order exponential decay kinetics, with half-lives ranging from 0.81 to 20.44 d. Degradation of PPCPs in soils appeared to be influenced by the soil organic matter and clay contents. Sterilization generally decreased the degradation rates, indicating microbial activity played a significant role in the degradation in soils. The degradation rate constant decreased with increasing initial chemical concentrations in soil, implying that the microbial activity was inhibited with high chemical loading levels.

Efficient, environmentally-friendly and specific valorization of lignin: promising role of non-radical lignolytic enzymes.

PubMed

Wang, Wenya; Zhang, Chao; Sun, Xinxiao; Su, Sisi; Li, Qiang; Linhardt, Robert J

2017-06-01

Lignin is the second most abundant bio-resource in nature. It is increasingly important to convert lignin into high value-added chemicals to accelerate the development of the lignocellulose biorefinery. Over the past several decades, physical and chemical methods have been widely explored to degrade lignin and convert it into valuable chemicals. Unfortunately, these developments have lagged because of several difficulties, of which high energy consumption and non-specific cleavage of chemical bonds in lignin remain the greatest challenges. A large number of enzymes have been discovered for lignin degradation and these are classified as radical lignolytic enzymes and non-radical lignolytic enzymes. Radical lignolytic enzymes, including laccases, lignin peroxidases, manganese peroxidases and versatile peroxidases, are radical-based bio-catalysts, which degrade lignins through non-specific cleavage of chemical bonds but can also catalyze the radical-based re-polymerization of lignin fragments. In contrast, non-radical lignolytic enzymes selectively cleave chemical bonds in lignin and lignin model compounds and, thus, show promise for use in the preparation of high value-added chemicals. In this mini-review, recent developments on non-radical lignolytic enzymes are discussed. These include recently discovered non-radical lignolytic enzymes, their metabolic pathways for lignin conversion, their recent application in the lignin biorefinery, and the combination of bio-catalysts with physical/chemical methods for industrial development of the lignin refinery.

Treatment of low level radioactive liquid waste containing appreciable concentration of TBP degraded products.

PubMed

Valsala, T P; Sonavane, M S; Kore, S G; Sonar, N L; De, Vaishali; Raghavendra, Y; Chattopadyaya, S; Dani, U; Kulkarni, Y; Changrani, R D

2011-11-30

The acidic and alkaline low level radioactive liquid waste (LLW) generated during the concentration of high level radioactive liquid waste (HLW) prior to vitrification and ion exchange treatment of intermediate level radioactive liquid waste (ILW), respectively are decontaminated by chemical co-precipitation before discharge to the environment. LLW stream generated from the ion exchange treatment of ILW contained high concentrations of carbonates, tributyl phosphate (TBP) degraded products and problematic radio nuclides like (106)Ru and (99)Tc. Presence of TBP degraded products was interfering with the co-precipitation process. In view of this a modified chemical treatment scheme was formulated for the treatment of this waste stream. By mixing the acidic LLW and alkaline LLW, the carbonates in the alkaline LLW were destroyed and the TBP degraded products got separated as a layer at the top of the vessel. By making use of the modified co-precipitation process the effluent stream (1-2 μCi/L) became dischargeable to the environment after appropriate dilution. Based on the lab scale studies about 250 m(3) of LLW was treated in the plant. The higher activity of the TBP degraded products separated was due to short lived (90)Y isotope. The cement waste product prepared using the TBP degraded product was having good chemical durability and compressive strength. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of Nanoparticle Technology to Reduce the Anti-Microbial Resistance through β-Lactam Antibiotic-Polymer Inclusion Nano-Complex.

PubMed

Salamanca, Constain H; Yarce, Cristhian J; Roman, Yony; Davalos, Andrés F; Rivera, Gustavo R

2018-02-10

Biocompatible polymeric materials with potential to form functional structures in association with different therapeutic molecules have a high potential for biological, medical and pharmaceutical applications. Therefore, the capability of the inclusion of nano-Complex formed between the sodium salt of poly(maleic acid- alt -octadecene) and a β-lactam drug (ampicillin trihydrate) to avoid the chemical and enzymatic degradation and enhance the biological activity were evaluated. PAM-18Na was produced and characterized, as reported previously. The formation of polymeric hydrophobic aggregates in aqueous solution was determined, using pyrene as a fluorescent probe. Furthermore, the formation of polymer-drug nano-complexes was characterized by Differential Scanning Calorimetry-DSC, viscometric, ultrafiltration/centrifugation assays, zeta potential and size measurements were determined by dynamic light scattering-DLS. The PAM-18Na capacity to avoid the chemical degradation was studied through stress stability tests. The enzymatic degradation was evaluated from a pure β-lactamase, while the biological degradation was determined by different β-lactamase producing Staphylococcus aureus strains. When ampicillin was associated with PAM-18Na, the half-life time in acidic conditions increased, whereas both the enzymatic degradation and the minimum inhibitory concentration decreased to a 90 and 75%, respectively. These results suggest a promissory capability of this polymer to protect the β-lactam drugs against chemical, enzymatic and biological degradation.

Application of Nanoparticle Technology to Reduce the Anti-Microbial Resistance through β-Lactam Antibiotic-Polymer Inclusion Nano-Complex

PubMed Central

Yarce, Cristhian J.; Roman, Yony; Davalos, Andrés F.; Rivera, Gustavo R.

2018-01-01

Biocompatible polymeric materials with potential to form functional structures in association with different therapeutic molecules have a high potential for biological, medical and pharmaceutical applications. Therefore, the capability of the inclusion of nano-Complex formed between the sodium salt of poly(maleic acid-alt-octadecene) and a β-lactam drug (ampicillin trihydrate) to avoid the chemical and enzymatic degradation and enhance the biological activity were evaluated. PAM-18Na was produced and characterized, as reported previously. The formation of polymeric hydrophobic aggregates in aqueous solution was determined, using pyrene as a fluorescent probe. Furthermore, the formation of polymer-drug nano-complexes was characterized by Differential Scanning Calorimetry-DSC, viscometric, ultrafiltration/centrifugation assays, zeta potential and size measurements were determined by dynamic light scattering-DLS. The PAM-18Na capacity to avoid the chemical degradation was studied through stress stability tests. The enzymatic degradation was evaluated from a pure β-lactamase, while the biological degradation was determined by different β-lactamase producing Staphylococcus aureus strains. When ampicillin was associated with PAM-18Na, the half-life time in acidic conditions increased, whereas both the enzymatic degradation and the minimum inhibitory concentration decreased to a 90 and 75%, respectively. These results suggest a promissory capability of this polymer to protect the β-lactam drugs against chemical, enzymatic and biological degradation. PMID:29439391

Preparation of Husk-Based Porous Carbon-TiO2 Composites for Adsorption-Photocatalytic Degradation of Toluene in Aqueous Solution

NASA Astrophysics Data System (ADS)

Shi, Ning; Zhao, Lei; Liang, Shuran; Guo, Fengnan; Zhang, Dan; Liu, Xue; Li, Menghan; Peng, Xiao; Wu, Yan

2017-12-01

In this study, PC-nanoTiO2 and PC-P25 were prepared via chemical-deposition and mixture-calcination methods, respectively. Both of PC-nanoTiO2 and PC-P25 were employed to adsorb and photocatalytic degrade toluene in aqueous solution. The characterization results show that distribution of TiO2 nanoparticles in PC-nanoTiO2 and PC-P25 were different, but their binding force between PC and TiO2 were both chemical bonds. Due to synergy of adsorption and photocatalytic degradation, both PC-nanoTiO2 and PC-P25 exhibit good effect in removing toluene in aqueous solution, and both PC-nanoTiO2 and PC-P25 could be utilized for treating wastewater generated from hazardous chemicals leakage accidents emergency.

Chemical Degradation of PCBs in Alaskan Soils

DTIC Science & Technology

2011-04-01

problem was encountered by the Hawaii District (i.e., small volumes of PCB -contaminated soils at remote island sites). A previous study conducted by ERDC... Marshall . 2007. Simultaneous mobilization of heavy metals and polychlorinated biphenyl ( PCB ) compounds from soil with cyclodextrin and EDTA in...ER D C/ EL T R- 11 -3 Innovative Technology Advocate – Formerly Used Defense Sites Chemical Degradation of PCBs in Alaskan Soils En vi

A comparison of organophosphate degradation genes and bioremediation applications.

PubMed

Iyer, Rupa; Iken, Brian; Damania, Ashish

2013-12-01

Organophosphates (OPs) form the bulk of pesticides that are currently in use around the world accounting for more than 30% of the world market. They also form the core for many nerve-based warfare agents including sarin and soman. The widespread use and the resultant build-up of OP pesticides and chemical nerve agents has led to the development of major health problems due to their extremely toxic interaction with any biological system that encounters them. Growing concern over the accumulation of OP compounds in our food products, in the soils from which they are harvested and in wastewater run-off has fuelled a growing interest in microbial biotechnology that provides cheap, efficient OP detoxification to supplement expensive chemical methods. In this article, we review the current state of knowledge of OP pesticide and chemical agent degradation and attempt to clarify confusion over identification and nomenclature of two major families of OP-degrading enzymes through a comparison of their structure and function. The isolation, characterization, utilization and manipulation of the major detoxifying enzymes and the molecular basis of degradation of OP pesticides and chemical nerve agents are discussed as well as the achievements and technological advancements made towards the bioremediation of such compounds. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

Biological Degradation of Chinese Fir with Trametes Versicolor (L.) Lloyd

PubMed Central

Chen, Meiling; Wang, Chuangui; Fei, Benhua; Ma, Xinxin; Zhang, Bo; Zhang, Shuangyan; Huang, Anmin

2017-01-01

Chinese fir (Cunninghamia lanceolata (Lamb.) Hook.) has been an important afforestation species in northeast China. It has obvious defects of buckling and cracking easily, which are caused by its chemical components. Trametes versicolor (L.) Lloyd, a white-rot fungus, can decompose the cellulose, hemicellulose, and lignin in the wood. White-rot fungus was used to biologically degrade Chinese fir wood. The effects of different degradation time on the Chinese fir wood’s mechanical properties, micromorphology, chemical components, and crystallinity were studied. The results showed that the heartwood of Chinese fir was more durable than the sapwood and the durability class of Chinese fir was III. Trametes versicolor (L.) Lloyd had a greater influence on the mechanical properties (especially with respect to the modulus of elasticity (MOE)) for the sapwood. Trametes versicolor (L.) Lloyd degraded Chinese fir and colonized the lumen of various wood cell types in Chinese fir, penetrated cell walls via pits, caused erosion troughs and bore holes, and removed all cell layers. The ability of white-rot fungus to change the chemical composition mass fraction for Chinese fir was: hemicellulose > lignin > cellulose. The durability of the chemical compositions was: lignin > cellulose > hemicellulose. The crystallinity of the cellulose decreased and the mean size of the ordered (crystalline) domains increased after being treated by white-rot fungus. PMID:28773191

Demonstrating In-Cell Target Engagement Using a Pirin Protein Degradation Probe (CCT367766)

PubMed Central

2017-01-01

Demonstrating intracellular protein target engagement is an essential step in the development and progression of new chemical probes and potential small molecule therapeutics. However, this can be particularly challenging for poorly studied and noncatalytic proteins, as robust proximal biomarkers are rarely known. To confirm that our recently discovered chemical probe 1 (CCT251236) binds the putative transcription factor regulator pirin in living cells, we developed a heterobifunctional protein degradation probe. Focusing on linker design and physicochemical properties, we generated a highly active probe 16 (CCT367766) in only three iterations, validating our efficient strategy for degradation probe design against nonvalidated protein targets. PMID:29240418

Investigations of Chemical and Biological Treatment Options for the Attenuation of Hexahydro-1,3,5-trinitro-1,3,5-triazine Contamination in Groundwater at Los Alamos, New Mexico

NASA Astrophysics Data System (ADS)

Heerspink, B. P.; Wang, D.; Ware, D.; Marina, O.; Perkins, G.; WoldeGabriel, G. W.; Goering, T.; Boukhalfa, H.

2017-12-01

High-explosive compounds including hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) were used extensively in weapons research and testing at Los Alamos National Laboratory (LANL) in Los Alamos, NM. Liquid effluents containing RDX released at LANL's Technical Area 16 (TA-16) resulted in the contamination of alluvial, perched-intermediate, and regional groundwater bodies. Past investigations have shown persistent RDX contamination in the perched-intermediate zone located between 225 to 311 m below ground surface, where transport studies have shown that RDX and its degradation products transport conservatively. In this study, we compared RDX degradation by chemical treatments using reduction by sodium dithionite, oxidation by potassium permanganate, and alkaline hydrolysis by carbonate/bicarbonate buffering, with microbial degradation under biostimulated conditions. The experiments were conducted using groundwater and sediments representative of the contaminated aquifer beneath TA-16. Batch testing showed that all chemical treatments degraded RDX very rapidly, with half-lives ranging from 50 minutes to 22 hours. Comparatively, RDX degradation in biostimulated reactors under strict anaerobic conditions was significantly slower, with half-lives of about 3 weeks. Results from column experiments with chemically treated sediments deviated from the results of the batch testing. Dithionite treated sediments reduced RDX with no breakthrough observed before clogging occurred at 50 pour volumes. Treatments by oxidation using potassium permanganate, and hydrolysis under buffered alkaline conditions, were less effective with complete RDX breakthrough after 2 pore volumes. No known degradation products were observed in the column effluents. RDX degradation in biostimulated columns was very effective initially for both treatments. However, the column biostimulated with safflower oil clogged very rapidly. The column biostimulated with molasses was very effective when molasses was continuously supplied but less effective after molasses injection stopped. Degradation products (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine [MNX]; hexahydro-1,3-dinitro-5-nitro-1,3,5-triazine [DNX]; 2,4,6-trinitroxylene [TNX]) were visible in the effluents from the biostimulated columns.

Tryptophan oxidation catabolite, N-formylkynurenine, in photo degraded cell culture medium results in reduced cell culture performance.

PubMed

McElearney, Kyle; Ali, Amr; Gilbert, Alan; Kshirsagar, Rashmi; Zang, Li

2016-01-01

Chemically defined media have been widely used in the biopharmaceutical industry to enhance cell culture productivities and ensure process robustness. These media, which are quite complex, often contain a mixture of many components such as vitamins, amino acids, metals and other chemicals. Some of these components are known to be sensitive to various stress factors including photodegradation. Previous work has shown that small changes in impurity concentrations induced by these potential stresses can have a large impact on the cell culture process including growth and product quality attributes. Furthermore, it has been shown to be difficult to detect these modifications analytically due to the complexity of the cell culture media and the trace level of the degradant products. Here, we describe work performed to identify the specific chemical(s) in photodegraded medium that affect cell culture performance. First, we developed a model system capable of detecting changes in cell culture performance. Second, we used these data and applied an LC-MS analytical technique to characterize the cell culture media and identify degradant products which affect cell culture performance. Riboflavin limitation and N-formylkynurenine (NFK), a tryptophan oxidation catabolite, were identified as chemicals which results in a reduction in cell culture performance. © 2015 American Institute of Chemical Engineers.

Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

PubMed

Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

2014-01-28

Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

Characterization of the chemicals used in hydraulic fracturing fluids for wells located in the Marcellus Shale Play.

PubMed

Chen, Huan; Carter, Kimberly E

2017-09-15

Hydraulic fracturing, coupled with the advances in horizontal drilling, has been used for recovering oil and natural gas from shale formations and has aided in increasing the production of these energy resources. The large volumes of hydraulic fracturing fluids used in this technology contain chemical additives, which may be toxic organics or produce toxic degradation byproducts. This paper investigated the chemicals introduced into the hydraulic fracturing fluids for completed wells located in Pennsylvania and West Virginia from data provided by the well operators. The results showed a total of 5071 wells, with average water volumes of 5,383,743 ± 2,789,077 gal (mean ± standard deviation). A total of 517 chemicals was introduced into the formulated hydraulic fracturing fluids. Of the 517 chemicals listed by the operators, 96 were inorganic compounds, 358 chemicals were organic species, and the remaining 63 cannot be identified. Many toxic organics were used in the hydraulic fracturing fluids. Some of them are carcinogenic, including formaldehyde, naphthalene, and acrylamide. The degradation of alkylphenol ethoxylates would produce more toxic, persistent, and estrogenic intermediates. Acrylamide monomer as a primary degradation intermediate of polyacrylamides is carcinogenic. Most of the chemicals appearing in the hydraulic fracturing fluids can be removed when adopting the appropriate treatments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Teardown analysis for detecting shelf-life degradation

NASA Technical Reports Server (NTRS)

Eckstein, A. S.

1971-01-01

Analysis is guideline in examining component materials, analytically determining physical properties and chemical compositions, and developing control data necessary for ascertaining effects of environments and their influence on deterioration and degradation mechanisms.

Degradations and Rearrangement Reactions

NASA Astrophysics Data System (ADS)

Zhang, Jianbo

This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

Iminosugar inhibitors of carbohydrate-active enzymes that underpin cereal grain germination and endosperm metabolism

PubMed Central

Andriotis, Vasilios M. E.; Rejzek, Martin; Rugen, Michael D.; Svensson, Birte; Smith, Alison M.; Field, Robert A.

2016-01-01

Starch is a major energy store in plants. It provides most of the calories in the human diet and, as a bulk commodity, it is used across broad industry sectors. Starch synthesis and degradation are not fully understood, owing to challenging biochemistry at the liquid/solid interface and relatively limited knowledge about the nature and control of starch degradation in plants. Increased societal and commercial demand for enhanced yield and quality in starch crops requires a better understanding of starch metabolism as a whole. Here we review recent advances in understanding the roles of carbohydrate-active enzymes in starch degradation in cereal grains through complementary chemical and molecular genetics. These approaches have allowed us to start dissecting aspects of starch degradation and the interplay with cell-wall polysaccharide hydrolysis during germination. With a view to improving and diversifying the properties and uses of cereal grains, it is possible that starch degradation may be amenable to manipulation through genetic or chemical intervention at the level of cell wall metabolism, rather than simply in the starch degradation pathway per se. PMID:26862201

Degradation kinetics of aflatoxin B1 and B2 in solid medium by using pulsed light irradiation.

PubMed

Wang, Bei; Mahoney, Noreen E; Khir, Ragab; Wu, Bengang; Zhou, Cunshan; Pan, Zhongli; Ma, Haile

2018-04-10

Pulsed light (PL) is a new potential technology to degrade aflatoxin. The objective of this study was to investigate the degradation characters of aflatoxin B 1 (AFB 1 ) and B 2 (AFB 2 ) treated under PL irradiation. A kinetic degradation study of AFB 1 and AFB 2 in solid medium was performed under PL irradiation at different initial concentrations of AFB 1 (229.9, 30.7 and 17.8 μg kg -1 ) and AFB 2 (248.2, 32.2 and 19.5 μg kg -1 ) and irradiation intensities (2.86, 1.60 and 0.93 W cm -2 ) of PL. A second-order reaction model was applied to describe degradation of AFB 1 and AFB 2 . The results showed that the degradation of AFB 1 and AFB 2 followed the second-order reaction kinetic model well (R 2  > 0.97). The degradation rate was proportional to the intensities of PL irradiation and the initial concentrations of aflatoxins. It is concluded that the degradation of AFB 1 and AFB 2 with the use of PL could be accurately described using the second-order reaction kinetic model. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

In situ chemical degradation of DNAPLS in contaminated soils and sediments

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

Gates, D.D.; Korte, N.E.; Siegrist, R.L.

1996-08-01

An emerging approach to in situ treatment of organic contaminants is chemical degradation. The specific processes discussed in this chapter are in situ chemical oxidation using either hydrogen peroxide (H{sub 2}O{sub 2}) or potassium permanganate (KMnO{sub 4}) and in situ dechlorination of halogenated hydrocarbons using zero-valence base metals such as iron. These technologies are primarily chemical treatment processes, where the treatment goal is to manipulate the chemistry of the subsurface environment in such a manner that the contaminants of interest are destroyed and/or rendered non-toxic. Chemical properties that can be altered include pH, ionic strength, oxidation and reduction potential, andmore » chemical equilibria. In situ contaminant destruction processes alter or destroy contaminants in place and are typically applied to compounds that can be either converted to innocuous species such as CO{sub 2} and water, or can be degraded to species that are non-toxic or amenable to other in situ processes (i.e., bioremediation). With in situ chemical oxidation, the delivery and distribution of chemical reagents are critical to process effectiveness. In contrast, published approaches for the use of zero valence base metals suggest passive approaches in which the metals are used in a permeable reaction wall installed in situ in the saturated zone. Both types of processes are receiving increasing attention and are being applied both in technology demonstration and as final solutions to subsurface contaminant problems. 43 refs., 9 figs., 1 tab.« less

Thermal degradation of wood fibers during hot-pressing of MDF composites. Part I, Relative effects and benefits of thermal exposure

Treesearch

Jerrold E. Winandy; Andrzej M. Krzysik

2007-01-01

This research evaluated the potential of wood fiber to chemically decompose during hot-pressing. We evaluated changes in carbohydrate composition and structure as a function of multiple press temperatures (180°, 200°, and 220°C) and an array of hot-pressing durations from 180 to 2500 s. Results show how this thermal degradation in chemical composition directly results...

Chemically mediated behavior of recruiting corals and fishes: A tipping point that may limit reef recovery

PubMed Central

Dixson, Danielle L; Abrego, David; Hay, Mark E

2015-01-01

Coral reefs are in global decline, converting from dominance by coral to dominance by seaweed. Once seaweeds become abundant, coral recovery is suppressed unless herbivores return to remove seaweeds, and corals then recruit. Variance in the recovery of fishes and corals is not well understood. We show that juveniles of both corals and fishes are repelled by chemical cues from fished, seaweed-dominated reefs but attracted to cues from coral-dominated areas where fishing is prohibited. Chemical cues of specific seaweeds from degraded reefs repulsed recruits, and cues from specific corals that are typical of healthy reefs attracted recruits. Juveniles were present at but behaviorally avoided recruiting to degraded reefs dominated by seaweeds. For recovery, degraded reefs may need to be managed to produce cues that attract, rather than repel, recruiting corals and fishes. PMID:25146281

Reef ecology. Chemically mediated behavior of recruiting corals and fishes: a tipping point that may limit reef recovery.

PubMed

Dixson, Danielle L; Abrego, David; Hay, Mark E

2014-08-22

Coral reefs are in global decline, converting from dominance by coral to dominance by seaweed. Once seaweeds become abundant, coral recovery is suppressed unless herbivores return to remove seaweeds, and corals then recruit. Variance in the recovery of fishes and corals is not well understood. We show that juveniles of both corals and fishes are repelled by chemical cues from fished, seaweed-dominated reefs but attracted to cues from coral-dominated areas where fishing is prohibited. Chemical cues of specific seaweeds from degraded reefs repulsed recruits, and cues from specific corals that are typical of healthy reefs attracted recruits. Juveniles were present at but behaviorally avoided recruiting to degraded reefs dominated by seaweeds. For recovery, degraded reefs may need to be managed to produce cues that attract, rather than repel, recruiting corals and fishes. Copyright © 2014, American Association for the Advancement of Science.

Degradation Of Carbon/Phenolic Composites By NaOH

NASA Technical Reports Server (NTRS)

King, H. M.; Semmel, M. L.; Goldberg, B. E.; Clinton, Raymond G., Jr.

1989-01-01

Effects of sodium hydroxide contamination level on physical and chemical properties of phenolic resin and carbon/phenolic composites described in report. NaOH degrades both carbon and phenolic components of carbon/phenolic laminates.

Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions.

PubMed

Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias; Guan, Zhibin; Huang, Zheng

2016-06-01

Polyethylene (PE) is the largest-volume synthetic polymer, and its chemical inertness makes its degradation by low-energy processes a challenging problem. We report a tandem catalytic cross alkane metathesis method for highly efficient degradation of polyethylenes under mild conditions. With the use of widely available, low-value, short alkanes (for example, petroleum ethers) as cross metathesis partners, different types of polyethylenes with various molecular weights undergo complete conversion into useful liquid fuels and waxes. This method shows excellent selectivity for linear alkane formation, and the degradation product distribution (liquid fuels versus waxes) can be controlled by the catalyst structure and reaction time. In addition, the catalysts are compatible with various polyolefin additives; therefore, common plastic wastes, such as postconsumer polyethylene bottles, bags, and films could be converted into valuable chemical feedstocks without any pretreatment.

Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions

PubMed Central

Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias; Guan, Zhibin; Huang, Zheng

2016-01-01

Polyethylene (PE) is the largest-volume synthetic polymer, and its chemical inertness makes its degradation by low-energy processes a challenging problem. We report a tandem catalytic cross alkane metathesis method for highly efficient degradation of polyethylenes under mild conditions. With the use of widely available, low-value, short alkanes (for example, petroleum ethers) as cross metathesis partners, different types of polyethylenes with various molecular weights undergo complete conversion into useful liquid fuels and waxes. This method shows excellent selectivity for linear alkane formation, and the degradation product distribution (liquid fuels versus waxes) can be controlled by the catalyst structure and reaction time. In addition, the catalysts are compatible with various polyolefin additives; therefore, common plastic wastes, such as postconsumer polyethylene bottles, bags, and films could be converted into valuable chemical feedstocks without any pretreatment. PMID:27386559

Degradation of dimethyl disulphide in soil with or without biochar amendment.

PubMed

Han, Dawei; Yan, Dongdong; Cao, Aocheng; Fang, Wensheng; Liu, Pengfei; Li, Yuan; Ouyang, Canbin; Wang, Qiuxia

2017-09-01

Dimethyl disulphide (DMDS) is a new and effective alternative to methyl bromide for soil fumigation. The effect of biochar on the fate of DMDS in soil is not fully understood. The objective of this study was to determine the degradation kinetics of DMDS in different soils and evaluate the effect of biochar amendment on DMDS degradation using incubation experiments. The degradation half-life of DMDS was between 1.05 and 6.66 days under non-sterile conditions, and 12.63 to 22.67 days under sterile conditions in five types of soil. Seven out of the eight tested biochar amendments (BC-2 to BC-8) delayed the degradation of DMDS in soil, increasing the half-life of DMDS in Fangshan soil from 1.05 to 1.16-5.87 days following amendment with 1% (w/w) biochar. The degradation rate of DMDS in Fangshan soil accelerated as the amendment rate of BC-1 increased, and decreased as the amendment rate of BC-7 increased. Biodegradation is an important degradation route for DMDS in soil, and DMDS degraded faster in alkaline soil. The effects of biochar amendments on DMDS degradation in soil are determined by complex multiple factors (such as surface area, pH and physicochemical composition), rather than by any single property of biochar. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Degradation rates of phorbol esters in Jatropha curcas L. oil and pressed seeds under different storage conditions.

PubMed

Phasukarratchai, Naphatsarnan; Damrongsiri, Seelawut; Tongcumpou, Chantra

2017-03-01

Phorbol esters (PEs), found in Jatropha curcas crude oil (JCO) and J. curcas pressed seeds (JPS), are known as bioactive compounds in agricultural and pharmaceutical applications. The degradation rates of PEs in JCO and JPS under various conditions is important for the utilisation of PEs. Thus the objective of this study was to determine the PE degradation rates in JCO and JPS under different storage conditions. PE degradation rates were found to be first-order reactions. The slowest degradation rate was at 0.9 × 10 -3 d -1 for both JCO and JPS unexposed to light at 4 °C. Light intensity (1097 lx and 4690 lx, representing diffused sunlight and fluorescent lighting, respectively) and temperature (25 to 35 °C) were the significant degradation factors. Light exposure led to 280% to 380% higher degradation rates in JCO than in JPS due to light penetration through the transparent oil. Dried and sterilised JPS showed an 80% to 90% lower PE degradation rate than untreated JPS under all storage conditions since biodegradation was assembly limited. The PEs were unstable under the studied conditions, especially when exposed to light and room temperature. To protect against PE degradation, a material should be stored in a light-protected container and below 4 °C. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Chemical modification and degradation of atrazine in Medicago sativa through multiple pathways.

PubMed

Zhang, Jing Jing; Lu, Yi Chen; Yang, Hong

2014-10-08

Atrazine is a member of the triazine herbicide family intensively used to control weeds for crop production. In this study, atrazine residues and its degraded products in alfalfa (Medicago sativa) were characterized using UPLC-TOF-MS/MS. Most of atrazine absorbed in plants was found as chemically modified derivatives like deisopropylated atrazine (DIA), dehydrogenated atrazine (DHA), or methylated atrazine (MEA), and some atrazine derivatives were conjugated through different functional groups such as sugar, glutathione, and amino acids. Interestingly, the specific conjugates DHA+hGSH (homoglutathione) and MEA-HCl+hGSH in alfalfa were detected. These results suggest that atrazine in alfalfa can be degraded through different pathways. The increased activities of glycosyltransferase and glutathione S-transferase were determined to support the atrazine degradation models. The outcome of the work uncovered the detailed mechanism for the residual atrazine accumulation and degradation in alfalfa and will help to evaluate whether the crop is suitable to be cultivated in the atrazine-polluted soil.

How copper corrosion can be retarded--New ways investigating a chronic problem for cellulose in paper.

PubMed

Ahn, Kyujin; Hofmann, Christa; Horsky, Monika; Potthast, Antje

2015-12-10

To better assess the stabilization effects of chemical treatments on Cu(II)-catalyzed cellulose degradation, we developed Cu(II)-containing model rag paper with typical copper corrosion characteristics using e-beam radiation. The paper can be prepared homogeneously and quickly compared to tedious pre-aging methods. Using the Cu(II)-containing model rag paper, the stabilization effects of various chemicals on Cu(II)-catalyzed degradation of cellulose were tested. Benzotriazol was highly effective in retarding the degradation of the Cu(II)-containing model rag paper under hot and humid aging condition, as well as under photo-oxidative stress. Tetrabutylammonium bromide reduced Cu(II)-catalyzed degradation of cellulose, but its efficacy was dependent on the accelerated aging conditions. The results with the alkaline treatments and gelatin treatment suggested that their roles in the degradation mechanisms of cellulose in the presence of Cu(II) differ from those of benzotriazol and tetrabutylammonium bromide. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4.

PubMed

Neppolian, B; Choi, H C; Sakthivel, S; Arabindoo, B; Murugesan, V

2002-03-01

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.

Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

PubMed

Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

2014-05-01

Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

A Novel Approach to Detect Accelerated Aged and Surface-Mediated Degradation in Explosives by UPLC-ESI-MS.

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

Beppler, Christina L

2015-12-01

A new approach was created for studying energetic material degradation. This approach involved detecting and tentatively identifying non-volatile chemical species by liquid chromatography-mass spectrometry (LC-MS) with multivariate statistical data analysis that form as the CL-20 energetic material thermally degraded. Multivariate data analysis showed clear separation and clustering of samples based on sample group: either pristine or aged material. Further analysis showed counter-clockwise trends in the principal components analysis (PCA), a type of multivariate data analysis, Scores plots. These trends may indicate that there was a discrete shift in the chemical markers as the went from pristine to aged material, andmore » then again when the aged CL-20 mixed with a potentially incompatible material was thermally aged for 4, 6, or 9 months. This new approach to studying energetic material degradation should provide greater knowledge of potential degradation markers in these materials.« less

Pseudomonas aeruginosa biofilm formation and UV/irradiation exposure change surface and chemical structures of Pre-Production Resin Pellets

NASA Astrophysics Data System (ADS)

Stam, C. N.; Neal, A.; Park, S.; Mielke, R.; Tsapin, A. I.; Bhartia, R.; Salas, E.; Hug, W.; Behar, A. E.; Nadeau, J. L.

2011-12-01

Microbial interactions with synthetic polymers in open ocean is poorly understood. Plastics are a major and persistent contaminant of ocean waters. Many of these plastics are contaminated with toxic and synthetic chemicals that persist in the environment with minimal degradation. The purpose of this study is to look at the effects that microbial biofilm communities have on both surface and chemical structures of pre-production resin pellets (PRPs). Pseudomonas aeruignosa was grown with PRPs under multiple growth and nutrient conditions. These conditions were combined with varying lengths of UV exposures common to ocean environments. Material degradation of the PRPs and the changing surface and chemical structures of these synthetic polymers was evaluated using a combination of Fourier transform infrared spectroscopy, environmental scanning electron microscopy, scanning transmission electron microscopy, X-ray microtomography, and ArcGIS mapping. This study correlates with previous studies conducted on environmental PRP's , collected on the 2009 Project Kaisei expedition in the Subtropical Convergence Zone of the North Pacific Gyre. Further studies are needed to develop a full understanding of degradation rates of synthetic polymers in oceanic environments.

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry.

PubMed

Ryder, Christopher R; Wood, Joshua D; Wells, Spencer A; Yang, Yang; Jariwala, Deep; Marks, Tobin J; Schatz, George C; Hersam, Mark C

2016-06-01

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)-a layered two-dimensional semiconductor-exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

NASA Astrophysics Data System (ADS)

Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

2016-06-01

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

Chemical composition and ruminal nutrient degradability of fresh and ensiled amaranth forage.

PubMed

Seguin, Philippe; Mustafa, Arif F; Donnelly, Danielle J; Gélinas, Bruce

2013-12-01

Amaranth is a crop with potential as a source of forage for ruminants that has not been well characterized. A study was conducted to determine the impact of ensiling on the nutritional quality and ruminal degradability of forage from two amaranth cultivars adapted to North America (i.e. Plainsman and D136). In particular, quantification and some microscopic characterization of oxalate found in amaranth were performed as it is an antiquality compound of concern. There were limited interactions between cultivars and ensiling for most variables. Differences in chemical composition between amaranth cultivars were also limited. Ensiling reduced non-structural carbohydrate and true protein contents. The proportion of acid detergent protein was high in fresh and ensiled forages of both cultivars (average of 177 g kg(-1) crude protein). Total oxalate content averaged 30 and 25 g kg(-1) in fresh and ensiled forages respectively. Ensiling reduced soluble oxalate content. Crystals observed in amaranth were calcium oxalate druses found mostly in idioblast cells in leaf mesophyll and parenchyma of primary and secondary veins. In situ ruminal degradability data indicated that both fresh and ensiled amaranth are highly degradable in the rumen. This study confirms that amaranth is a suitable forage for ruminant animals. Its chemical composition is comparable, for most variables, to that of other commonly used forage species. © 2013 Society of Chemical Industry.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

PubMed

Sun, Peizhe; Lee, Wan-Ning; Zhang, Ruochun; Huang, Ching-Hua

2016-12-20

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Bioremediation of Uranium-Contaminated Groundwater using Engineered Injection and Extraction

NASA Astrophysics Data System (ADS)

Greene, J. A.; Neupauer, R.; Ye, M.; Kasprzyk, J. R.; Mays, D. C.; Curtis, G. P.

2017-12-01

During in-situ remediation of contaminated groundwater, a treatment chemical is injected into the contaminated groundwater to react with and degrade the contaminant, with reactions occurring where the treatment chemical contacts the contaminant. Traditional in-situ groundwater remediation relies on background groundwater flow for spreading of treatment chemicals into contaminant plumes. Engineered Injection and Extraction (EIE), in which time-varying induced flow fields are used to actively spread the treatment chemical into the contaminant plume, has been developed to increase contact between the contaminant and treatment chemical, thereby enhancing contaminant degradation. EIE has been investigated for contaminants that degrade through irreversible bimolecular reaction with a treatment chemical, but has not been investigated for a contaminant governed by reversible reactions. Uranium primarily occurs in its aqueous, mobile form, U(VI), in the environment but can be bioreduced to its sparingly soluble, immobile form, U(IV), by iron reducing bacteria stimulated by an acetate amendment. In this study, we investigate the ability of EIE to facilitate and sustain favorable conditions to immobilize uranium during remediation, and to prevent re-mobilization of uranium into the aqueous phase after active remediation has ended. Simulations in this investigation are conducted using a semi-synthetic model based on physical and chemical conditions at the Naturita Uranium Mill Tailings Remedial Action (UMTRA) site in southwestern Colorado and the Old Rifle UMTRA site in western Colorado. The EIE design is optimized for the synthetic model using the Borg multi-objective evolutionary algorithm.

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing

NASA Astrophysics Data System (ADS)

Xiong, B.; Tasker, T.; Miller, Z.; Roman-White, S.; Farina, B.; Piechowicz, B.; Burgos, W.; Joshi, P.; Zhu, L.; Gorski, C.; Zydney, A.; Kumar, M.

2017-12-01

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus shale outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by two orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluid. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-M hydroxyl radical concentrations. The shale sample adsorbed some PAM ( 30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals.

PubMed

Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

2016-04-15

Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035-2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals.

Modelling drug degradation in a spray dried polymer dispersion using a modified Arrhenius equation.

PubMed

Patterson, Adele; Ferreira, Ana P; Banks, Elizabeth; Skeene, Kirsty; Clarke, Graham; Nicholson, Sarah; Rawlinson-Malone, Clare

2015-01-15

The Pharmaceutical industry is increasingly utilizing amorphous technologies to overcome solubility challenges. A common approach is the use of drug in polymer dispersions to prevent recrystallization of the amorphous drug. Understanding the factors affecting chemical and physical degradation of the drug within these complex systems, e.g., temperature and relative humidity, is an important step in the selection of a lead formulation, and development of appropriate packaging/storage control strategies. The Arrhenius equation has been used as the basis of a number of models to predict the chemical stability of formulated product. In this work, we investigate the increase in chemical degradation seen for one particular spray dried dispersion formulation using hydroxypropyl methylcellulose acetate succinate (HPMC-AS). Samples, prepared using polymers with different substitution levels, were placed on storage for 6 months under a range of different temperature and relative humidity conditions and the degradant level monitored using high-performance liquid chromatography (HPLC). While the data clearly illustrates the impact of temperature and relative humidity on the degradant levels detected, it also highlighted that these terms do not account for all the variability in the data. An extension of the Arrhenius equation to include a term for the polymer chemistry, specifically the degree of succinoyl substitution on the polymer backbone, was shown to improve the fit of the model to the data. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing.

PubMed

Xiong, Boya; Miller, Zachary; Roman-White, Selina; Tasker, Travis; Farina, Benjamin; Piechowicz, Bethany; Burgos, William D; Joshi, Prachi; Zhu, Liang; Gorski, Christopher A; Zydney, Andrew L; Kumar, Manish

2018-01-02

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including decisions on strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by 2 orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluids. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-μM hydroxyl radical concentrations. The shale sample adsorbed some PAM (∼30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe 2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Air pollutants degrade floral scents and increase insect foraging times

NASA Astrophysics Data System (ADS)

Fuentes, Jose D.; Chamecki, Marcelo; Roulston, T.'ai; Chen, Bicheng; Pratt, Kenneth R.

2016-09-01

Flowers emit mixtures of scents that mediate plant-insect interactions such as attracting insect pollinators. Because of their volatile nature, however, floral scents readily react with ozone, nitrate radical, and hydroxyl radical. The result of such reactions is the degradation and the chemical modification of scent plumes downwind of floral sources. Large Eddy Simulations (LES) are developed to investigate dispersion and chemical degradation and modification of floral scents due to reactions with ozone, hydroxyl radical, and nitrate radical within the atmospheric surface layer. Impacts on foraging insects are investigated by utilizing a random walk model to simulate insect search behavior. Results indicate that even moderate air pollutant levels (e.g., ozone mixing ratios greater than 60 parts per billion on a per volume basis, ppbv) substantially degrade floral volatiles and alter the chemical composition of released floral scents. As a result, insect success rates of locating plumes of floral scents were reduced and foraging times increased in polluted air masses due to considerable degradation and changes in the composition of floral scents. Results also indicate that plant-pollinator interactions could be sensitive to changes in floral scent composition, especially if insects are unable to adapt to the modified scentscape. The increase in foraging time could have severe cascading and pernicious impacts on the fitness of foraging insects by reducing the time devoted to other necessary tasks.

Possible atmospheric lifetimes and chemical reaction mechanisms for selected HCFCs, HFCs, CH3CCl3, and their degradation products against dissolution and/or degradation in seawater and cloudwater

NASA Technical Reports Server (NTRS)

Wine, P. H.; Chameides, W. L.

1990-01-01

For a wide variety of atmospheric species including CO2, HNO3, and SO2, dissolution in seawater or cloudwater followed by hydrolysis or chemical reaction represents a primary pathway for removal from the atmosphere. In order to determine if this mechanism can also remove significant amounts of atmospheric chlorofluorocarbons (HCFC's), fluorocarbons (HFC's), and their degradation products, an investigation was undertaken as part of the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS). In this investigation, the rates at which CHCl2CF3 (HCFC-123), CCl2FCH3 (HCFC-141b), CClF2CH3 (HCFC-142b), CHClF2 (HCFC-22), CHClFCF3 (HCFC-124) CH2FCF3 (HFC-134a) CHF2CH3 (HFC-152a), CHF2CF3 (HFC-125), and CH3CCl3 can be dissolved in the oceans and in cloudwater were estimated from the species' thermodynamic and chemical properties using simple mathematical formulations to simulate the transfer of gases from the atmosphere to the ocean or cloudwater. The ability of cloudwater and rainwater to remove gas phase degradation products of these compounds was also considered as was the aqueous phase chemistry of the degradation products. The results of this investigation are described.

Catechol degradation on hematite/silica–gas interface as affected by gas composition and the formation of environmentally persistent free radicals

PubMed Central

Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

2016-01-01

Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035–2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals. PMID:27079263

Advanced Oxidation of Tartrazine and Brilliant Blue with Pulsed Ultraviolet Light Emitting Diodes

PubMed Central

Scott, Robert; Mudimbi, Patrick; Miller, Michael E.; Magnuson, Matthew; Willison, Stuart; Phillips, Rebecca; Harper, Willie F.

2018-01-01

This study investigated the effect of ultraviolet light-emitting diodes (UVLEDs) coupled with hydrogen peroxide as an advanced oxidation process (AOP) for the degradation of two test chemicals. Brilliant Blue FCF consistently exhibited greater degradation than tartrazine, with 83% degradation after 300 minutes at the 100% duty cycle compared with only 17% degradation of tartrazine under the same conditions. These differences are attributable to the structural properties of the compounds. Duty cycle was positively correlated with the first-order rate constants (k) for both chemicals but, interestingly, negatively correlated with the normalized first-order rate constants (k/duty cycle). Synergistic effects of both hydraulic mixing and LED duty cycle were manifested as novel oscillations in the effluent contaminant concentration. Further, LED output and efficiency were dependent upon duty cycle and less efficient over time perhaps due to heating effects on semiconductor performance. PMID:28236826

STUDIES ON THE MECHANISM OF THE FORMATION OF THE PENICILLIN ANTIGEN

PubMed Central

Levine, Bernard B.

1960-01-01

Seven highly purified degradation products of penicillin G (PG) were examined with regard to their ability to cross-react allergically with PG. Guinea pig allergic contact dermatitis was employed as the test system. Three of these degradation products, D-benzylpenicillenic acid (BPE), D-penicillamine, and D-α-benzylpenicilloic acid were found to cross-react with PG and also to be capable of inducing delayed contact allergy in the guinea pig. BPE and PG cross-reacted with particularly intense reactions, and other immunologic experiments indicated that PG and BPE introduce identical allergic determinant groups into epidermal proteins. These experimental results were correlated with the results of previous studies concerning the degradation pathways of PG under physiological conditions in vitro, and the chemical reactivities of these degradation products. Based on these immunologic and chemical data, a schema is proposed which suggests the chemical pathways by which PG may react with epidermal proteins in vivo to form the penicillin antigen. The identity of the specific antigenic determinant groups of the penicillin antigen is suggested. The relationship between PG allergy of the contact dermatitis type in the guinea pig and PG allergy of the immediate type in man is discussed. PMID:13761469

Pathways for degradation of plastic polymers floating in the marine environment.

PubMed

Gewert, Berit; Plassmann, Merle M; MacLeod, Matthew

2015-09-01

Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

Stress-induced NQO1 controls stability of C/EBPα against 20S proteasomal degradation to regulate p63 expression with implications in protection against chemical-induced skin cancer.

PubMed

Patrick, B A; Jaiswal, A K

2012-10-04

Previously, we have shown a role of cytosolic NAD(P)H:quinone oxidoreductase 1 (NQO1) in the stabilization of p63 against 20S proteasomal degradation resulting in thinning of the epithelium and chemical-induced skin cancer (Oncogene (2011) 30, 1098-1107). Current studies have demonstrated that NQO1 control of CCAAT-enhancer binding protein (C/EBPα) against 20S proteasomal degradation also contributes to the upregulation of p63 expression and protection. Western and immunohistochemistry analysis revealed that disruption of the NQO1 gene in mice and mouse keratinocytes led to degradation of C/EBPα and loss of p63 gene expression. p63 promoter mutagenesis, transfection and chromatin immunoprecipitation assays identified a C/EBPα-binding site between nucleotide position -185 and -174 that bound to C/EBPα and upregulated p63 gene expression. Co-immunoprecipitation and immunoblot analysis demonstrated that 20S proteasomes directly interacted and degraded C/EBPα. NQO1 direct interaction with C/EBPα led to stabilization of C/EBPα against 20S proteasomal degradation. NQO1 protection of C/EBPα required binding of NADH with NQO1. Exposure of skin and keratinocytes to the chemical stress agent benzo(a)pyrene led to induction of NQO1 and stabilization of C/EBPα protein, resulting in an increase in p63 RNA and protein in wild-type but not in NQO1-/- mice. Collectively, the current data combined with previous data suggest that stress induction of NQO1 through both stabilization of C/EBPα and increase in p63 and direct stabilization of p63 controls keratinocyte differentiation, leading to protection against chemical-induced skin carcinogenesis. The studies are significant as 2-4% human individuals are homozygous and 23% are heterozygous for the NQO1P187S mutation and might be susceptible to stress-induced skin diseases.

Influence of subsurface environment on oxidant activation and 1,4-dioxane degradation by in-situ chemical oxidation

NASA Astrophysics Data System (ADS)

Yan, N.; Brusseau, M. L. L.; Liu, F.

2017-12-01

The influence of groundwater and soil constituents on oxidant activation and 1,4-dioxane (dioxane) degradation by hydrogen peroxide coupled with persulfate was investigated through a series of batch experiments. The degradation of dioxane was considerably slower in groundwater compared to the tests conducted with ultrapure water. Additional tests were conducted to examine potential inhibitory effects of selected ions in isolation. The inhibition effect of anions on dioxane degradation, from strongest inhibition to weakest, was bicarbonate (HCO3-) > sulfate (SO42-) > chloride (Cl-). The inhibition effect of cations on dioxane degradation, from strongest inhibition to weakest, was calcium (Ca2+) > potassium (K+) > magnesium (Mg2+). Bicarbonate and calcium ions, which are the most abundant ions in the groundwater used herein, resulted in the greatest decrease in dioxane degradation rate compared to the other constituents. The impact of soil constituents was investigated by comparing dioxane degradation for bulk soil (soil without treatment), soil treated to remove organic matter (mineral fraction), and soil treated to remove organic matter and manganese oxides (iron fraction). Radical generation was measured by electron paramagnetic resonance (EPR) spectroscopy. The results of this study reveal potential inhibitory and synergistic effects caused by groundwater and soil constituents during the application of in-situ chemical oxidation.

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes.

PubMed

Rybnikova, V; Usman, M; Hanna, K

2016-09-01

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe(0), Fe/Ni, Fe3O4, Fe3 - x Ni x O4). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H2O2 or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe3O4) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe(0) and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe(0) and Fe/Ni (18-19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250-500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.

Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

PubMed

Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

2017-12-01

With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

Biodegradation of RDX and MNX with Rhodococcus sp. Strain DN22: New Insights into the Degradation Pathway

DTIC Science & Technology

2010-11-15

denitrosation of MNX by DN22 did not involve direct participation of either oxygen or water, but both played major roles in subsequent secondary chemical and... secondary reactions and products distributions would pro- vide new insights into the degradation pathway of RDX and thus help in the development of...not involve direct participation of either oxygen or water, but both played major roles in subsequent secondary chemical and biochemical reactions of

High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HRMAS NMR) for Studies of Reactive Fabrics

DTIC Science & Technology

2015-11-01

Group Chemistry, 2010, 9, 205-219. 6 C. A. S. Brevett and K. B. Sumpter, “ Sulfur Mustard Degradation on Ambient and Moist Concrete ”, ECBC Technical...reactions of reagents including chemical weapons on materials like concrete , soil, and sand, as well as reactive polymers.3,4,5,6,7 There are...Sumpter, G. W. Wagner, “Degradation of Mustard on Concrete : GC/MSD and SSMAS,” ECBC Technical Report ECBC-TR-482, Edgewood Chemical Biological Center

Biodegradation of Jet Fuel-4 (JP-4) in Sequencing Batch Reactors

DTIC Science & Technology

1992-06-01

nalw~eo %CUMENTATION PAGE__ _ _ _ _ _ _ _ _O 74S Ab -A258 020 L AW POi~W6 DATI .~ TYP AIMqm ,-& 0 U. glbs A~ I ma"&LFUN Mu BIODEGRADATION OF JET FUEL...Specific Objectives of This Proposal Are: 1. To assess the ability of C. resinae , P. chrysosporium and selected bacterial consortia to degrade individual...chemical components of JP-4. 2. To develop a sequencing batch reactor that utilizes C. resinae to degrade chemical components of JP-4 in contaminated

Environmental Decontamination of a Chemical Warfare Simulant Utilizing a Membrane Vesicle-Encapsulated Phosphotriesterase.

PubMed

Alves, Nathan J; Moore, Martin; Johnson, Brandy J; Dean, Scott N; Turner, Kendrick B; Medintz, Igor L; Walper, Scott A

2018-05-09

While technologies for the remediation of chemical contaminants continue to emerge, growing interest in green technologies has led researchers to explore natural catalytic mechanisms derived from microbial species. One such method, enzymatic degradation, offers an alternative to harsh chemical catalysts and resins. Recombinant enzymes, however, are often too labile or show limited activity when challenged with nonideal environmental conditions that may vary in salinity, pH, or other physical properties. Here, we demonstrate how phosphotriesterase encapsulated in a bacterial outer membrane vesicle can be used to degrade the organophosphate chemical warfare agent (CWA) simulant paraoxon in environmental water samples. We also carried out remediation assays on solid surfaces, including glass, painted metal, and fabric, that were selected as representative materials, which could potentially be contaminated with a CWA.

[Studies on photo-electron-chemical catalytic degradation of the malachite green].

PubMed

Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

2010-07-01

A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.

Influences of specific ions in groundwater on concrete degradation in subsurface engineered barrier system.

PubMed

Lin, Wen-Sheng; Liu, Chen-Wuing; Li, Ming-Hsu

2016-01-01

Many disposal concepts currently show that concrete is an effective confinement material used in engineered barrier systems (EBS) at a number of low-level radioactive waste (LLW) disposal sites. Cement-based materials have properties for the encapsulation, isolation, or retardation of a variety of hazardous contaminants. The reactive chemical transport model of HYDROGEOCHEM 5.0 was applied to simulate the effect of hydrogeochemical processes on concrete barrier degradation in an EBS which has been proposed to use in the LLW disposal site in Taiwan. The simulated results indicated that the main processes that are responsible for concrete degradation are the species induced from hydrogen ion, sulfate, and chloride. The EBS with the side ditch drainage system effectively discharges the infiltrated water and lowers the solute concentrations that may induce concrete degradation. The redox processes markedly influence the formations of the degradation materials. The reductive environment in the EBS reduces the formation of ettringite in concrete degradation processes. Moreover, the chemical conditions in the concrete barriers maintain an alkaline condition after 300 years in the proposed LLW repository. This study provides a detailed picture of the long-term evolution of the hydrogeochemical environment in the proposed LLW disposal site in Taiwan.

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation, chemical and advanced oxidation processes.

PubMed

Bagal, Manisha V; Gogate, Parag R

2013-09-01

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3-6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3-11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H2O2), ferrous activated persulfate (HC/Na2S2O8/FeSO4) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO4/H2O2), advanced Fenton (HC/Fe/H2O2) and Fenton-like process (HC/CuO/H2O2) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes. Copyright © 2013 Elsevier B.V. All rights reserved.

Coupled Metagenomic and Chemical Analyses of Degrading Fungal Necromass and Implications for Fungal contributions to Stable Soil Organic Carbon

NASA Astrophysics Data System (ADS)

Egerton-Warburton, L. M.; Schreiner, K. M.; Morgan, B. S. T.; Schultz, J.; Blair, N. E.

2016-12-01

Fungi comprise a significant portion of total soil biomass, the turnover of which must represent a dominant flux within the soil carbon cycle. Fungal organic carbon (OC) can turn over on time scales of days to months, but this process is poorly understood. Here, we examined temporal changes in the chemical and microbial community composition of fungal necromass during a 2-month decomposition experiment in which Fusarium avenaceum (a common saprophyte) was exposed to a natural soil microbial community. Over the course of the experiment, residual fungal necromass was harvested and analyzed using FTIR and thermochemolysis-GCMS to examine chemical changes in the tissue. In addition, genomic DNA was extracted from tissues, amplified with barcoded ITS primers, and sequenced using the high-throughput Illumina platform to examine changes in microbial community composition. Up to 80% of the fungal necromass turned over in the first week. This rapid degradation phase corresponded to colonization of the necromass by known chitinolytic soil fungi including Mortierella species. Members of the Zygomycota and Ascomycota were among the dominant fungal groups involved in degradation with very small contributions from Basidiomycota. At the end of the 2-month degradation, only 15% of the original necromass remained. The residual material was rich in amide and C-O moieties which is consistent with previous work predicting that peptidoglycans are the main residual product from microbial tissue degradation. Straight-chain fatty acids exhibited varying degradation profiles, with some fatty acids (e.g. C16, C18:1) degrading more rapidly than bulk tissue while others maintained steady concentrations relative to bulk OC (C18) or increased in concentration throughout the degradation sequence (C24). These results indicate that the turnover of fungal necromass has the potential to rapidly and significantly influence a variety of soil OC properties including C/N ratios, lipid biomarker distributions, and OC turnover times.

Coupled Metagenomic and Chemical Analyses of Degrading Fungal Necromass and Implications for Microbial Contributions to Stable Soil OC

NASA Astrophysics Data System (ADS)

Schreiner, K. M.; Morgan, B. S. T.; Schultz, J.; Blair, N. E.; Egerton-Warburton, L. M.

2014-12-01

Fungi comprise a significant portion of total soil biomass, the turnover of which must represent a dominant flux within the soil carbon cycle. Fungal OC can turn over on time scales of days to months, but this process is poorly understood. Here, we examined temporal changes in the chemical and microbial community composition of fungal necromass during a 2 month decomposition experiment in which Fusarium avenaceum (a common saprophyte) was exposed to a natural soil microbial community. Over the course of the experiment, residual fungal necromass was harvested and analyzed using FTIR and thermochemolysis-GCMS to examine chemical changes in the tissue. Additionally, genomic DNA was extracted from tissues, amplified with barcoded ITS primers, and sequenced using the high-throughput Illumina platform to examine changes in microbial community composition. Up to 80% of the fungal necromass turned over in the first week. This rapid degradation phase corresponded to colonization of the necromass by known chitinolytic soil fungi including Mortierella species. Zygomycetes and Ascomycetes were among the dominant fungal species involved in degradation with very small contributions from Basidiomycetes. At the end of the 2 month degradation, only 15% of the original necromass remained. The residual material was rich in amide and C-O moieties which is consistent with previous work predicting that peptidoglycans are the main residual product from microbial tissue degradation. Straight-chain fatty acids exhibit varying degradation profiles, with some fatty acids (e.g. C16 and C18:1) degrading more rapidly than bulk tissue, others maintaining steady concentrations relative to bulk OC (e.g. C18), and some increasing in concentration throughout the degradation (e.g. C24). These results indicate that the turnover of fungal necromass has the potential to significantly influence a variety of soil OC properties, including C/N ratios, lipid biomarker distributions, and OC turnover times.

Correlation between mechanical and chemical degradation after outdoor and accelerated laboratory aging for multilayer photovoltaic backsheets

NASA Astrophysics Data System (ADS)

Lin, Chiao-Chi; Lyu, Yadong; Yu, Li-Chieh; Gu, Xiaohong

2016-09-01

Channel cracking fragmentation testing and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy were utilized to study mechanical and chemical degradation of a multilayered backsheet after outdoor and accelerated laboratory aging. A model sample of commercial PPE backsheet, namely polyethylene terephthalate/polyethylene terephthalate/ethylene vinyl acetate (PET/PET/EVA) was investigated. Outdoor aging was performed in Gaithersburg, Maryland, USA for up to 510 days, and complementary accelerated laboratory aging was conducted on the NIST (National Institute of Standards and Technology) SPHERE (Simulated Photodegradation via High Energy Radiant Exposure). Fracture energy, mode I stress intensity factor and film strength were analyzed using an analytical model based on channel cracking fragmentation testing results. The correlation between mechanical and chemical degradation was discussed for both outdoor and accelerated laboratory aging. The results of this work provide preliminary understanding on failure mechanism of backsheets after weathering, laying the groundwork for linking outdoor and indoor accelerated laboratory testing for multilayer photovoltaic backsheets.

Lifetime Extension Report: Progress on the SAVY-4000 Lifetime Extension Program

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

Welch, Cynthia F.; Smith, Paul Herrick; Weis, Eric M.

The 3-year accelerated aging study of the SAVY-4000 O-ring shows very little evidence of significant degradation to samples subjected to aggressive elevated temperature and radiation conditions. Whole container thermal aging studies followed by helium leakage testing and compression set measurements were used to establish an estimate for a failure criterion for O-ring compression set of ≥65 %. The whole container aging studies further show that the air flow and efficiency functions of the filter do not degrade significantly after thermal aging. However, the degradation of the water-resistant function leads to water penetration failure after four months at 210°C, but doesmore » not cause failure after 10 months at 120°C (130°C is the maximum operating temperature for the PTFE membrane). The thermal aging data for O-ring compression set do not meet the assumptions of standard time-temperature superposition analysis for accelerated aging studies. Instead, the data suggest that multiple degradation mechanisms are operative, with a reversible mechanism operative at low aging temperatures and an irreversible mechanism dominating at high aging temperatures. To distinguish between these mechanisms, we have measured compression set after allowing the sample to physically relax, thereby minimizing the effect of the reversible mechanism. The resulting data were analyzed using two distinct mathematical methods to obtain a lifetime estimate based on chemical degradation alone. Both methods support a lifetime estimate of greater than 150 years at 80°C. Although the role of the reversible mechanism is not fully understood, it is clear that the contribution to the total compression set is small in comparison to that due to the chemical degradation mechanism. To better understand the chemical degradation mechanism, thermally aged O-ring samples have been characterized by Fourier Transform Infrared (FTIR), Electron Paramagnetic Resonance (EPR), Gel Permeation Chromatography (GPC), and Differential Scanning Calorimetry (DSC). These experiments detect no significant O-ring degradation below 80°C. Furthermore, durometer measurements indicate that there is no significant change in O-ring hardness at all aging conditions examined. Therefore, our current conservative lifetime estimate for the O-ring and the filter is 10 years at 80°C. In FY17, we will continue to probe the chemical degradation mechanism using oxygen consumption measurements under accelerated aging conditions to reveal temperatures at which oxidation occurs, along with any differences in oxidation rate at the low vs. high aging temperatures. We will also refine the failure criteria and finalize the radiation/thermal synergistic studies to determine a final design lifetime.« less

Biodegradation of Polyethylene and Plastic Mixtures in Mealworms (Larvae of Tenebrio molitor) and Effects on the Gut Microbiome.

PubMed

Brandon, Anja Malawi; Gao, Shu-Hong; Tian, Renmao; Ning, Daliang; Yang, Shan-Shan; Zhou, Jizhong; Wu, Wei-Min; Criddle, Craig S

2018-06-05

Recent studies have demonstrated the ability for polystyrene (PS) degradation within the gut of mealworms ( Tenebrio molitor). To determine whether plastics may be broadly susceptible to biodegradation within mealworms, we evaluated the fate of polyethylene (PE) and mixtures (PE + PS). We find that PE biodegrades at comparable rates to PS. Mass balances indicate conversion of up 49.0 ± 1.4% of the ingested PE into a putative gas fraction (CO 2 ). The molecular weights ( M n ) of egested polymer residues decreased by 40.1 ± 8.5% in PE-fed mealworms and by 12.8 ± 3.1% in PS-fed mealworms. NMR and FTIR analyses revealed chemical modifications consistent with degradation and partial oxidation of the polymer. Mixtures likewise degraded. Our results are consistent with a nonspecific degradation mechanism. Analysis of the gut microbiome by next-generation sequencing revealed two OTUs ( Citrobacter sp. and Kosakonia sp.) strongly associated with both PE and PS as well as OTUs unique to each plastic. Our results suggest that adaptability of the mealworm gut microbiome enables degradation of chemically dissimilar plastics.

Application of calcium peroxide activated with Fe(II)-EDDS complex in trichloroethylene degradation.

PubMed

Zhang, Xiang; Gu, Xiaogang; Lu, Shuguang; Miao, Zhouwei; Xu, Minhui; Fu, Xiaori; Qiu, Zhaofu; Sui, Qian

2016-10-01

This study was conducted to assess the application of calcium peroxide (CP) activated with Fe(II) chelated by (S,S)-ethylenediamine-N,N'-disuccinic acid (EDDS) to enhance trichloroethylene (TCE) degradation in aqueous solution. It was indicated that EDDS prevented soluble iron from precipitation, and the optimum molar ratio of Fe(II)/EDDS to accelerate TCE degradation was 1/1. The influences of initial TCE, CP and Fe(II)-EDDS concentration were also investigated. The combination of CP and Fe(II)-EDDS complex rendered the efficient degradation of TCE at near neutral pH range. Chemical probe and scavenger tests identified that TCE degradation mainly owed to the oxidation of HO while O2(-) promoted HO generation. Cl(-), HCO3(-) and humic acid were found to inhibit CP/Fe(II)-EDDS performance on different levels. In conclusion, the application of CP activated with Fe(II)-EDDS complex is a promising technology in chemical remediation of groundwater, while further research in practical implementation is needed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of salt additives on concrete degradation (Phase II). Executive summary

DOT National Transportation Integrated Search

1995-02-01

This research builds on a previous investigation, which found that corrosion-inhibitor-added deicing salts caused degradation of concrete by both anions and cations. The latest research phase looked at methods to detect the chemical reactions between...

Chemical biology based on target-selective degradation of proteins and carbohydrates using light-activatable organic molecules.

PubMed

Toshima, Kazunobu

2013-05-01

Proteins and carbohydrates play crucial roles in a wide range of biological processes, including serious diseases. The development of novel and innovative methods for selective control of specific proteins and carbohydrates functions has attracted much attention in the field of chemical biology. In this account article, the development of novel chemical tools, which can degrade target proteins and carbohydrates by irradiation with a specific wavelength of light under mild conditions without any additives, is introduced. This novel class of photochemical agents promise bright prospects for finding not only molecular-targeted bioprobes for understanding of the structure-activity relationships of proteins and carbohydrates but also novel therapeutic drugs targeting proteins and carbohydrates.

Reactive Transport of Petroleum Hydrocarbon Constituents in a Shallow Aquifer: Modeling Geochemical Interactions Between Organic and Inorganic Species

NASA Astrophysics Data System (ADS)

McNab, W. W.; Narasimhan, T. N.

1995-08-01

Dissolved organic contaminants such as petroleum hydrocarbon constituents are often observed to degrade in groundwater environments through biologically mediated transformation reactions into carbon dioxide, methane, or intermediate organic compounds. Such transformations are closely tied to local geochemical conditions. Favorable degradation pathways depend upon local redox conditions through thermodynamic constraints and the availability of appropriate mediating microbial populations. Conversely, the progress of the degradation reactions may affect the chemical composition of groundwater through changes in electron donor/acceptor speciation and pH, possibly inducing mineral precipitation/dissolution reactions. Transport of reactive organic and inorganic aqueous species through open systems may enhance the reaction process by mixing unlike waters and producing a state of general thermodynamic disequilibrium. In this study, field data from an aquifer contaminated by petroleum hydrocarbons have been analyzed using a mathematical model which dynamically couples equilibrium geochemistry of inorganic constituents, kinetically dominated sequential degradation of organic compounds, and advective-dispersive chemical transport. Simulation results indicate that coupled geochemical processes inferred from field data, such as organic biodegradation, iron reduction and dissolution, and methanogenesis, can be successfully modeled using a partial-redox-disequilibrium approach. The results of this study also suggest how the modeling approach can be used to study system sensitivity to various physical and chemical parameters, such as the effect of dispersion on the position of chemical fronts and the impact of alternative buffering mineral phases (e.g., goethite versus amorphous Fe(OH)3) on water chemistry.

USING QSAR AND SAR TO PREDICT THE TOXICITY AND DEGRADABILITY OF CHEMICALS IN SEDIMENTS AND WATER: AN EVALUATION USING QUADRICYCLANE AND IT'S ANALOGS

EPA Science Inventory

The NRC has examined the availability of toxicity endpoints for industrial chemicals and concluded that many of these chemicals lack even minimum testing. One way of carrying out risk assessments of chemicals having insufficient experimental data is by using Quantitative Structur...

HYDROLYSIS

EPA Science Inventory

Hydrolytic processes provide the baseline loss rate for any chemical in an aqueous envi- ronment. Although various hydrolytic pathways account for significant degradation of certain classes of organic chemicals, other organic structures are completely inert. Strictly speaking, hy...

Degradation of pesticides with RSDL® (reactive skin decontamination lotion kit) lotion: LC-MS investigation.

PubMed

Fentabil, Messele; Gebremedhin, Mulu; Purdon, J Garfield; Cochrane, Laura; Goldman, Virginia Streusand

2018-09-01

This study examined the degradation of organophosphate (OP) and carbamate pesticides using RSDL ® (Reactive Skin Decontamination Lotion Kit) lotion. Degradation occurs from a nucleophilic substitution (SN) reaction between an ingredient in the RSDL lotion, potassium 2,3-butanedione monoximate (KBDO), with susceptible sites in the pesticides. Evaluation at several molar ratios of KBDO:test articles using liquid chromatography-mass spectrometry (LC-MS) techniques was performed. The OP test articles, parathion, paraoxon, parathion-methyl, paraoxon-methyl and chlorpyrifos were effectively degraded at molar ratios of four and above in less than 6min contact time. Malathion and malaoxon were similarly converted to inactive by-products at molar ratios as low as two in less than 4min. A minimum molar ratio of nine was found to be effective against the carbamate pesticide carbofuran. In the case of aldicarb, complete destruction was achieved at a molar ratio of fifteen and a reaction time of one hour. It is important to note that these studies are based on a direct liquid phase RSDL lotion reaction with the toxic chemicals without the added physical removal decontamination efficacy component provided by the sponge component of the RSDL kit. The RSDL kit is intended to be used to remove or neutralize chemical warfare agents (CWA) and T-2 toxin from the skin. In actual use, the majority of the CWA decontamination occurs through the combined action of the sponge in both removing the chemical from the skin, and in rapidly mixing the chemicals at a high molar ratio of KBDO:CWA within the pores of the sponge to enhance rapid neutralization of the chemical. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Heitkamp, M.A.; Adams, W.J.; Camel, V.

Immobilized bacteria technology (IBT) utilizes inert biocarriers to support high concentrations of chemical-degrading bacteria in reactors designed to provide optimal conditions for microbial activity. This study evaluated IBT performance inpacked bed reactors (PBRs) using a porous inorganic biocarrier (diatomaceous earth), nonporous biocarriers (glass beads), and organic biocarriers having carbon adsorption properties (granular activated carbon) with different porosity. Each reactor was challenged with high chemical loading, acid, dryness, and heat shock conditions. Benchtop PBSs inoculated with a p-nitrophenol (PNP)-degrading Pseudomonas sp. and fed a synthetic waste containing 100 to 1,300 mg/L of PNP showed removal of PNP from effluents within 24more » h of start-up. Chemical loading studies showed maximum PNP removal rates of 6.45 to 7.35 kg/m[sup 3]/d for bacteria in PBRs containing diatomaceous earth beads, glass beads, and activated coconut carbon. A lower PNP removal rate of 1.47 kg/m[sup 3]/d was determined for the activated anthracite carbon, and this PBR responded more slowly to increases in chemical loading. The PBR containing bacteria immobilized on activated coconut carbon showed exceptional tolerance to acid shocking, drying, and heat shocking by maintaining PNP removal rates > 85% throughout the entire study. The other biocarriers showed nearly complete loss of PNP degradation during the perturbations, but all recovered high rates of PNP degradation (> 98% removal) within 48 h after an acid shock at pH2, within 8 d after an acid shock at pH 1.0, within 24 h after drying for 72 h, and within 48 h of heat shocking. The resiliency and high chemical removal efficiency demonstrated by immobilized bacteria in this study support the concept of using IBT for the biotreatment of industrial wastes..« less

MODELING THREE-DIMENSIONAL SUBSURFACE FLOW, FATE AND TRANSPORT OF MICROBES AND CHEMICALS (3DFATMIC)

EPA Science Inventory

A three-dimensional model simulating the subsurface flow, microbial growth and degradation, microbial-chemical reaction, and transport of microbes and chemicals has been developed. he model is designed to solve the coupled flow and transport equations. asically, the saturated-uns...

Towards an improved understanding of processes controlling absorption efficiency and biomagnification of organic chemicals by fish.

PubMed

Xiao, Ruiyang; Arnot, Jon A; MacLeod, Matthew

2015-11-01

Dietary exposure is considered the dominant pathway for fish exposed to persistent, hydrophobic chemicals in the environment. Here we present a dynamic, fugacity-based three-compartment bioaccumulation model that describes the fish body as one compartment and the gastrointestinal tract (GIT) as two compartments. The model simulates uptake from the GIT by passive diffusion and micelle-mediated diffusion, and chemical degradation in the fish and the GIT compartments. We applied the model to a consistent measured dietary uptake and depuration dataset for rainbow trout (n=215) that is comprised of chlorinated benzenes, biphenyls, dioxins, diphenyl ethers, and polycyclic aromatic hydrocarbons (PAHs). Model performance relative to the measured data is statistically similar regardless of whether micelle-mediated diffusion is included; however, there are considerable uncertainties in modeling this process. When degradation in the GIT is assumed to be negligible, modeled chemical elimination rates are similar to measured rates; however, predicted concentrations of the PAHs are consistently higher than measurements by up to a factor of 20. Introducing a kinetic limit on chemical transport from the fish compartment to the GIT and increasing the rate constant for degradation of PAHs in tissues of the liver and/or GIT are required to achieve good agreement between the modelled and measured concentrations for PAHs. Our results indicate that the apparent low absorption efficiency of PAHs relative to the chemicals with similar hydrophobicity is attributable to biotransformation in the liver and/or the GIT. Our results provide process-level insights about controls on the extent of bioaccumulation of chemicals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Degradation of microbial polyesters.

PubMed

Tokiwa, Yutaka; Calabia, Buenaventurada P

2004-08-01

Microbial polyhydroxyalkanoates (PHAs), one of the largest groups of thermoplastic polyesters are receiving much attention as biodegradable substitutes for non-degradable plastics. Poly(D-3-hydroxybutyrate) (PHB) is the most ubiquitous and most intensively studied PHA. Microorganisms degrading these polyesters are widely distributed in various environments. Although various PHB-degrading microorganisms and PHB depolymerases have been studied and characterized, there are still many groups of microorganisms and enzymes with varying properties awaiting various applications. Distributions of PHB-degrading microorganisms, factors affecting the biodegradability of PHB, and microbial and enzymatic degradation of PHB are discussed in this review. We also propose an application of a new isolated, thermophilic PHB-degrading microorganism, Streptomyces strain MG, for producing pure monomers of PHA and useful chemicals, including D-3-hydroxycarboxylic acids such as D-3-hydroxybutyric acid, by enzymatic degradation of PHB.

Simultaneous sound velocity and thickness measurement by the ultrasonic pitch-catch method for corrosion-layer-forming polymeric materials.

PubMed

Kusano, Masahiro; Takizawa, Shota; Sakai, Tetsuya; Arao, Yoshihiko; Kubouchi, Masatoshi

2018-01-01

Since thermosetting resins have excellent resistance to chemicals, fiber reinforced plastics composed of such resins and reinforcement fibers are widely used as construction materials for equipment in chemical plants. Such equipment is usually used for several decades under severe corrosive conditions so that failure due to degradation may result. One of the degradation behaviors in thermosetting resins under chemical solutions is "corrosion-layer-forming" degradation. In this type of degradation, surface resins in contact with a solution corrode, and some of them remain asa corrosion layer on the pristine part. It is difficult to precisely measure the thickness of the pristine part of such degradation type materials by conventional pulse-echo ultrasonic testing, because the sound velocity depends on the degree of corrosion of the polymeric material. In addition, the ultrasonic reflection interface between the pristine part and the corrosion layer is obscure. Thus, we propose a pitch-catch method using a pair of normal and angle probes to measure four parameters: the thicknesses of the pristine part and the corrosion layer, and their respective sound velocities. The validity of the proposed method was confirmed by measuring a two-layer sample and a sample including corroded parts. The results demonstrate that the pitch-catch method can successfully measure the four parameters and evaluate the residual thickness of the pristine part in the corrosion-layer-forming sample. Copyright © 2017 Elsevier B.V. All rights reserved.

ESR Analysis of Polymer Photo-Oxidation

NASA Technical Reports Server (NTRS)

Kim, Soon Sam; Liang, Ranty Hing; Tsay, Fun-Dow; Gupta, Amitave

1987-01-01

Electron-spin resonance identifies polymer-degradation reactions and their kinetics. New technique enables derivation of kinetic model of specific chemical reactions involved in degradation of particular polymer. Detailed information provided by new method enables prediction of aging characteristics long before manifestation of macroscopic mechanical properties.

Analysis of weather patterns associated with air quality degradation and potential health impacts

EPA Science Inventory

Emissions from anthropogenic and natural sources into the atmosphere are determined in large measure by prevailing weather conditions through complex physical, dynamical and chemical processes. Air pollution episodes are characterized by degradation in air quality as reflected by...

DEGRADATION OF POLYNUCLEAR AROMATIC HYDROCARBONS UNDER BENCH-SCALE COMPOST CONDITIONS

EPA Science Inventory

The relationship between biomass growth and degradation of polynuclear aromatic hydrocarbons (PAHs) in soil, and subsequent toxicity reduction, was evaluated in 10 in-vessel, bench-scale compost units. Field soil was aquired from the Reilly Tar and Chemical Company Superfund site...

Monitoring of Gasoline-ethanol Degradation In Undisturbed Soil

NASA Astrophysics Data System (ADS)

Österreicher-Cunha, P.; Nunes, C. M. F.; Vargas, E. A.; Guimarães, J. R. D.; Costa, A.

Environmental contamination problems are greatly emphasised nowadays because of the direct threat they represent for human health. Traditional remediation methods fre- quently present low efficiency and high costs; therefore, biological treatment is being considered as an accessible and efficient alternative for soil and water remediation. Bioventing, commonly used to remediate petroleum hydrocarbon spills, stimulates the degradation capacity of indigenous microorganisms by providing better subsur- face oxygenation. In Brazil, gasoline and ethanol are mixed (78:22 v/v); some authors indicate that despite gasoline high degradability, its degradation in subsurface is hin- dered by the presence of much more rapidly degrading ethanol. Contaminant distribu- tion and degradation in the subsurface can be monitored by several physical, chemical and microbiological methodologies. This study aims to evaluate and follow the degra- dation of a gasoline-ethanol mixture in a residual undisturbed tropical soil from Rio de Janeiro. Bioventing was used to enhance microbial degradation. Shifts in bacte- rial culturable populations due to contamination and treatment effects were followed by conventional microbiology methods. Ground Penetrating Radar (GPR) measure- ments, which consist of the emission of electro-magnetic waves into the soil, yield a visualisation of contaminant degradation because of changes in soil conductivity due to microbial action on the pollutants. Chemical analyses will measure contaminant residue in soil. Our results disclosed contamination impact as well as bioventing stim- ulation on soil culturable heterotrophic bacterial populations. This multidisciplinary approach allows for a wider evaluation of processes occurring in soil.

Low effect of phenanthrene bioaccessibility on its biodegradation in diffusely contaminated soil.

PubMed

Crampon, M; Cébron, A; Portet-Koltalo, F; Uroz, S; Le Derf, F; Bodilis, J

2017-06-01

This study focused on the role of bioaccessibility in the phenanthrene (PHE) biodegradation in diffusely contaminated soil, by combining chemical and microbiological approaches. First, we determined PHE dissipation rates and PHE sorption/desorption isotherms for two soils (PPY and Pv) presenting similar chronic PAH contamination, but different physico-chemical properties. Our results revealed that the PHE dissipation rate was significantly higher in the Pv soil compared to the PPY soil, while PHE sorption/desorption isotherms were similar. Interestingly, increases of PHE desorption and potentially of PHE bioaccessibility were observed for both soils when adding rhamnolipids (biosurfactants produced by Pseudomonas aeruginosa). Second, using 13 C-PHE incubated in the same soils, we analyzed the PHE degrading bacterial communities. The combination of stable isotope probing (DNA-SIP) and 16S rRNA gene pyrosequencing revealed that Betaproteobacteria were the main PHE degraders in the Pv soil, while a higher bacterial diversity (Alpha-, Beta-, Gammaproteobacteria and Actinobacteria) was involved in PHE degradation in the PPY soil. The amendment of biosurfactants commonly used in biostimulation methods (i.e. rhamnolipids) to the two soils clearly modified the PHE sorption/desorption isotherms, but had no significant impact on PHE degradation rates and PHE-degraders identity. These results demonstrated that increasing the bioaccessibility of PHE has a low impact on its degradation and on the functional populations involved in this degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Silage fermentation and ruminal degradation of stylo prepared with lactic acid bacteria and cellulase.

PubMed

Li, Mao; Zhou, Hanlin; Zi, Xuejuan; Cai, Yimin

2017-10-01

In order to improve the silage fermentation of stylo (Stylosanthes guianensis) in tropical areas, stylo silages were prepared with commercial additives Lactobacillus plantarum Chikuso-1 (CH1), L. rhamnasus Snow Lact L (SN), Acremonium cellulase (CE) and their combination as SN+CE or CH1 + CE, and the fermentation quality, chemical composition and ruminal degradation of these silages were studied. Stylo silages treated with lactic acid bacteria (LAB) or cellulase, the pH value and NH 3 -N ⁄ total-N were significantly (P < 0.05) decreased while the ruminal degradability of dry matter (DM), crude protein (CP), neutral detergent fiber (aNDFom) and acid detergent fiber (ADFom) were significantly (P < 0.05) increased compared to control. Compared to LAB or cellulase-treated silages, the DM, CP contents and relative feed value (RFV), and the ruminal degradability in LAB plus cellulase-treated silages were significantly (P < 0.05) higher, but the aNDFom content was significantly (P < 0.05) lower. CH1 + CE treatment was more effective in silage fermentation and ruminal degradation than SN+CE treatment. The results confirmed that LAB or LAB plus cellulase treatment could improve the fermentation quality, chemical composition and ruminal degradation of stylo silage. Moreover, the combined treatment with LAB and cellulase may have beneficial synergistic effects on ruminal degradation. © 2017 Japanese Society of Animal Science.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

PubMed

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

The application of electrochemistry to pharmaceutical stability testing--comparison with in silico prediction and chemical forced degradation approaches.

PubMed

Torres, Susana; Brown, Roland; Szucs, Roman; Hawkins, Joel M; Zelesky, Todd; Scrivens, Garry; Pettman, Alan; Taylor, Mark R

2015-11-10

The aim of this study was to evaluate the use of electrochemistry to generate oxidative degradation products of a model pharmaceutical compound. The compound was oxidized at different potentials using an electrochemical flow-cell fitted with a glassy carbon working electrode, a Pd/H2 reference electrode and a titanium auxiliary electrode. The oxidative products formed were identified and structurally characterized by LC-ESI-MS/MS using a high resolution Q-TOF mass spectrometer. Results from electrochemical oxidation using electrolytes of different pH were compared to those from chemical oxidation and from accelerated stability studies. Additionally, oxidative degradation products predicted using an in silico commercially available software were compared to those obtained from the various experimental methods. The electrochemical approach proved to be useful as an oxidative stress test as all of the final oxidation products observed under accelerated stability studies could be generated; previously reported reactive intermediate species were not observed most likely because the electrochemical mechanism differs from the oxidative pathway followed under accelerated stability conditions. In comparison to chemical degradation tests electrochemical degradation has the advantage of being much faster and does not require the use of strong oxidizing agents. Moreover, it enables the study of different operating parameters in short periods of time and optimisation of the reaction conditions (pH and applied potential) to achieve different oxidative products mixtures. This technique may prove useful as a stress test condition for the generation of oxidative degradation products and may help accelerate structure elucidation and development of stability indicating analytical methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Physical-chemical characterization of the textile dye Azo Ab52 degradation by corona plasma

NASA Astrophysics Data System (ADS)

Gómez, A.; Torres-Arenas, A. J.; Vergara-Sánchez, J.; Torres, C.; Reyes, P. G.; Martínez, H.; Saldarriaga-Noreña, Hugo

2017-10-01

This work characterizes the degradation of the textile dye azo Acid Black 52 by measuring several physical and chemical parameters. A corona plasma was created at atmospheric pressure and applied on the liquid-air interface of water samples containing the dye. 1.0 mM of ferrous sulfate (FeSO4) was added to 1.0 mM dye solution, for a total volume of 250 mL. For each treatment, a number of parameters were quantified. These were voltage, current, temperature, loss of volume, pH, electrical conductivity, concentration, optical mission spectra, chemical oxygen demand (COD), total organic carbon (TOC), and the removal ratio. Because of the increase in the sample temperature, the volume lost by evaporation was explored. The results show that the efficiency of the dye degradation by plasma is a function of treatment time. Moreover, the reactive concentration of FeSO4 and the exposition time of the plasma were varied at a constant volume, leading to the determination of the concentrations and optimal times. Considering the degradation and removal parameters, at the maximum treated time of 80 min, it found that COD was of 96.36%, TOC of 93.93%, and the removal ratio of 97.47%.

Scenarios and methods that induce protruding or released CNTs after degradation of nanocomposite materials.

PubMed

Hirth, Sabine; Cena, Lorenzo; Cox, Gerhard; Tomović, Zeljko; Peters, Thomas; Wohlleben, Wendel

2013-04-01

Nanocomposite materials may be considered as a low-risk application of nanotechnology, if the nanofillers remain embedded throughout the life-cycle of the products in which they are embedded. We hypothesize that release of free CNTs occurs by a combination of mechanical stress and chemical degradation of the polymer matrix. We experimentally address limiting cases: Mechanically released fragments may show tubular protrusions on their surface. Here we identify these protrusions unambiguously as naked CNTs by chemically resolved microscopy and a suitable preparation protocol. By size-selective quantification of fragments we establish as a lower limit that at least 95 % of the CNTs remain embedded. Contrary to classical fiber composite approaches, we link this phenomenon to matrix materials with only a few percent elongation at break, predicting which materials should still cover their CNT nanofillers after machining. Protruding networks of CNTs remain after photochemical degradation of the matrix, and we show that it takes the worst case combinations of weathering plus high-shear wear to release free CNTs in the order of mg/m 2 /year. Synergy of chemical degradation and mechanical energy input is identified as the priority scenario of CNT release, but its lab simulation by combined methods is still far from real-world validation.

Ionic liquid biodegradability depends on specific wastewater microbial consortia.

PubMed

Docherty, Kathryn M; Aiello, Steven W; Buehler, Barbara K; Jones, Stuart E; Szymczyna, Blair R; Walker, Katherine A

2015-10-01

Complete biodegradation of a newly-synthesized chemical in a wastewater treatment plant (WWTP) eliminates the potential for novel environmental pollutants. However, differences within- and between-WWTP microbial communities may alter expectations for biodegradation. WWTP communities can also serve as a source of unique consortia that, when enriched, can metabolize chemicals that tend to resist degradation, but are otherwise promising green alternatives. We tested the biodegradability of three ionic liquids (ILs): 1-octyl-3-methylpyridinium bromide (OMP), 1-butyl-3-methylpyridinium bromide (BMP) and 1-butyl-3-methylimidazolium chloride (BMIM). We performed tests using communities from two WWTPs at three time points. Site-specific and temporal variation both influenced community composition, which impacted the success of OMP biodegradability. Neither BMP nor BMIM degraded in any test, suggesting that these ILs are unlikely to be removed by traditional treatment. Following standard biodegradation assays, we enriched for three consortia that were capable of quickly degrading OMP, BMP and BMIM. Our results indicate WWTPs are not functionally redundant with regard to biodegradation of specific ionic liquids. However, consortia can be enriched to degrade chemicals that fail biodegradability assays. This information can be used to prepare pre-treatment procedures and prevent environmental release of novel pollutants. Copyright © 2015 Elsevier Ltd. All rights reserved.

Radiation and chemical degradation of UVR protection characteristics of fabrics.

PubMed

Khazova, M; O'Hagan, J B; Grainger, K J-L

2007-01-01

Clothing can provide substantial protection against solar ultraviolet radiation (UVR) and quantifying the amount of protection can have useful applications to recreational, occupational and medical situations. However, exposure of fabrics to sunlight and sea water can alter their physical and chemical properties, resulting in a change of UVR attenuation characteristics. The objective of the current study was to evaluate the effects of environmental degradation of fabrics on their UVR protection characteristics. The methodologies applied in this study can be used also for the assessment of protective clothing against occupational exposure.

[Photocatalytic Degradation of Perfluorooctanoic Acid by Pd-TiO2 Photocatalyst].

PubMed

Liu, Qing; Yu, Ze-bin; Zhang, Rui-han; Li, Ming-jie; Chen, Ying; Wang, Li; Kuang, Yu; Zhang, Bo; Zhu, You-hui

2015-06-01

Perfluorooctanoic acid (PFOA) is a new persistent organic pollutant which has got global concern for its wide distribution, high bioaccumulation and strong biological toxicity. In present study, the photocatalytic degradation of PFOA using palladium doped TiO2 (Pd-TiO2) prepared by chemical reduction method was investigated. The photocatalysts were characterized by XRD, FESEM and UV-vis DRS and were used for PFOA degradation under 365 nm UV irradiation. The results indicated that the grain size of TiO2 was smaller while the specific surface area increased and the absorption of ultraviolet light also enhanced after using chemical reduction method, but all these changes had no influence on PFOA degradation. However, the degradation was significantly enhanced because of the deposition of Pd, the fluoride concentration of PFOA was 6.62 mg x L(-1) after 7 h irradiation which was 7.3 times higher than that of TiO2 (P25). Experiments with the addition of trapping agent and nitrogen indicated that *OH played an important role in PFOA degradation while the presence of O2 accelerated the degradation. The main intermediate products of photocatalytic degradation of PFOA were authenticated by an ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry systems (UPLC-QTOF-MS). The probable photocatalytic degradation mechanism involves h+ attacking the carboxyl of PFOA and resulting in decarboxylation. The produced *CnF(2n +1) was oxidized by *OH underwent defluorinetion to form shorter-chain perfluorinated carboxylic acids. The significant enhancement of PFOA degradation can be ascribed to the palladium deposits, acting as electron traps on the Pd-TiO2 surface, which facilitated the transfer of photogenerated electrons and retarded the accumulation of electrons.

Sampling and Analysis of Emerging Pollutants

EPA Science Inventory

Historically, environmental monitoring programs have focused on organic chemicals which are known to resist degradation, bioaccumulate in the fatty tissues of organisms and have a known adverse toxicological effect. The Stockholm Convention identified several classes of chemical...

Screening of nitrogen mustards and their degradation products in water and decontamination solution by liquid chromatography-mass spectrometry.

PubMed

Chua, Hoe-Chee; Lee, Hoi-Sim; Sng, Mui-Tiang

2006-01-13

Analysing nitrogen mustards and their degradation products in decontamination emulsions posed a significant challenge due to the different phases present in such matrices. Extensive sample preparation may be required to isolate target analytes. Furthermore, numerous reaction products are formed in the decontamination emulsion. A fast and effective qualitative screening procedure was developed for these compounds, using liquid chromatography-mass spectrometry (LC-MS). This eliminated the need for additional sample handling and derivatisation that are required for gas chromatographic-mass spectrometric (GC-MS) analysis. A liquid chromatograph with mixed mode column and isocratic elution gave good chromatography. The feasibility of applying this technique for detecting these compounds in spiked water and decontamination emulsion was demonstrated. Detailed characterisation of the degradation products in these two matrices was carried out. The results demonstrated that N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA) and triethanolamine (TEA) are not the major degradation products of their respective nitrogen mustards. Degradation profiles of nitrogen mustards in water were also established. In verification analysis, it is important not only to develop methods for the identification of the actual chemical agents; the methods must also encompass degradation products of the chemical agents as well so as to exclude false negatives. This study demonstrated the increasingly pivotal role that LC-MS play in verification analysis.

Sonodegradation of cyanidin-3-glucosylrutinoside: degradation kinetic analysis and its impact on antioxidant capacity in vitro.

PubMed

Sun, Jianxia; Li, Xinghua; Lin, Xinyu; Mei, Zhouxiong; Li, Yitao; Ding, Lijun; Bai, Weibin

2017-03-01

As an alternative preservation method for thermal treatment, ultrasound comprises a novel non-thermal processing technology that can significantly avoid undesirable nutritional changes. However, the recent literature indicates that anthocyanin degradation occurs when ultrasound is applied in juice at high amplitude parameters. Such work has mainly focussed on the effect of ultrasound on stability, the antioxidant capacity of cyanidin-3-glucosylrutinoside (Cy-3-glc-rut) and the correlation between anthocyanin degradation and ·OH generation in a simulated system. The spectral intensities of Cy-3-glc-rut at 518 and 282 nm decreased with increasing ultrasound power and treatment time. The degradation of Cy-3-glc-rut was consistent with first-order reaction kinetics (r 2  > 0.9000) and there was a good linear correlation between anthocyanin degradation and hydroxyl radical formation induced by ultrasound (r 2  = 0.9258). Moreover, a decrease in the antioxidant activity of Cy-3-glc-rut after ultrasound evaluated by the 1,1-diphenyl-2-picrylhydrazyl and ferric reducing antioxidant power methods was observed. Overall, the results of the present study show that ultrasound will accelerate the degradation of Cy-3-glc-rut with the growth of power over time. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Solar-driven thermo- and electrochemical degradation of nitrobenzene in wastewater: Adaptation and adoption of solar STEP concept.

PubMed

Gu, Di; Shao, Nan; Zhu, Yanji; Wu, Hongjun; Wang, Baohui

2017-01-05

The STEP concept has successfully been demonstrated for driving chemical reaction by utilization of solar heat and electricity to minimize the fossil energy, meanwhile, maximize the rate of thermo- and electrochemical reactions in thermodynamics and kinetics. This pioneering investigation experimentally exhibit that the STEP concept is adapted and adopted efficiently for degradation of nitrobenzene. By employing the theoretical calculation and thermo-dependent cyclic voltammetry, the degradation potential of nitrobenzene was found to be decreased obviously, at the same time, with greatly lifting the current, while the temperature was increased. Compared with the conventional electrochemical methods, high efficiency and fast degradation rate were markedly displayed due to the co-action of thermo- and electrochemical effects and the switch of the indirect electrochemical oxidation to the direct one for oxidation of nitrobenzene. A clear conclusion on the mechanism of nitrobenzene degradation by the STEP can be schematically proposed and discussed by the combination of thermo- and electrochemistry based the analysis of the HPLC, UV-vis and degradation data. This theory and experiment provide a pilot for the treatment of nitrobenzene wastewater with high efficiency, clean operation and low carbon footprint, without any other input of energy and chemicals from solar energy. Copyright © 2016 Elsevier B.V. All rights reserved.

Chemical dispersants can suppress the activity of natural oil-degrading microorganisms

PubMed Central

Kleindienst, Sara; Seidel, Michael; Ziervogel, Kai; Grim, Sharon; Loftis, Kathy; Harrison, Sarah; Malkin, Sairah Y.; Perkins, Matthew J.; Field, Jennifer; Sogin, Mitchell L.; Dittmar, Thorsten; Passow, Uta; Medeiros, Patricia M.; Joye, Samantha B.

2015-01-01

During the Deepwater Horizon oil well blowout in the Gulf of Mexico, the application of 7 million liters of chemical dispersants aimed to stimulate microbial crude oil degradation by increasing the bioavailability of oil compounds. However, the effects of dispersants on oil biodegradation rates are debated. In laboratory experiments, we simulated environmental conditions comparable to the hydrocarbon-rich, 1,100 m deep plume that formed during the Deepwater Horizon discharge. The presence of dispersant significantly altered the microbial community composition through selection for potential dispersant-degrading Colwellia, which also bloomed in situ in Gulf deep waters during the discharge. In contrast, oil addition to deepwater samples in the absence of dispersant stimulated growth of natural hydrocarbon-degrading Marinobacter. In these deepwater microcosm experiments, dispersants did not enhance heterotrophic microbial activity or hydrocarbon oxidation rates. An experiment with surface seawater from an anthropogenically derived oil slick corroborated the deepwater microcosm results as inhibition of hydrocarbon turnover was observed in the presence of dispersants, suggesting that the microcosm findings are broadly applicable across marine habitats. Extrapolating this comprehensive dataset to real world scenarios questions whether dispersants stimulate microbial oil degradation in deep ocean waters and instead highlights that dispersants can exert a negative effect on microbial hydrocarbon degradation rates. PMID:26553985

DEGRADATION OF MTBE INTERMEDIATES USING FENTON'S REAGENT

EPA Science Inventory

In a previous study, the chemical oxidation of MTBE at low concentrations in water using the Fenton's reagent (FR) was investigated. At certain reaction conditions the process achieved 99.99% degradation of MTBE but it did not result in complete MTBE mineralization. In the pres...

Photo, thermal and chemical degradation of riboflavin

PubMed Central

Kazi, Sadia Hafeez; Ahmed, Sofia; Anwar, Zubair; Ahmad, Iqbal

2014-01-01

Summary Riboflavin (RF), also known as vitamin B2, belongs to the class of water-soluble vitamins and is widely present in a variety of food products. It is sensitive to light and high temperature, and therefore, needs a consideration of these factors for its stability in food products and pharmaceutical preparations. A number of other factors have also been identified that affect the stability of RF. These factors include radiation source, its intensity and wavelength, pH, presence of oxygen, buffer concentration and ionic strength, solvent polarity and viscosity, and use of stabilizers and complexing agents. A detailed review of the literature in this field has been made and all those factors that affect the photo, thermal and chemical degradation of RF have been discussed. RF undergoes degradation through several mechanisms and an understanding of the mode of photo- and thermal degradation of RF may help in the stabilization of the vitamin. A general scheme for the photodegradation of RF is presented. PMID:25246959

Exploring anaerobic environments for cyanide and cyano-derivatives microbial degradation.

PubMed

Luque-Almagro, Víctor M; Cabello, Purificación; Sáez, Lara P; Olaya-Abril, Alfonso; Moreno-Vivián, Conrado; Roldán, María Dolores

2018-02-01

Cyanide is one of the most toxic chemicals for living organisms described so far. Its toxicity is mainly based on the high affinity that cyanide presents toward metals, provoking inhibition of essential metalloenzymes. Cyanide and its cyano-derivatives are produced in a large scale by many industrial activities related to recovering of precious metals in mining and jewelry, coke production, steel hardening, synthesis of organic chemicals, and food processing industries. As consequence, cyanide-containing wastes are accumulated in the environment becoming a risk to human health and ecosystems. Cyanide and related compounds, like nitriles and thiocyanate, are degraded aerobically by numerous bacteria, and therefore, biodegradation has been offered as a clean and cheap strategy to deal with these industrial wastes. Anaerobic biological treatments are often preferred options for wastewater biodegradation. However, at present very little is known about anaerobic degradation of these hazardous compounds. This review is focused on microbial degradation of cyanide and related compounds under anaerobiosis, exploring their potential application in bioremediation of industrial cyanide-containing wastes.

Evaluating paper degradation progress. Cross-linking between chromatographic, spectroscopic and chemical results

NASA Astrophysics Data System (ADS)

Łojewski, Tomasz; Zięba, Katarzyna; Knapik, Arkadiusz; Bagniuk, Jacek; Lubańska, Anna; Łojewska, Joanna

2010-09-01

The study presents an overview of the chromatographic (SEC), spectroscopic (FTIR, UV/VIS), viscometric (DP) and chemical methods (titration, pH) used for the evaluation of the degradation progress of various kinds of paper under various conditions. The methods were chosen to follow different routes of paper degradation. Model paper samples represented boundary paper types from pure cellulose cotton paper, through softwood to low quality acidic, sized groundwood paper The accelerated ageing conditions were adjusted to achieve maximum effect (climatic chamber RH 59%, 90oC) and also to mimic the environment inside books (closed vials). The results were settled on the literature data on the degradation mechanisms and compared in terms of the paper types and ageing conditions. The estimators of coupled de-polymerisation and oxidation have been proposed based on the correlation between SEC, UV/VIS and titrative coppper number determination. The overall oxidation index derived from FTIR results was shown to correlate with the summary -CHO and -COOH concentration determined by titrative methods.

Kinetics of microbial degradation of deicing chemicals in percolated porous media - the modeling perspective

NASA Astrophysics Data System (ADS)

Wehrer, Markus; Lissner, Heidi; Totsche, Kai

2013-04-01

A quantitative knowledge of the fate of deicing chemicals in the subsurface can be provided by analysis of laboratory and field experiments with numerical simulation models. In the present study, experimental data of microbial degradation of the deicing chemical propylene glycol (PG) under flow conditions in soil columns and field lysimeters were simulated to analyze the process conditions of degradation and to obtain the according parameters. Results from the column experiment were evaluated applying different scenarios of an advection-dispersion model using HYDRUS-1D. To reconstruct the data, different competing degradation models were included, i.e., zero order, first order and inclusion of a growing and decaying biomass. The general breakthrough behavior of propylene glycol in soil columns can be simulated well using a coupled model of solute transport and degradation with growth and decay of biomass. The susceptibility of the model to non-unique solutions was investigated using systematical forward and inverse simulations. We found that the model tends to equifinal solutions under certain conditions. Complex experimental boundary conditions can help to avoid this. Under field conditions, the situation is far more complex than in the laboratory. Studying the fate of PG with undisturbed lysimeters we found that aerobic and anaerobic degradation occurs simultaneously. We attribute this to the physical structure and the aggregated nature of the undisturbed soil material . This results in the presence of spatially disjoint oxidative and reductive regions of microbial activity and requires, but is not fully reflected by a dual porosity model. Currently, the numerical simulation of this system is in progress, considering several flow and transport models. A stochastic global search algorithm (DREAM-ZS) is used in conjuction with HYDRUS-1D to avoid local minima in the inverse simulations. The study shows the current limitations and potentials of modeling degradation in an aggregated and structured system under flow conditions.

Spectral properties of Titan's impact craters imply chemical weathering of its surface

PubMed Central

Barnes, J. W.; Sotin, C.; MacKenzie, S.; Soderblom, J. M.; Le Mouélic, S.; Kirk, R. L.; Stiles, B. W.; Malaska, M. J.; Le Gall, A.; Brown, R. H.; Baines, K. H.; Buratti, B.; Clark, R. N.; Nicholson, P. D.

2015-01-01

Abstract We examined the spectral properties of a selection of Titan's impact craters that represent a range of degradation states. The most degraded craters have rims and ejecta blankets with spectral characteristics that suggest that they are more enriched in water ice than the rims and ejecta blankets of the freshest craters on Titan. The progression is consistent with the chemical weathering of Titan's surface. We propose an evolutionary sequence such that Titan's craters expose an intimate mixture of water ice and organic materials, and chemical weathering by methane rainfall removes the soluble organic materials, leaving the insoluble organics and water ice behind. These observations support the idea that fluvial processes are active in Titan's equatorial regions. PMID:27656006

Surface catalytic degradation study of two linear perfluoropolyalkylethers at 345 C

NASA Technical Reports Server (NTRS)

Morales, Wilfredo

1987-01-01

Thin-liquid-film degradation studies of two commercially available perfluoropolyalkylether fluids (PFAE) were performed at 345 C, in nitrogen and air atmospheres, on iron and 440 C stainless steel surfaces. It was found that one fluid degraded on both iron and 440 C stainless steel surfaces in an air atmosphere, whereas the other fluid did not degrade. Chemical analysis revealed that the test fluid degraded to lower molecular weight products and that the degradation was accompanied by the formation of a brownish deposit on both the iron and 440 C stainless steel surfaces. Surface analysis of the deposit revealed a susbstantial amount of iron oxide (Fe2O3). It was hypothesized that the fluid which degraded did so because of its acetal structure. The other fluid, lacking the acetal structure, did not degrade.

Varying Conditions for Hexanoic Acid Degradation with BioTiger™

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

Foreman, Koji; Milliken, Charles; Brigmon, Robin

BioTiger™ (BT) is a consortium of 12 bacteria designed for petroleum waste biodegradation. BT is currently being studied and could be considered for bioremediation of the Athabasca oil sands refineries in Canada and elsewhere. The run-off ponds from the petroleum extraction processes, called tailings ponds, are a mixture of polycyclic aromatic hydrocarbons, naphthenic acids, hydrocarbons, toxic chemicals like heavy metals, water, and sand. Due to environmental regulations the oil industry would like to separate and degrade the hazardous chemical species from the tailings ponds while recycling the water. It has been shown that BT at 30 C° is able tomore » completely degrade 10 mM hexanoic acid (HA) co-metabolically with 0.2% yeast extract (w/v) in 48 hours when starting at 0.4 OD 600nm. After establishing this stable degradation capability, variations were tested to explore the wider parameters of BT activity in temperature, pH, intermediate degradation, co-metabolic dependence, and transfer stability. Due to the vast differences in temperature at various points in the refineries, a wide range of temperatures were assessed. The results indicate that BT retains the ability to degrade HA, a model surrogate for tailings pond contaminants, at temperatures ranging from 15°C to 35°C. Hexanamide (HAM) was shown to be an intermediate generated during the degradation of HA in an earlier work and HAM is completely degraded after 48 hours, indicating that HAM is not the final product of HA degradation. Various replacements for yeast extract were attempted. Glucose, a carbon source; casein amino acids, a protein source; additional ammonia, mimicking known media; and additional phosphate with Wolffe’s vitamins and minerals all showed no significant degradation of HA compared to control. Decreasing the yeast extract concentration (0.05%) demonstrated limited but significant degradation. Finally, serial inoculations of BT were performed to determine the stability of degradation over several generations. Overall, BT has shown to be moderately flexible for HA co-metabolic biodegradation.« less

Development of the HS-SPME-GC-MS/MS method for analysis of chemical warfare agent and their degradation products in environmental samples.

PubMed

Nawała, Jakub; Czupryński, Krzysztof; Popiel, Stanisław; Dziedzic, Daniel; Bełdowski, Jacek

2016-08-24

After World War II approximately 50,000 tons of chemical weapons were dumped in the Baltic Sea by the Soviet Union under the provisions of the Potsdam Conference on Disarmament. These dumped chemical warfare agents still possess a major threat to the marine environment and to human life. Therefore, continue monitoring of these munitions is essential. In this work, we present the application of new solid phase microextraction fibers in analysis of chemical warfare agents and their degradation products. It can be concluded that the best fiber for analysis of sulfur mustard and its degradation products is butyl acrylate (BA), whereas for analysis of organoarsenic compounds and chloroacetophenone, the best fiber is a co-polymer of methyl acrylate and methyl methacrylate (MA/MMA). In order to achieve the lowest LOD and LOQ the samples should be divided into two subsamples. One of them should be analyzed using a BA fiber, and the second one using a MA/MMA fiber. When the fast analysis is required, the microextraction should be performed by use of a butyl acrylate fiber because the extraction efficiency of organoarsenic compounds for this fiber is acceptable. Next, we have elaborated of the HS-SPME-GC-MS/MS method for analysis of CWA degradation products in environmental samples using laboratory obtained fibers The analytical method for analysis of organosulfur and organoarsenic compounds was optimized and validated. The LOD's for all target chemicals were between 0.03 and 0.65 ppb. Then, the analytical method developed by us, was used for the analysis of sediment and pore water samples from the Baltic Sea. During these studies, 80 samples were analyzed. It was found that 25 sediments and 5 pore water samples contained CWA degradation products such as 1,4-dithiane, 1,4-oxathiane or triphenylarsine, the latter being a component of arsine oil. The obtained data is evidence that the CWAs present in the Baltic Sea have leaked into the general marine environment. Copyright © 2016 Elsevier B.V. All rights reserved.

MICROCOSM STUDY OF DEGRADATION OF CHLORINATED SOLVENTS ON SYNTHETIC GREEN RUST MINERALS

EPA Science Inventory

Green rust minerals contain ferrous ion in their structure that can potentially serve as a chemical reductant for degradation of chlorinated solvents. Green rusts are found in zerovalent iron based permeable reactive barriers and in certain soil and sediments. Some previous labor...

Application of compost for effective bioremediation of organic contaminants and pollutants in soil.

PubMed

Kästner, Matthias; Miltner, Anja

2016-04-01

Soils contaminated with hazardous chemicals worldwide are awaiting remediation activities; bioremediation is often considered as a cost-effective remediation approach. Potential bioapproaches are biostimulation, e.g. by addition of nutrients, fertiliser and organic substrates, and bioaugmentation by addition of compound-degrading microbes or of organic amendments containing active microorganisms, e.g. activated sludge or compost. In most contaminated soils, the abundance of the intrinsic metabolic potential is too low to be improved by biostimulation alone, since the physical and chemical conditions in these soils are not conducive to biodegradation. In the last few decades, compost or farmyard manure addition as well as composting with various organic supplements have been found to be very efficient for soil bioremediation. In the present minireview, we provide an overview of the composting and compost addition approaches as 'stimulants' of natural attenuation. Laboratory degradation experiments are often biased either by not considering the abiotic factors or by focusing solely on the elimination of the chemicals without taking the biotic factors and processes into account. Therefore, we first systemise the concepts of composting and compost addition, then summarise the relevant physical, chemical and biotic factors and mechanisms for improved contaminant degradation triggered by compost addition. These factors and mechanisms are of particular interest, since they are more relevant and easier to determine than the composition of the degrading community, which is also addressed in this review. Due to the mostly empirical knowledge and the nonstandardised biowaste or compost materials, the field use of these approaches is highly challenging, but also promising. Based on the huge metabolic diversity of microorganisms developing during the composting processes, a highly complex metabolic diversity is established as a 'metabolic memory' within developing and mature compost materials. Compost addition can thus be considered as a 'super-bioaugmentation' with a complex natural mixture of degrading microorganisms, combined with a 'biostimulation' by nutrient containing readily to hardly degradable organic substrates. It also improves the abiotic soil conditions, thus enhancing microbial activity in general. Finally, this minireview also aims at guiding potential users towards full exploitation of the potentials of this approach.

Chemical characterization, energy values, protein and carbohydrate fractions, degradation kinetics of frost damaged wheat (with severely overall weight loss) in ruminants.

PubMed

Yu, Peiqiang; Racz, Vern

2009-04-01

In Canada, frost damage can result in millions of tonnes of wheat that is not suitable for human consumption (such wheat is referred to as 'frozen') each year. There is a need to systematically evaluate the nutritive value of frozen wheat for ruminants. So far, little research has been conducted to determine the magnitude of the differences in nutritive value between frozen and normal wheat. The objectives of this study were to compare frozen wheat and normal wheat (AC Barrie) in terms of (i) chemical characteristics; (ii) protein and carbohydrate fractions; (iii) energy value; and (iv) rumen degradation kinetics. The results showed that the overall yield losses of the frozen wheat were around 24%. The frozen wheat was significantly lower (P < 0.05) in starch (47 vs. 62%DM), non-structural carbohydrates (60 vs. 70%DM), and non-protein N (63 vs. 93%SCP); and higher (P < 0.05) in crude fat (3 vs. 2%DM), acid (6 vs. 2%DM), neutral detergent fiber (22 vs. 10%DM), lignin (2 vs. 1%DM), acid (3 vs. 1%CP) and neutral detergent insoluble CP (19 vs. 14%CP). The frozen wheat was also lower in (P < 0.05) energy (TDN, DE(3X), ME(3X,) NEL(3X), DE(4X), ME(4X,) NEL(4X) for dairy; ME, NE(m), and NE(g) beef cattle). After partitioning of protein and carbohydrate (CHO) subfractions, the results showed that the frozen wheat was lower (P < 0.05) in the intermediately degradable CP (PB2: 47 vs. 59%CP); and higher in rapidly degradable CP (PB1: 12 vs. 2%CP) and unavailable CP (PC: 3 vs. 1%CP). The frozen wheat was also lower (P < 0.05) in intermediately degradable CHO (CB1: 60 vs. 77%CHO); and higher (P < 0.05) in slowly degradable CHO (CB2: 20 vs. 8%CHO) and unavailable CHO (CC: 5 vs. 2%CHO). The in situ results showed that the frozen wheat had different patterns in rumen degradation kinetics of protein and starch. The extent of the changes varied according to the specific nutrient examined. In conclusion, the frozen wheat differed in chemical characteristics, TDN and energy values, protein and carbohydrate fractions and in situ degradation behavior from normal wheat. The chemical and nutritional characterization of wheat was highly associated with climate condition (frost damage). The frost damage to the wheat reduced nutrient content and availability and thus reduced nutrient supply to ruminants.

Removal of organics and degradation products from industrial wastewater by a membrane bioreactor integrated with ozone or UV/H₂O₂ treatment.

PubMed

Laera, G; Cassano, D; Lopez, A; Pinto, A; Pollice, A; Ricco, G; Mascolo, G

2012-01-17

The treatment of a pharmaceutical wastewater resulting from the production of an antibacterial drug (nalidixic acid) was investigated employing a membrane bioreactor (MBR) integrated with either ozonation or UV/H(2)O(2) process. This was achieved by placing chemical oxidation in the recirculation stream of the MBR. A conventional configuration with chemical oxidation as polishing for the MBR effluent was also tested as a reference. The synergistic effect of MBR when integrated with chemical oxidation was assessed by monitoring (i) the main wastewater characteristics, (ii) the concentration of nalidixic acid, (iii) the 48 organics identified in the raw wastewater and (iv) the 55 degradation products identified during wastewater treatment. Results showed that MBR integration with ozonation or UV/H(2)O(2) did not cause relevant drawbacks to both biological and filtration processes, with COD removal rates in the range 85-95%. Nalidixic acid passed undegraded through the MBR and was completely removed in the chemical oxidation step. Although the polishing configuration appeared to give better performances than the integrated system in removing 15 out of 48 secondary organics while similar removals were obtained for 19 other compounds. The benefit of the integrated system was however evident for the removal of the degradation products. Indeed, the integrated system allowed higher removals for 34 out of 55 degradation products while for only 4 compounds the polishing configuration gave better performance. Overall, results showed the effectiveness of the integrated treatment with both ozone and UV/H(2)O(2).

Chemical chaperones reduce endoplasmic reticulum stress and prevent mutant HFE aggregate formation.

PubMed

de Almeida, Sérgio F; Picarote, Gonçalo; Fleming, John V; Carmo-Fonseca, Maria; Azevedo, Jorge E; de Sousa, Maria

2007-09-21

HFE C282Y, the mutant protein associated with hereditary hemochromatosis (HH), fails to acquire the correct conformation in the endoplasmic reticulum (ER) and is targeted for degradation. We have recently shown that an active unfolded protein response (UPR) is present in the cells of patients with HH. Now, by using HEK 293T cells, we demonstrate that the stability of HFE C282Y is influenced by the UPR signaling pathway that promotes its degradation. Treatment of HFE C282Y-expressing cells with tauroursodeoxycholic acid (TUDCA), a bile acid derivative with chaperone properties, or with the chemical chaperone sodium 4-phenylbutyrate (4PBA) impeded the UPR activation. However, although TUDCA led to an increased stability of the mutant protein, 4PBA contributed to a more efficient disposal of HFE C282Y to the degradation route. Fluorescence microscopy and biochemical analysis of the subcellular localization of HFE revealed that a major portion of the C282Y mutant protein forms intracellular aggregates. Although neither TUDCA nor 4PBA restored the correct folding and intracellular trafficking of HFE C282Y, 4PBA prevented its aggregation. These data suggest that TUDCA hampers the UPR activation by acting directly on its signal transduction pathway, whereas 4PBA suppresses ER stress by chemically enhancing the ER capacity to cope with the expression of misfolded HFE, facilitating its degradation. Together, these data shed light on the molecular mechanisms involved in HFE C282Y-related HH and open new perspectives on the use of orally active chemical chaperones as a therapeutic approach for HH.

Chemical modification

Treesearch

R. M. Rowell

2004-01-01

Wood is a hygroscopic resource that was designed to perform, in nature, in a wet environment. Nature is programmed to recycle wood in a timely way through biological, thermal, aqueous, photochemical, chemical, and mechanical degradations. In simple terms, nature builds wood from carbon dioxide and water and has all the tools to recycle it back to the starting chemicals...

Characterization of designer biochar produced at different temperatures and their effects on a loamy sand

USDA-ARS?s Scientific Manuscript database

Biochar supplements to degraded soils have the potential to improve crop yield and soil quality. We hypothesize that the biochar chemical production process can be tailored to form designer biochars that have specific chemical characteristics matched to selective chemical and/or physical issues of a...

Enhanced degradation of chitosan by applying plasma treatment in combination with oxidizing agents for potential use as an anticancer agent.

PubMed

Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Watthanaphanit, Anyarat; Theeramunkong, Sewan; Saito, Nagahiro; Yamashita, Kazuko; Arakawa, Ryuichi

2017-07-01

Solution plasma (SP) treatment in combination with oxidizing agents, i.e., hydrogen peroxide (H 2 O 2 ), potassium persulfate (K 2 S 2 O 8 ) and sodium nitrite (NaNO 2 ) were adopted to chitosan degradation in order to achieve fast degradation rate, low chemicals used and high yield of low-molecular-weight chitosan and chitooligosaccharide (COS). Among the studied oxidizing agents, H 2 O 2 was found to be the best choice in terms of appreciable molecular weight reduction without major change in chemical structure of the degraded products of chitosan. By the combination with SP treatment, dilute solution of H 2 O 2 (4-60mM) was required for effective degradation of chitosan. The combination of SP treatment and dilute solution of H 2 O 2 (60mM) resulted in the great reduction of molecular weight of chitosan and water-soluble chitosan was obtained as a major product. The resulting water-soluble chitosan was precipitated to obtain COS. An inhibitory effect against cervical cancer cell line (HeLa cells) of COS was also examined. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabricating 3D porous PANI/TiO2-graphene hydrogel for the enhanced UV-light photocatalytic degradation of BPA

NASA Astrophysics Data System (ADS)

Chen, Fangyuan; An, Weijia; Li, Yao; Liang, Yinghua; Cui, Wenquan

2018-01-01

Polyaniline (PANI)/TiO2 composite graphene hydrogel was successfully prepared by chemical reduction method. TiO2 and PANI were uniformly dispersed in the three-dimensional network of graphene hydrogels. This rich network of macroscopic structures not only provides desirable conditions for synergistic adsorption and photocatalytic degradation of pollutants, but also improves the chemical stability of composites. Specifically, 80% PANI/TiO2-reduced graphene oxide hydrogel (rGH) can completely degrade BPA in 40 min, and BPA was almost completely mineralized into small molecules in 65 min. After five cycles of experiments, the degradation rate of PANI/TiO2-rGH for BPA was more than 90%. XPS analysis indicated that there is a strong interaction between PANI and TiO2. Hydrogen bonding between TiO2 and rGH was also demonstrated. Quenching experiments indicated •O2- and h+ are the main active species in the degradation of BPA by PANI/TiO2-rGH and •OH and h+ are the main active species by PANI/TiO2, suggesting that rGH and PANI acts as a transmitter for e- and h+, respectively.

Magnitude Differences in Bioactive Compounds, Chemical Functional Groups, Fatty Acid Profiles, Nutrient Degradation and Digestion, Molecular Structure, and Metabolic Characteristics of Protein in Newly Developed Yellow-Seeded and Black-Seeded Canola Lines.

PubMed

Theodoridou, Katerina; Zhang, Xuewei; Vail, Sally; Yu, Peiqiang

2015-06-10

Recently, new lines of yellow-seeded (CS-Y) and black-seeded canola (CS-B) have been developed with chemical and structural alteration through modern breeding technology. However, no systematic study was found on the bioactive compounds, chemical functional groups, fatty acid profiles, inherent structure, nutrient degradation and absorption, or metabolic characteristics between the newly developed yellow- and black-seeded canola lines. This study aimed to systematically characterize chemical, structural, and nutritional features in these canola lines. The parameters accessed include bioactive compounds and antinutrition factors, chemical functional groups, detailed chemical and nutrient profiles, energy value, nutrient fractions, protein structure, degradation kinetics, intestinal digestion, true intestinal protein supply, and feed milk value. The results showed that the CS-Y line was lower (P ≤ 0.05) in neutral detergent fiber (122 vs 154 g/kg DM), acid detergent fiber (61 vs 99 g/kg DM), lignin (58 vs 77 g/kg DM), nonprotein nitrogen (56 vs 68 g/kg DM), and acid detergent insoluble protein (11 vs 35 g/kg DM) than the CS-B line. There was no difference in fatty acid profiles except C20:1 eicosenoic acid content (omega-9) which was in lower in the CS-Y line (P < 0.05) compared to the CS-B line. The glucosinolate compounds differed (P < 0.05) in terms of 4-pentenyl, phenylethyl, 3-CH3-indolyl, and 3-butenyl glucosinolates (2.9 vs 1.0 μmol/g) between the CS-Y and CS-B lines. For bioactive compounds, total polyphenols tended to be different (6.3 vs 7.2 g/kg DM), but there were no differences in erucic acid and condensed tannins with averages of 0.3 and 3.1 g/kg DM, respectively. When protein was portioned into five subfractions, significant differences were found in PA, PB1 (65 vs 79 g/kg CP), PB2, and PC fractions (10 vs 33 g/kg CP), indicating protein degradation and supply to small intestine differed between two new lines. In terms of protein structure spectral profile, there were no significant differences in functional groups of amides I and II, α helix, and β-sheet structure as well as their ratio between the two new lines, indicating no difference in protein structure makeup and conformation between the two lines. In terms of energy values, there were significant differences in total digestible nutrient (TDN; 149 vs 133 g/kg DM), metabolizable energy (ME; 58 vs 52 MJ/kg DM), and net energy for lactation (NEL; 42 vs 37 MJ/kg DM) between CS-Y and CS-B lines. For in situ rumen degradation kinetics, the two lines differed in soluble fraction (S; 284 vs 341 g/kg CP), potential degradation fraction (D; 672 vs 590 g/kg CP), and effective degraded organic matter (EDOM; 710 vs 684 g/kg OM), but no difference in degradation rate. CS-Y had higher digestibility of rumen bypass protein in the intestine than CS-B (566 vs 446 g/kg of RUP, P < 0.05). Modeling nutrient supply results showed that microbial protein synthesis (MCP; 148 vs 171 g/kg DM) and rumen protein degraded balance (DPB; 108 vs 127 g/kg DM) were lower in the CS-Y line, but there were no differences in total truly digested protein in small intestine (DVE) and feed milk value (FMV) between the two lines. In conclusion, the new yellow line had different nutritional, chemical, and structural features compared to the black line. CS-Y provided better nutrient utilization and availability.

Physical Morphology and Quantitative Characterization of Chemical Changes of Weathered PVC/Pine Composites

DTIC Science & Technology

2009-12-22

occurred by oxidation process. Also, oxidation and lignin (from the wood) degradation influenced the color (light- ness) of PVC based WPC upon weathering...and lignin (from the wood) degradation influenced the color (lightness) of PVC based WPC upon weathering. 15. SUBJECT TERMS 16. SECURITY...with DEab. More importantly, previous report showed that color change in wood during weathering was due to the lignin degradation [33]. Infrared spectra

Thermal Characterization and Flammability of Structural Epoxy Adhesive and Carbon/Epoxy Composite with Environmental and Chemical Degradation (Postprint)

DTIC Science & Technology

2012-01-01

this study). TGA scans show the thermal degradation of carbon/ epoxy composite by fuel additive at room temperature. Through Microscale Combustion...concerns regarding the durability of structural epoxy adhesive contaminated by hydraulic fluid or fuel additive , under simplified test conditions (no...higher than room tem- perature) or fuel additive (at all temperatures of this study). TGA scans show the thermal degradation of carbon/ epoxy composite

Effect of ethylenediamine on chemical degradation of insulin aspart in pharmaceutical solutions.

PubMed

Poulsen, Christian; Jacobsen, Dorte; Palm, Lisbeth

2008-11-01

To examine the effect of different amine compounds on the chemical degradation of insulin aspart at pharmaceutical formulation conditions. Insulin aspart preparations containing amine compounds or phosphate (reference) were prepared and the chemical degradation was assessed following storage at 37 degrees C using chromatographic techniques. Ethylenediamine was examined at multiple concentrations and the resulting insulin-ethylenediamine derivates were structurally characterized using matrix assisted laser desorption ionization time-of-flight mass spectroscopy. The effects on ethylenediamine when omitting glycerol or phenolic compounds from the formulations were investigated. Ethylenediamine was superior in terms of reducing formation of high molecular weight protein and insulin aspart related impurities compared to the other amine compounds and phosphate. Monotransamidation of insulin aspart in the presence of ethylenediamine was observed at all of the six possible Asn/Gln residues with Asn(A21) having the highest propensity to react with ethylenediamine. Data from formulations studies suggests a dual mechanism of ethylenediamine and a mandatory presence of phenolic compounds to obtain the effect. The formation of high molecular weight protein and insulin aspart related impurities was reduced by ethylenediamine in a concentration dependant manner.

Visible light assisted photoelectrocatalytic degradation of sugarcane factory wastewater by sprayed CZTS thin films

NASA Astrophysics Data System (ADS)

Hunge, Y. M.; Mahadik, M. A.; Patil, V. L.; Pawar, A. R.; Gadakh, S. R.; Moholkar, A. V.; Patil, P. S.; Bhosale, C. H.

2017-12-01

Highly crystalline Cu2ZnSnS4 (CZTS) thin films have been deposited onto glass and FTO coated glass substrates by simple chemical spray-pyrolysis technique. It is an important material for solar energy conversion through the both photovoltaics and photocatalysis. The effect of substrate temperatures on the physico-chemical properties of the CZTS films is studied. The XRD study shows the formation of single phase CZTS with kesterite structure. FE-SEM analysis reveals nano flakes architecture with pin-hole and crake free surface with more adherent. The film deposited at optimized substrate temperature exhibits optical band gap energy of 1.90 eV, which lies in the visible region of the solar spectrum and useful for photocatalysis application. The photoelectrocatalytic activities of the large surface area (10 × 10 cm2) deposited CZTS thin film photocatalysts were evaluated for the degradation of sugarcane factory wastewater under visible light irradiation. The results show that the CZTS thin film photocatalyst exhibited about 90% degradation of sugar cane factory wastewater. The mineralization of sugarcane factory wastewater is studied by measuring chemical oxygen demand (COD) values.

Impact of excipient interactions on solid dosage form stability.

PubMed

Narang, Ajit S; Desai, Divyakant; Badawy, Sherif

2012-10-01

Drug-excipient interactions in solid dosage forms can affect drug product stability in physical aspects such as organoleptic changes and dissolution slowdown, or chemically by causing drug degradation. Recent research has allowed the distinction in chemical instability resulting from direct drug-excipient interactions and from drug interactions with excipient impurities. A review of chemical instability in solid dosage forms highlights common mechanistic themes applicable to multiple degradation pathways. These common themes include the role of water and microenvironmental pH. In addition, special aspects of solid-state reactions with excipients and/or excipient impurities add to the complexity in understanding and modeling reaction pathways. This paper discusses mechanistic basis of known drug-excipient interactions with case studies and provides an overview of common underlying themes. Recent developments in the understanding of degradation pathways further impact methodologies used in the pharmaceutical industry for prospective stability assessment. This paper discusses these emerging aspects in terms of limitations of drug-excipient compatibility studies, emerging paradigms in accelerated stability testing, and application of mathematical modeling for prediction of drug product stability.

Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

NASA Astrophysics Data System (ADS)

Huang, Q.

2016-12-01

Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.

Optimization of remediation strategies using vadose zone monitoring systems

NASA Astrophysics Data System (ADS)

Dahan, Ofer

2016-04-01

In-situ bio-remediation of the vadose zone depends mainly on the ability to change the subsurface hydrological, physical and chemical conditions in order to enable development of specific, indigenous, pollutants degrading bacteria. As such the remediation efficiency is much dependent on the ability to implement optimal hydraulic and chemical conditions in deep sections of the vadose zone. These conditions are usually determined in laboratory experiments where parameters such as the chemical composition of the soil water solution, redox potential and water content of the sediment are fully controlled. Usually, implementation of desired optimal degradation conditions in deep vadose zone at full scale field setups is achieved through infiltration of water enriched with chemical additives on the land surface. It is assumed that deep percolation into the vadose zone would create chemical conditions that promote biodegradation of specific compounds. However, application of water with specific chemical conditions near land surface dose not necessarily results in promoting of desired chemical and hydraulic conditions in deep sections of the vadose zone. A vadose-zone monitoring system (VMS) that was recently developed allows continuous monitoring of the hydrological and chemical properties of deep sections of the unsaturated zone. The VMS includes flexible time-domain reflectometry (FTDR) probes which allow continuous monitoring of the temporal variation of the vadose zone water content, and vadose-zone sampling ports (VSPs) which are designed to allow frequent sampling of the sediment pore-water and gas at multiple depths. Implementation of the vadose zone monitoring system in sites that undergoes active remediation provides real time information on the actual chemical and hydrological conditions in the vadose zone as the remediation process progresses. Up-to-date the system has been successfully implemented in several studies on water flow and contaminant transport in the unsaturated zone including enhanced bioremediation of contaminated deep vadose zone (40 m depth). Manipulating subsurface conditions for enhanced bioremediation was demonstrated through two remediation projects. One site is characterized by 20 m deep vadose zone that is contaminated with gasoline products and the other is a 40 m deep vadose zone that is contaminated with perchlorate. In both cases temporal variation of the sediment water content as well as the variations in the vadose zone chemical and isotopic composition allowed real time detection of water flow velocities, contaminants transport rates and bio-degradation degree. Results and conclusions from each wetting cycle were used to improve the following wetting cycles in order to optimize contaminants degradation conditions while minimizing leaching of contaminants to the groundwater.

Degradation of Biofumigant Isothiocyanates and Allyl Glucosinolate in Soil and Their Effects on the Microbial Community Composition

PubMed Central

Hanschen, Franziska S.; Yim, Bunlong; Winkelmann, Traud; Smalla, Kornelia; Schreiner, Monika

2015-01-01

Brassicales species rich in glucosinolates are used for biofumigation, a process based on releasing enzymatically toxic isothiocyanates into the soil. These hydrolysis products are volatile and often reactive compounds. Moreover, glucosinolates can be degraded also without the presence of the hydrolytic enzyme myrosinase which might contribute to bioactive effects. Thus, in the present study the stability of Brassicaceae plant-derived and pure glucosinolates hydrolysis products was studied using three different soils (model biofumigation). In addition, the degradation of pure 2-propenyl glucosinolate was investigated with special regard to the formation of volatile breakdown products. Finally, the influence of pure glucosinolate degradation on the bacterial community composition was evaluated using denaturing gradient gel electrophoresis of 16S rRNA gene amplified from total community DNA. The model biofumigation study revealed that the structure of the hydrolysis products had a significant impact on their stability in the soil but not the soil type. Following the degradation of pure 2-propenyl glucosinolate in the soils, the nitrile as well as the isothiocyanate can be the main degradation products, depending on the soil type. Furthermore, the degradation was shown to be both chemically as well as biologically mediated as autoclaving reduced degradation. The nitrile was the major product of the chemical degradation and its formation increased with iron content of the soil. Additionally, the bacterial community composition was significantly affected by adding pure 2-propenyl glucosinolate, the effect being more pronounced than in treatments with myrosinase added to the glucosinolate. Therefore, glucosinolates can have a greater effect on soil bacterial community composition than their hydrolysis products. PMID:26186695

Investigation of the persistence of nerve agent degradation analytes on surfaces through wipe sampling and detection with ultrahigh performance liquid chromatography-tandem mass spectrometry.

PubMed

Willison, Stuart A

2015-01-20

The persistence of chemical warfare nerve agent degradation analytes on surfaces is important, from indicating the presence of nerve agent on a surface to guiding environmental restoration of a site after a release. Persistence was investigated for several chemical warfare nerve agent degradation analytes on indoor surfaces and presents an approach for wipe sampling of surfaces, followed by wipe extraction and liquid chromatography-tandem mass spectrometry detection. Commercially available wipe materials were investigated to determine optimal wipe recoveries. Tested surfaces included porous/permeable (vinyl tile, painted drywall, and wood) and largely nonporous/impermeable (laminate, galvanized steel, and glass) surfaces. Wipe extracts were analyzed by ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). UPLC provides a separation of targeted degradation analytes in addition to being nearly four times faster than high-performance liquid chromatography, allowing for greater throughput after a large-scale contamination incident and subsequent remediation events. Percent recoveries from nonporous/impermeable surfaces were 60-103% for isopropyl methylphosphonate (IMPA), GB degradate; 61-91% for ethyl methylphosphonate (EMPA), VX degradate; and 60-98% for pinacolyl methylphosphonate (PMPA), GD degradate. Recovery efficiencies for methyl phosphonate (MPA), nerve agent degradate, and ethylhydrogen dimethylphosphonate (EHDMAP), GA degradate, were lower, perhaps due to matrix effects. Diisopropyl methylphosphonate, GB impurity, was not recovered from surfaces. The resulting detection limits for wipe extracts were 0.065 ng/cm(2) for IMPA, 0.079 ng/cm(2) for MPA, 0.040 ng/cm(2) for EMPA, 0.078 ng/cm(2) for EHDMAP, and 0.013 ng/cm(2) for PMPA. The data indicate that laboratories may hold wipe samples for up to 30 days prior to analysis. Target analytes were observed to persist on surfaces for at least 6 weeks.

Degradation of aqueous synthesized CdTe/ZnS quantum dots in mice: differential blood kinetics and biodistribution of cadmium and tellurium

PubMed Central

2013-01-01

Background Quantum dots (QDs) have been used as novel fluorescent nanoprobes for various bioapplications. The degradation of QDs, and consequent release of free cadmium ions, have been suggested to be the causes of their overall toxicity. However, in contrast to sufficient investigations regarding the biological fate of QDs, a paucity of studies have reported their chemical fate in vivo. Therefore, the overall aim of our study was to understand the chemical fate of QDs in vivo and explore analytical techniques or methods that could be used to define the chemical fate of QDs in vivo. Methods Male ICR mice were administered a single intravenous dose (0.2 μmol/kg) of aqueous synthesized CdTe/ZnS aqQDs. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to simultaneously measure the concentrations of cadmium (Cd) and tellurium (Te) in the blood and tissues over the course of a 28 day period. We compared the blood kinetic parameters and biodistributions of Cd and Te, and used the molar ratio of Cd:Te as a marker for QDs degradation. Results Cd and Te display different blood kinetics and biodistribution profiles. The Cd:Te ratio in the blood did not vary significantly within the first hour compared with intact CdTe/ZnS aqQDs. The Cd:Te ratio decreased gradually over time from the 6 h time point on. Cd accumulated in the liver, kidneys, and spleen. Te was distributed primarily to the kidneys. Sharp time-dependent increases in the Cd:Te ratio were found in liver tissues. Conclusions QDs can undergo degradation in vivo. In vitro, QDs are chemically stable and do not elicit the same biological responses or consequences as they do in vivo. Our methods might provide valuable information regarding the degradation of QDs in vivo and may enable the design and development of QDs for biological and biomedical applications. PMID:23915017

Degradation of aqueous synthesized CdTe/ZnS quantum dots in mice: differential blood kinetics and biodistribution of cadmium and tellurium.

PubMed

Liu, Na; Mu, Ying; Chen, Yi; Sun, Hubo; Han, Sihai; Wang, Mengmeng; Wang, Hui; Li, Yanbo; Xu, Qian; Huang, Peili; Sun, Zhiwei

2013-08-06

Quantum dots (QDs) have been used as novel fluorescent nanoprobes for various bioapplications. The degradation of QDs, and consequent release of free cadmium ions, have been suggested to be the causes of their overall toxicity. However, in contrast to sufficient investigations regarding the biological fate of QDs, a paucity of studies have reported their chemical fate in vivo. Therefore, the overall aim of our study was to understand the chemical fate of QDs in vivo and explore analytical techniques or methods that could be used to define the chemical fate of QDs in vivo. Male ICR mice were administered a single intravenous dose (0.2 μmol/kg) of aqueous synthesized CdTe/ZnS aqQDs. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to simultaneously measure the concentrations of cadmium (Cd) and tellurium (Te) in the blood and tissues over the course of a 28 day period. We compared the blood kinetic parameters and biodistributions of Cd and Te, and used the molar ratio of Cd:Te as a marker for QDs degradation. Cd and Te display different blood kinetics and biodistribution profiles. The Cd:Te ratio in the blood did not vary significantly within the first hour compared with intact CdTe/ZnS aqQDs. The Cd:Te ratio decreased gradually over time from the 6 h time point on. Cd accumulated in the liver, kidneys, and spleen. Te was distributed primarily to the kidneys. Sharp time-dependent increases in the Cd:Te ratio were found in liver tissues. QDs can undergo degradation in vivo. In vitro, QDs are chemically stable and do not elicit the same biological responses or consequences as they do in vivo. Our methods might provide valuable information regarding the degradation of QDs in vivo and may enable the design and development of QDs for biological and biomedical applications.

A novel combined solar pasteurizer/TiO2 continuous-flow reactor for decontamination and disinfection of drinking water.

PubMed

Monteagudo, José María; Durán, Antonio; Martín, Israel San; Acevedo, Alba María

2017-02-01

A new combined solar plant including an annular continuous-flow compound parabolic collector (CPC) reactor and a pasteurization system was designed, built, and tested for simultaneous drinking water disinfection and chemical decontamination. The plant did not use pumps and had no electricity costs. First, water continuously flowed through the CPC reactor and then entered the pasteurizer. The temperature and water flow from the plant effluent were controlled by a thermostatic valve located at the pasteurizer outlet that opened at 80 °C. The pasteurization process was simulated by studying the effect of heat treatment on the death kinetic parameters (D and z values) of Escherichia coli K12 (CECT 4624). 99.1% bacteria photo-inactivation was reached in the TiO 2 -CPC system (0.60 mg cm -2 TiO 2 ), and chemical decontamination in terms of antipyrine degradation increased with increasing residence time in the TiO 2 -CPC system, reaching 70% degradation. The generation of hydroxyl radicals (between 100 and 400 nmol L -1 ) was a key factor in the CPC system efficiency. Total thermal bacteria inactivation was attained after pasteurization in all cases. Chemical degradation and bacterial photo-inactivation in the TiO 2 -CPC system were improved with the addition of 150 mg L -1 of H 2 O 2 , which generated approximately 2000-2300 nmol L -1 of HO ● radicals. Finally, chemical degradation and bacterial photo-inactivation kinetic modelling in the annular CPC photoreactor were evaluated. The effect of the superficial liquid velocity on the overall rate constant was also studied. Both antipyrine degradation and E. coli photo-inactivation were found to be controlled by the catalyst surface reaction rate. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2008-12-01

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

Intracellular degradation of chemically functionalized carbon nanotubes using a long-term primary microglial culture model.

PubMed

Bussy, Cyrill; Hadad, Caroline; Prato, Maurizio; Bianco, Alberto; Kostarelos, Kostas

2016-01-07

Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study.

Non-invasive monitoring of the degradation of organic contaminants: A laboratory investigation

NASA Astrophysics Data System (ADS)

Fernandez, Perrine M.; Bloem, Esther; Philippe, Romain; Binley, Andrew; French, Helen K.

2016-04-01

Degradation of organic chemicals under various fluid saturation conditions is a process highly relevant to the protection of groundwater quality. Redox potential drives the degradation of organic compounds; its variation affects the water chemistry, gas release and also the geo-electrical signature. This study explores how non-invasive measurements sensitive to geo-electrical properties provides quantitative information about the in-situ redox conditions. Our laboratory experiment focuses on the degradation of de-icing chemicals commonly used, for example, in Norwegian airports. The experiment was conducted in a number of (1.0x0.5x0.4 m) sand boxes. Two ends of each box was contaminated with propylene glycol, an aircraft deicing fluid. Each source was placed near the water table under static hydraulic conditions. At one side of the tank, a conductor linking the contamination zone, near the water table and the unsaturated zone with a low water content, was placed to improve the degradation by facilitating the electron exchange. At the other side, degradation occurred under natural conditions. Each box was equipped with 288 electrodes, distributed on six faces to perform 3D resistivity measurements. In addition, self-potential measurements were taken from electrodes on the sand surface. Four observation wells were installed above and below the water table to provide more information on the degradation processes. Moreover, measurements of carbon dioxide on the surface were performed as higher concentrations were expected where the pollutant degraded. We would like to present and discuss a selection of the preliminary results of 3D electrical resistivity and self-potential techniques from our laboratory setup.

3D resistivity method to monitor degradation of an organic contaminant in sand boxes

NASA Astrophysics Data System (ADS)

Fernandez, P. M.; Bloem, E.; Philippe, R.; French, H. K.

2015-12-01

Degradation of organic chemicals under various saturation conditions is a process highly relevant to protect groundwater. The redox potential drives the degradation of organic compounds. Its variation affects the water chemistry, gas release and responses of the geo-electrical signature. This study explores how non-invasive measurements sensitive to geo-electrical properties provides quantitative information about the in-situ redox situation. During this presentation, the preliminary results of a laboratory experiment to study the degradation of deicing chemicals with 3D resistivity and self-potential techniques, water samples will be shown. The experiment consists of sand boxes (1.0x0.5x0.4 m) to which both sides of each box is contaminated with propylene glycol, an aircraft deicing fluid, commonly used in Norwegian airports. Each source is placed near the water table with static conditions. At one side a conductor is placed, linking the contamination zone at the water table and the unsaturated zone with a low water content, to improve the degradation by facilitating the electron exchange. At the other side, degradation occurs under natural conditions. Each box is equipped with 288 electrodes, distributed on six faces to perform 3D resistivity measurements. In addition to the resistivity, self-potential measurements are taken from the sand surface. Six water wells are installed above and below the water table to provide more information on the degradation processes. Moreover, measurements of carbon dioxide on the surface are performed as higher concentrations are expected where the pollutant is degraded.

Restoring and Enhancing Productivity of Degraded Tephra-Derived Soils

Treesearch

Chuck Bulmer; Jim Archuleta; Mike Curran

2007-01-01

Soil restoration (sometimes termed enhancement) is an important strategy for sustaining the productivity of managed forest landscapes. Tephra-derived soils have unique physical and chemical characteristics that affect their response to disturbance and restoration. A variety of factors reduce forest productivity on degraded soils. Site-specific information on soil...

Potential transport and degradation of “Aged” pesticide residues in soil

USDA-ARS?s Scientific Manuscript database

“Aging” has been shown to affect the sorption-desorption of pesticides in the soil, which in turn can control transport and degradation processes. Aging effects have been characterized by batch sequential extraction methods, in which sorption coefficients (i.e. Kd) are determined for the chemical re...

Metal organic frameworks (MOFs) for degradation of nerve agent simulant parathion

USDA-ARS?s Scientific Manuscript database

Parathion, a simulant of nerve agent VX, has been studied for degradation on Fe3+, Fe2+ and zerovalent iron supported on chitosan. Chitosan, a naturally occurring biopolymer derivative of chitin, is a very good adsorbent for many chemicals including metals. Chitosan is used as supporting biopolymer ...

Weathering of wood

Treesearch

R. Sam Williams

2005-01-01

Weathering is the general term used to define the slow degradation of materials exposed to the weather. The degradation mechanism depends on the type of material, but the cause is a combination of factors found in nature: moisture, sunlight, heat/cold, chemicals, abrasion by windblown materials, and biological agents. Tall mountains weather by the complex and...

Heme-Containing Metal-Organic Frameworks for the Oxidative Degradation of Chemical Warfare Agents

DTIC Science & Technology

2016-04-14

stability of the oxo without sacrificing its inherent reactivity, we have synthesized a new framework featuring fluorinated groups in the ortho...especially suitable for the degradation of electrophilic phosphorous center, leading to the cleavage of P-S or P-O bond present in VX nerve agents

Destruction of chemical warfare agents using metal-organic frameworks

NASA Astrophysics Data System (ADS)

Mondloch, Joseph E.; Katz, Michael J.; Isley, William C., III; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W.; Hall, Morgan G.; Decoste, Jared B.; Peterson, Gregory W.; Snurr, Randall Q.; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.

2015-05-01

Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

Destruction of chemical warfare agents using metal-organic frameworks.

PubMed

Mondloch, Joseph E; Katz, Michael J; Isley, William C; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W; Hall, Morgan G; DeCoste, Jared B; Peterson, Gregory W; Snurr, Randall Q; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

2015-05-01

Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

Estimation of hydrolysis rate constants for carbamates

EPA Science Inventory

Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism...

Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

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

Choe, Yoong-Kee; Henson, Neil J.; Kim, Yu Seung

2015-12-31

Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane shouldmore » enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.« less

What Happens to Bio-degradables in the Ocean? Due to the increasing amount of plastic that ends up in the ocean there is much alarm about it killing sea life from ingestion and changing chemical properties of the ocean. But what really happens t these products in the ocean, and how do they affect the ocean.

NASA Astrophysics Data System (ADS)

Lavoie, A.

2016-12-01

What Happens to Bio-degradables in the Ocean? Due to the increasing amount of plastic that ends up in the ocean there is much alarm about it killing sea life from entanglement and ingestion and changing chemical properties of the ocean. Our society is trying to take action by purchasing and using materials that claim to be biodegradable. But how long do these materials take to degrade in ocean water and do they actually change the water composition? Answering these questions will determine if one should invest in these materials as an alternative to plastic.

Towards a synthetic osteo-odonto-keratoprosthesis.

PubMed

Viitala, Reeta; Franklin, Valerie; Green, David; Liu, Christopher; Lloyd, Andrew; Tighe, Brian

2009-01-01

Osteo-odonto-keratoprostheses (OOKP) is a unique form of keratoprosthesis involving surgical removal of a tooth root and surrounding bone from the patient which are then used to construct an osteo-odonto lamina into which an optical cylinder is cemented. The OOKP procedure is successful and capable of withstanding the very hostile ocular environments found in severe Stevens-Johnson syndrome, pemphigoid, chemical burns, trachoma and multiple corneal graft failure. The existing procedure is complex and time consuming in terms of operative time, and additionally involves sacrifice of the oral structures. This paper discusses the rational search for a "synthetic" analogue of the dental lamina, capable of mimicking those features of the natural system that are responsible for the success of OOKP. In this study the degradation of selected commercial and natural bioceramics was tested in vitro using a purpose-designed resorption assay. Degradation rate was compared with tooth and bone, which are currently used in OOKP lamina. At normal physiological pH the degradation of bioceramics was equivalent to tooth and bone; however, at pH 6.5-5.0, associated with infectious and inflamed tissues, the bioceramics degrade more rapidly. At lower pH the degradation rate decreased in the following order: calcium carbonate corals>biphasic calcium phosphates>hydroxyapatite. Porosity did not significantly influence these degradation rates. Such degradation is likely to compromise the stability and viability of the synthetic OOKP. Consequently more chemically stable materials are required that are optimized for the surrounding ocular environment.

Salvaging and Conserving Water Damaged Photographic Materials

NASA Astrophysics Data System (ADS)

Suzuki, Ryuji

Degradation of water damaged photographic materials is discussed; the most vulnerable elements are gelatin layers and silver image. A simple and inexpensive chemical treatment is proposed, consisting of a bath containing a gelatin-protecting biocide and a silver image protecting agent. These ingredients were selected among those used in manufacturing of silver halide photographic emulsions or processing chemicals. Experiments confirmed that this treatment significantly reduced oxidative attacks to silver image and bacterial degradation of gelatin layers. The treated material was also stable under intense light fading test. Method of hardening gelatin to suppress swelling is also discussed.

Development of novel assays for lignin degradation: comparative analysis of bacterial and fungal lignin degraders.

PubMed

Ahmad, Mark; Taylor, Charles R; Pink, David; Burton, Kerry; Eastwood, Daniel; Bending, Gary D; Bugg, Timothy D H

2010-05-01

Two spectrophotometric assays have been developed to monitor breakdown of the lignin component of plant lignocellulose: a continuous fluorescent assay involving fluorescently modified lignin, and a UV-vis assay involving chemically nitrated lignin. These assays have been used to analyse lignin degradation activity in bacterial and fungal lignin degraders, and to identify additional soil bacteria that show activity for lignin degradation. Two soil bacteria known to act as aromatic degraders, Pseudomonas putida and Rhodococcus sp. RHA1, consistently showed activity in these assays, and these strains were shown in a small scale experiment to breakdown lignocellulose, producing a number of monocyclic phenolic products. Using milled wood lignin prepared from wheat straw, pine, and miscanthus, some bacterial lignin degraders were found to show specificity for lignin type. These assays could be used to identify novel lignin degraders for breakdown of plant lignocellulose.

[BiOBr promoted the photocatalytic degradation of beta-cypermethrin under visible light].

PubMed

Peng, Yi-Zhu; Zhao, Xiao-Rong; Jia, Man-Ke; Zhou, Wei; Huang, Ying-Ping

2014-05-01

As a visible light photocatalyst, bismuth oxide bromide (BiOBr) was used to catalyze the degradation of beta-cypermethrin (beta-CP). The photocatalytic degradation of beta-CP was studied with gas chromatography. The effects of pH and catalyst dose on the photocatalytic degradation efficiency were discussed. The oxidization and mineralization of beta-CP were detected by chemical oxygen demand (COD) analyzer. The results showed that beta-CP could be effectively degraded under visible light irradiation using BiOBr as the catalyst. At given experimental conditions, the degradation rate of beta-CP reached 94. 68% after 10 h and the COD removal rate reached 67. 99% after 36 h. With the increase of catalyst dose and pH value, the degradation rate was improved. The photocatalytic oxidation species was determined by peroxidase method and terephthalic acid fluorescence method. These results suggested that the photocatalytic degradation process mainly referred to hydroxyl radical ( OH) mechanism.

Stability of citral in oil-in-water emulsions prepared with medium-chain triacylglycerols and triacetin.

PubMed

Choi, Seung Jun; Decker, Eric Andrew; Henson, Lulu; Popplewell, L Michael; McClements, David Julian

2009-12-09

Citral is widely used in the beverage, food, and fragrance industries for its characteristic flavor profile. However, it chemically degrades over time in aqueous solutions due to an acid-catalyzed reaction, which leads to loss of desirable flavor notes and formation of off-flavor notes. The objective of this research was to examine the impact of organic phase composition [triacetin and medium-chain triacylglycerols (MCT)] on the oil-water partitioning and chemical degradation of citral in oil-in-water emulsions. MCT was present as emulsion droplets (d approximately 900 nm), whereas triacetin was present as microemulsion droplets (d approximately 10 nm). In the absence of organic phase, the rate of citral degradation increased as the aqueous phase pH was reduced from 7 to 3. The percentage of citral within the aqueous phase increased with increasing triacetin concentration at both pH 3 and 7, which was attributed to a reduction in MCT droplet concentration. There was no significant change in the particle size distribution of the emulsions during storage, independent of triacetin concentration and pH, which indicated that they were physically stable. Both 5 wt % MCT as emulsion droplets and 5 wt % triacetin as microemulsion droplets were able to appreciably slow citral degradation at pH 3. These results may have important implications for understanding and improving the chemical stability of citral in beverage emulsions.

Electrolytic Manipulation of Persulfate Reactivity by Iron Electrodes for TCE Degradation in Groundwater

PubMed Central

Yuan, Songhu; Liao, Peng; Alshawabkeh, Akram N.

2014-01-01

Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater, and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053•Iv + 0.059 (−122 A/m3 ≤ Iv ≤ 244 A/m3) where k1 and Iv are the pseudo first-order rate constant (min−1) and volume normalized current (A/m3), respectively. Persulfate is mainly decomposed by Fe2+ produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe3+ reduction on the cathode. SO4•− and •OH co-contribute to TCE degradation, but •OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface. PMID:24328192

Bacterial Production and Contamination Mineralization in Sediments of the Ala Wai Canal, Oahu, Hawaii

DTIC Science & Technology

2009-09-29

fluoranthene (45 mCi mmol-1), and 9-14C- phenanthrene (55 mCi mmol-1) (Sigma Chemical), as well as the lignin degradation intermediate, UL-14C- catechol...intermediate involved in lignin degradation and areas where lignin and other more refractory materials are being metabolized may have more rapid mineralization...indicating much of the lignin -derived organic matter is likely from nonwoody tissue (Figure 25). Lignin degradation in sediment has been measured

Chemical Composition, In vitro Gas Production, Ruminal Fermentation and Degradation Patterns of Diets by Grazing Steers in Native Range of North Mexico

PubMed Central

Murillo, M.; Herrera, E.; Carrete, F. O.; Ruiz, O.; Serrato, J. S.

2012-01-01

The objective of the study was to quantify annual and seasonal differences in the chemical composition, in vitro gas production, in situ degradability and ruminal fermentation of grazing steers’ diets. Diet samples were collected with four esophageal cannulated steers (350±3 kg BW); and four ruminally cannulated heifers (342±1.5 kg BW) were used to study the dry matter degradation and fermentation in rumen. Data were analyzed with repeated measurements split plot design. The crude protein, in vitro dry matter digestibility and metabolizable energy were higher during the first year of trial and in the summer (p<0.01). The values of calcium, phosphorus, magnesium, zinc and copper were higher in summer (p<0.05). The gas produced by the soluble and insoluble fractions, as well as the constant rate of gas production were greater in summer and fall (p<0.01). The ammonia nitrogen (NH3N) and total volatile fatty acids concentrations in rumen, the soluble and degradable fractions, the constant rate of degradation and the effective degradability of DM and NDF were affected by year (p<0.05) and season (p<0.01). Our study provides new and useful knowledge for the formulation of protein, energetic and mineral supplements that grazing cattle need to improve their productive and reproductive performance. PMID:25049495

Bacteria contribute to pesticide degradation in cryoconite holes in an Alpine glacier.

PubMed

Ferrario, Claudia; Pittino, Francesca; Tagliaferri, Ilario; Gandolfi, Isabella; Bestetti, Giuseppina; Azzoni, Roberto Sergio; Diolaiuti, Guglielmina; Franzetti, Andrea; Ambrosini, Roberto; Villa, Sara

2017-11-01

Organic contaminants deposited on glacier snow and ice are subject to partitioning and degradation processes that determine their environmental fate and, consequently, their accumulation in ice bodies. Among these processes, organic compound degradation by supraglacial bacteria has been investigated to a lesser extent than photo- and chemical degradation. We investigated biodegradation of the organophosphorus insecticide chlorpyrifos (CPF), a xenobiotic tracer that accumulates on glaciers after atmospheric medium- and long-range transport, by installing in situ microcosms on an Alpine glacier to simulate cryoconite hole systems. We found that biodegradation contributed to the removal of CPF from the glacier surface more than photo- and chemical degradation. The high concentration of CPF (2-3 μg g -1 w.w.) detected in cryoconite holes and the estimated half-life of this compound (35-69 days in glacier environment) indicated that biodegradation can significantly reduce CPF concentrations on glaciers and its runoff to downstream ecosystems. The metabolic versatility of cryoconite bacteria suggests that these habitats might contribute to the degradation of a wide class of pollutants. We therefore propose that cryoconite acts as a "biofilter" by accumulating both pollutants and biodegradative microbial communities. The contribution of cryoconite to the removal of organic pollutants should be included in models predicting the environmental fate of these compounds in cold areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

EVALUATION OF UNSATURATED/VADOSE ZONE MODELS FOR SUPERFUND SITES

EPA Science Inventory

Mathematical models of water and chemical movement in soils are being used as decision aids for defining groundwater protection practices for Superfund sites. Numerous transport models exist for predicting movementand degradation of hazardous chemicals through soils. Many of thes...

EVALUATION OF UNSATURATED/VADOSE ZONE MODELS FOR SUPERFUND SITES

EPA Science Inventory

Mathematical models of water and chemical movement in soils are being used as decision aids for defining groundwater protection practices for Superfund sites. umerous transport models exist for predicting movement and degradation of hazardous chemicals through soil& Many of these...

40 CFR 161.153 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... ingredients with one or more other active or inert ingredients, without an intended chemical reaction, to... technical grade cannot be isolated) by chemical reaction. (k) Technical grade of active ingredient means a... unreacted starting materials, side reaction products, contaminants, and degradation products. (e) Impurity...

DETERMINATION OF PERFLUORINATED CHEMICALS (PFCS) IN SOILS, SEDIMENT AND OTHER MATRICES

EPA Science Inventory

Soils that receive land application of treated wastewater from carpet manufacturing plants were sampled for perfluorooctanoic acid (PFOA) and other perfluorinated chemicals (PFCs) that are potential degradation products of fluorotelomer-based polymers (FBPs). Soils from other pot...

Coloring, bleaching, and perming: influence on EtG content in hair.

PubMed

Kerekes, Isabelle; Yegles, Michel

2013-08-01

Hair analysis of ethyl glucuronide (EtG) has become, beside fatty acid ethyl ester, a valuable marker for the detection of moderate and chronic excessive alcohol consumption. So far, only few studies exist about the influence of cosmetic treatment on EtG content in hair. The aim of this study was to evaluate the effect of coloring, bleaching, and perming on the concentration of this alcohol marker in hair. Studies were also performed to evaluate the chemical stability of EtG in the presence of hydrogen peroxide and ammonium thioglycolate. Six air samples were treated in vitro by the different commercial cosmetics following the suppliers' instructions. After washing, pulverization, incubation in ultrasonic bath, and solid phase extraction, EtG was determined by GC/MS-NICI after solid phase extraction and heptafluorobutyric anhydride derivatization. The results showed that samples (n = 10) treated with the coloring product did not show any important change in the EtG results. In the bleaching study (n = 23), a mean decrease of 73.5% was observed. After incubation of a solution of EtG with hydrogen peroxide (15%), a decrease of 45% was shown supporting the hypothesis of a chemical degradation of EtG and a leaching out effect from the hair matrix. In the perm treatment study (n = 23), a mean decrease of 95.7% of EtG was found. Incubation of a solution of EtG with ammonium thioglycolate (5%) showed a total decrease of EtG supporting the hypothesis of a chemical degradation. Coloring treatment did not importantly influence EtG content in hair. However, an important decrease of EtG in hair could be found after bleaching and permanent wave treatment. This decrease seems to be because of a chemical degradation of EtG, after bleaching, and a leaching out effect from the matrix. After perming, it seems to be more of a chemical degradation of EtG. These data have to be considered for the correct interpretation of EtG amounts in hair.

Fungal degradation of an acetolactate synthase (ALS) inhibitor pyrazosulfuron-ethyl in soil.

PubMed

Sondhia, Shobha; Waseem, Uzma; Varma, R K

2013-11-01

Owing to reported phytotoxicity of some sulfonylurea class of herbicides in number of sensitive crops and higher persistence in soil, present study was conducted to isolate and identify pyrazosulfuron-ethyl degrading fungi from soil of rice field. Penicillium chrysogenum and Aspergillus niger, were isolated and identified from rhizospere soil of rice field, as potent pyrazosulfuron-ethyl degrading fungi. Degradation of pyrazosulfuron-ethyl by P. chrysogenum and A. niger, yielded transformation products/metabolites which were identified and characterized by LC/MS/MS. The rate of dissipation of pyrazosulfuron-ethyl was found higher in soil of rice field and soil inoculated with P. chrysogenum. This showed important route of degradation of pyrazosulfuron-ethyl by microbes apart from chemical degradation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Holistic approach to wood protection

Treesearch

Roger M. Rowell

2006-01-01

When untreated wood is exposed to adverse outdoor conditions, nature has a series of chemistries to degrade it to its original building blocks of carbon dioxide and water. Fungi, termites, heat, moisture, ultraviolet (UV) energy, and chemicals take their toll on the performance properties of wood. We tend to study each of these degradation chemistries as individual...

Fate of acetone in water

USGS Publications Warehouse

Rathbun, R.E.; Stephens, D.W.; Shultz, D.J.

1982-01-01

The physical, chemical, and biological processes that might affect the concentration of acetone in water were investigated in laboratory studies. Processes considered included volatilization, adsorption by sediments, photodecomposition, bacterial degradation, and absorption by algae and molds. It was concluded that volatilization and bacterial degradation were the dominant processes determining the fate of acetone in streams and rivers. ?? 1982.

Wood Products Thermal Degradation and Fire

Treesearch

Mark Dietenberger; Laura Hasburgh

2016-01-01

As wood reaches elevated temperatures, the different chemical components undergo thermal degradation that affect the performance of wood. The extent of these changes depends on the temperature level and length of time under exposure conditions. Permanent reductions in strength and modulus of elasticity can occur at temperatures >65 °C, with the amount depending...

Photodegradation of Dicloran in Freshwater and Seawater.

PubMed

Vebrosky, Emily N; Saranjampour, Parichehr; Crosby, Donald G; Armbrust, Kevin L

2018-03-21

Dicloran appears to be a model pesticide for investigating photodegradation processes in surface waters. Photodegradation processes are particularly relevant to this compound as it is applied to crops grown in proximity to freshwater and marine ecosystems. The photodegradation of dicloran under simulated sunlight was measured in distilled water, artificial seawater, phosphate buffer, and filter-sterilized estuarine water to determine its half-life, degradation rate, and photodegradation products. The half-life was approximately 7.5 h in all media. There was no significant difference in the rate of degradation between distilled water and artificial seawater for dicloran. For the intermediate products, a higher concentration of 2-chloro-1,4-benzoquinone was measured in artificial seawater versus distilled water, while a slightly higher concentration of 1,4-benzoquinone was measured in distilled water versus artificial seawater. The detection of chloride and nitrate ions after 2 h of light exposure suggests photonucleophilic substitution contributes to the degradation process. Differences in product distributions between water types suggest that salinity impacts on chemical degradation may need to be addressed in chemical exposure assessments.

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

NASA Technical Reports Server (NTRS)

Niki, Hiromi

1990-01-01

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Behavior of sulfur mustard in sand, concrete, and asphalt matrices: Evaporation, degradation, and decontamination.

PubMed

Jung, Hyunsook; Choi, Seungki

2017-10-15

The evaporation, degradation, and decontamination of sulfur mustard on environmental matrices including sand, concrete, and asphalt are described. A specially designed wind tunnel and thermal desorber in combination with gas chromatograph (GC) produced profiles of vapor concentration obtained from samples of the chemical agent deposited as a drop on the surfaces of the matrices. The matrices were exposed to the chemical agent at room temperature, and the degradation reactions were monitored and characterized. A vapor emission test was also performed after a decontamination process. The results showed that on sand, the drop of agent spread laterally while evaporating. On concrete, the drop of the agent was absorbed immediately into the matrix while spreading and evaporating. However, the asphalt surface conserved the agent and slowly released parts of the agent over an extended period of time. The degradation reactions of the agent followed pseudo first order behavior on the matrices. Trace amounts of the residual agent present at the surface were also released as vapor after decontamination, posing a threat to the exposed individual and environment.

Atrazine and its metabolites degradation in mineral salts medium and soil using an enrichment culture.

PubMed

Kumar, Anup; Singh, Neera

2016-03-01

An atrazine-degrading enrichment culture was used to study degradation of atrazine metabolites viz. hydroxyatrazine, deethylatrazine, and deisopropylatrazine in mineral salts medium. Results suggested that the enrichment culture was able to degrade only hydroxyatrazine, and it was used as the sole source of carbon and nitrogen. Hydroxyatrazine degradation slowed down when sucrose and/or ammonium hydrogen phosphate were supplemented as the additional sources of carbon and nitrogen, respectively. The enrichment culture could degrade high concentrations of atrazine (up to 110 μg/mL) in mineral salts medium, and neutral pH was optimum for atrazine degradation. Further, except in an acidic soil, enrichment culture was able to degrade atrazine in three soil types having different physico-chemical properties. Raising the pH of acidic soil to neutral or alkaline enabled the enrichment culture to degrade atrazine suggesting that acidic pH inhibited atrazine-degrading ability. The study suggested that the enrichment culture can be successfully utilized to achieve complete degradation of atrazine and its persistent metabolite hydroxyatrazine in the contaminated soil and water.

Pathway-based monitoring of biological effects at Great Lakes sites (Presntation)

EPA Science Inventory

The Great Lakes region suffers from degradation of water and environmental quality due to release of chemicals of emerging concern. Critical issues remain in delisting Areas of Concern (AOC) including determining sources of chemicals causing fish health impacts, relating health ...

Organic chemical degradation by remote study of the redox conditions

NASA Astrophysics Data System (ADS)

Fernandez, P. M.; Revil, A.; Binley, A. M.; Bloem, E.; French, H. K.

2014-12-01

Monitoring the natural (and enhanced) degradation of organic contaminants is essential for managing groundwater quality in many parts of the world. Contaminated sites often have limited access, hence non-intrusive methods for studying redox processes, which drive the degradation of organic compounds, are required. One example is the degradation of de-icing chemicals (glycols and organic salts) released to the soil near airport runways during winter. This issue has been broadly studied at Oslo airport, Gardermoen, Norway using intrusive and non-intrusive methods. Here, we report on laboratory experiments that aim to study the potential of using a self-potential, DCresistivity, and time-domain induced polarization for geochemical characterization of the degradation of Propylene Glycol (PG). PG is completely miscible in water, does not adsorb to soil particles and does not contribute to the electrical conductivity of the soil water. When the contaminant is in the unsaturated zone near the water table, the oxygen is quickly consumed and the gas exchange with the surface is insufficient to ensure aerobic degradation, which is faster than anaerobic degradation. Since biodegradation of PG is highly oxygen demanding, anaerobic pockets can exist causing iron and manganese reduction. It is hypothesised that nitrate would boost the degradation rate under such conditions. In our experiment, we study PG degradation in a sand tank. We provide the system with an electron highway to bridge zones with different redox potential. This geo-battery system is characterized by self-potential, resistivity and induced polarization anomalies. An example of preliminary results with self-potential at two different times of the experiment can be seen in the illustration. These will be supplemented with more direct information on the redox chemistry: in-situ water sampling, pH, redox potential and electrical conductivity measurements. In parallel, a series of batch experiments have been performed to study anoxic microbial degradation using gas and resistivity measurements.

Environmental effects on the tensile strength of chemically vapor deposited silicon carbide fibers

NASA Technical Reports Server (NTRS)

Bhatt, R. T.; Kraitchman, M. D.

1985-01-01

The room temperature and elevated temperature tensile strengths of commercially available chemically vapor-deposited (CVD) silicon carbide fibers were measured after 15 min heat treatment to 1600 C in various environments. These environments included oxygen, air, argon and nitrogen at one atmosphere and vacuum at 10/9 atmosphere. Two types of fibers were examined which differed in the SiC content of their carbon-rich coatings. Threshold temperature for fiber strength degradation was observed to be dependent on the as-received fiber-flaw structure, on the environment and on the coating. Fractographic analyses and flexural strength measurements indicate that tensile strength losses were caused by surface degradation. Oxidation of the surface coating is suggested as one possible degradation mechanism. The SiC fibers containing the higher percentage of SiC near the surface of the carbon-rich coating show better strength retention and higher elevated temperature strength.

Inhibition of citral degradation in an acidic aqueous environment by polyoxyethylene alkylether surfactants.

PubMed

Maswal, Masrat; Dar, Aijaz Ahmad

2013-06-15

Citral is a flavour component widely used in food and cosmetic industries, but is chemically unstable and degrades over time in aqueous solutions due to acid-catalysed and oxidative reactions leading to loss of desirable flavour. The present study reveals the effect of non-ionic micellar solutions of Brij30 and Brij35 on the extent of solubilisation and stabilisation of citral. The rate of chemical degradation of citral in acidic aqueous solutions was found to be highest, which was subsequently reduced significantly within these studied surfactant systems, suggesting protection of citral from an acidic environment once it is incorporated into the micelles. The work concludes that polyoxyethylene alkylether surfactants with lower HLB value, less dense hydrophilic corona and more hydrophobic core volume are efficient in solubilising and stabilising citral against an acidic environment. Copyright © 2012 Elsevier Ltd. All rights reserved.

Chemical dispersants: Oil biodegradation friend or foe?

PubMed

Rahsepar, Shokouh; Smit, Martijn P J; Murk, Albertinka J; Rijnaarts, Huub H M; Langenhoff, Alette A M

2016-07-15

Chemical dispersants were used in response to the Deepwater Horizon oil spill in the Gulf of Mexico, both at the sea surface and the wellhead. Their effect on oil biodegradation is unclear, as studies showed both inhibition and enhancement. This study addresses the effect of Corexit on oil biodegradation by alkane and/or aromatic degrading bacterial culture in artificial seawater at different dispersant to oil ratios (DORs). Our results show that dispersant addition did not enhance oil biodegradation. At DOR 1:20, biodegradation was inhibited, especially when only the alkane degrading culture was present. With a combination of cultures, this inhibition was overcome after 10days. This indicates that initial inhibition of oil biodegradation can be overcome when different bacteria are present in the environment. We conclude that the observed inhibition is related to the enhanced dissolution of aromatic compounds into the water, inhibiting the alkane degrading bacteria. Copyright © 2016 Elsevier Ltd. All rights reserved.

Different senescent HDPE pipe-risk: brief field investigation from source water to tap water in China (Changsha City).

PubMed

Tang, Jing; Tang, Lin; Zhang, Chang; Zeng, Guangming; Deng, Yaocheng; Dong, Haoran; Wang, Jingjing; Wu, Yanan

2015-10-01

Semi-volatile organic compounds (SVOCs) derived from plastic pipes widely used in water distribution definitely influence our daily drinking water quality. There are still few scientific or integrated studies on the release and degradation of the migrating chemicals in pipelines. This investigation was carried out at field sites along a pipeline in Changsha, China. Two chemicals, 2, 4-tert-buthylphenol and 1, 3-diphenylguanidine, were found to be migrating from high density polyethylene (HDPE) pipe material. New pipes released more of these two compounds than older pipes, and microorganisms living in older pipes tended to degrade them faster, indicating that the aged pipes were safer for water transmission. Microorganism degradation in water plays a dominant role in the control of these substances. To minimize the potential harm to human, a more detailed study incorporating assessment of their risk should be carried out, along with seeking safer drinking pipes.

Nanoscale zero-valent iron incorporated with nanomagnetic diatomite for catalytic degradation of methylene blue in heterogeneous Fenton system.

PubMed

Zha, Yiming; Zhou, Ziqing; He, Haibo; Wang, Tianlin; Luo, Liqiang

2016-01-01

Nanoscale zero-valent iron (nZVI) incorporated with nanomagnetic diatomite (DE) composite material was prepared for catalytic degradation of methylene blue (MB) in heterogeneous Fenton system. The material was constructed by two facile steps: Fe3O4 magnetic nanoparticles were supported on DE by chemical co-precipitation method, after which nZVI was incorporated into magnetic DE by liquid-phase chemical reduction strategy. The as-prepared catalyst was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, magnetic properties measurement and nitrogen adsorption-desorption isotherm measurement. The novel nZVI@Fe3O4-diatomite nanocomposites showed a distinct catalytic activity and a desirable effect for degradation of MB. MB could be completely decolorized within 8 min and the removal efficiency of total organic carbon could reach to 90% after reaction for 1 h.

Chemical nature and immunotoxicological properties of arachidonic acid degradation products formed by exposure to ozone

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

Madden, M.C.; Friedman, M.; Hanley, N.

1993-06-01

Ozone (O3) exposure in vivo has been reported to degrade arachidonic acid (AA) in the lungs of rodents. The O3-degraded AA products may play a role in the responses to this toxicant. To study the chemical nature and biological activity of O3-exposed AA, we exposed AA in a cell-free, aqueous environment to air, 0.1 ppm O3, or 1.0 ppm O3 for 30-120 min. AA exposed to air was not degraded. All O3 exposures degraded > 98% of the AA to more polar products, which were predominantly aldehydic substances (as determined by reactivity with 2,4-dinitrophenylhydrazine and subsequent separation by HPLC) andmore » hydrogen peroxide. The type and amount of aldehydic substances formed depended on the O3 concentration and exposure duration. A human bronchial epithelial cell line (BEAS-2B, S6 subclone) exposed in vitro to either 0.1 ppm or 1.0 ppm O3 for 1 hr produced AA-derived aldehydic substances, some of which eluted with similar retention times as the aldehydic substances derived from O3 degradation of AA in the cell-free system. In vitro, O3-degraded AA induced an increase in human peripheral blood polymorphonuclear leukocyte (PMN) polarization, decreased human peripheral blood T-lymphocyte proliferation in response to mitogens, and decreased human peripheral blood natural killer cell lysis of K562 target cells. The aldehydic substances, but not hydrogen peroxide, appeared to be the principal active agents responsible for the observed effects. O3-degraded AA may play a role in the PMN influx into lungs and in decreased T-lymphocyte mitogenesis and natural killer cell activity observed in humans and rodents exposed to O3.« less

Chemical characterization and sorption capacity measurements of degraded newsprint from a landfill

USGS Publications Warehouse

Chen, Lixia; Nanny, Mark A.; Knappe, Detlef R. U.; Wagner, Travis B.; Ratasuk, Nopawan

2004-01-01

Newsprint samples collected from 12−16 ft (top layer (TNP)), 20−24 ft (middle layer (MNP)), and 32−36 ft (bottom layer (BNP)) below the surface of the Norman Landfill (NLF) were characterized by infrared (IR) spectroscopy, cross-polarization, magic-angle spinning 13C nuclear magnetic resonance (CP-MAS 13C NMR) spectroscopy, and tetramethylammonium hydroxide (TMAH) thermochemolysis gas chromatography/mass spectrometry (GC/MS). The extent of NLF newsprint degradation was evaluated by comparing the chemical composition of NLF newsprint to that of fresh newsprint (FNP) and newsprint degraded in the laboratory under methanogenic conditions (DNP). The O-alkyl/alkyl, cellulose/lignin, and lignin/resin acid ratios showed that BNP was the most degraded, and that all three NLF newsprint samples were more degraded than DNP. 13C NMR and TMAH thermochemolysis data demonstrated selective enrichment of lignin over cellulose, and TMAH thermochemolysis further exhibited selective enrichment of resin acids over lignin. In addition, the crystallinity of cellulose in NLF newsprint samples was significantly lower relative to that of FNP and DNP as shown by 13C NMR spectra. The yield of lignin monomers from TMAH thermochemolysis suggested that hydroxyl groups were removed from the propyl side chain of lignin during the anaerobic decomposition of newsprint in the NLF. Moreover, the vanillyl acid/aldehyde ratio, which successfully describes aerobic lignin degradation, was not a good indicator of the anaerobic degradation of lignin on the basis of the TMAH data. The toluene sorption capacity increased as the degree of newsprint degradation increased or as the O-alkyl/alkyl ratio of newsprint decreased. The results of this study further verified that the sorbent O-alkyl/alkyl ratio is useful for predicting sorption capacities of natural organic materials for hydrophobic organic contaminants.

Real-time potentiometric sensor; an innovative tool for monitoring hydrolysis of chemo/bio-degradable drugs in pharmaceutical sciences.

PubMed

Ma'mun, Ahmed; Abd El-Rahman, Mohamed K; Abd El-Kawy, Mohamed

2018-05-30

In recent years, the whole field of ion-selective electrodes(ISEs) in pharmaceutical sciences has expanded far beyond its original roots. The diverse range of opportunities offered by ISEs was broadly used in a number of pharmaceutical applications, with topics presented ranging from bioanalysis of drugs and metabolites, to protein binding studies, green analytical chemistry, impurity profiling, and drug dissolution in biorelevant media. Inspired from these advances and with the aim of extending the functional capabilities of ISEs, the primary focus of the present paper is the utilization of ISE as a tool in personalized medicine. Given the opportunity to explore biological events in real-time (such as drug metabolism) could be central to personalized medicine. (ATR) is a chemo-degradable and bio-degradable pharmaceutically active drug. Laudanosine (LDS) is the major degradation product and metabolite of ATR and is potentially toxic and reported to possess epileptogenic activity which increases the risk of convulsive effects. In this work, ATR have been subjected to both chemical and biological hydrolysis, and the course of the reactions is monitored by means of a ISE. In this study, we have designed an efficient real-time tracking strategy which substantially resolve the challenges of the ATR chemical and biological degradation kinetics. By utilizing a potentiometric sensor, tracking of ATR chemical and biological degradation kinetics can be performed in a very short time with excellent accuracy. The LOD was calculated to be 0.23 μmol L -1 , the potential drift was investigated over a period of 60 min and the value was 0.25 mV h -1 . Real serum samples for measurement the rate of in vitro metabolism of ATR was performed. Furthermore, a full description of the fabricated screen-printed sensor was presented. Copyright © 2018 Elsevier B.V. All rights reserved.

Biodegradation of organophosphorus pesticides by soil bacteria

NASA Astrophysics Data System (ADS)

de Pasquale, C.; Fodale, R.; Lo Piccolo, L.; Palazzolo, E.; Alonzo, G.; Quatrini, P.

2009-04-01

A number of studies in the 1980s and 1990s showed that crop-protection products, applied to drained fields, could move downwards through the soil profile and to the groundwater. Organophosphorus insecticides (OPs) are used all over the world for crop protection, for other agricultural practices such as sheep dipping and, in aquaculture, for the control of sea lice. Ops besides showing a specific neurotoxicity and have also been related to various modern diseases, including Creutzfeldt-Jakob (CJD) and the Gulf War syndrome. Although OPs are less persistent than Organoclorine pesticides (OCs), they still constitute an environmental risks thus increasing the social concern about their levels in soils, surface waters, and ground waters. Degradation of OPs by microorganisms has been assessed for a few bacterial strains. In the present study the OPs degrading potential of indigenous soil microorganisms was investigated. Using enrichment cultures in which parathion was the only C and energy sources many bacterial strains were isolated from OPs contaminated and pristine agricultural soils characterized by different physico-chemical properties. More than 40 potential OPs degraders were isolated and grouped in operational taxonomic units (OTU) using analysis of polymorphism showed by the ribosomal internal transcribed spacer (ITS). Partial sequencing of 16S rRNA gene of representative isolates of each OTU revealed that most of them belong to Proteobacteria and Actinobacteria. All the analyzed soils showed the presence of putative OPs degraders: the highest diversity was found in organic cultivated soils, the lowest in chemically cultivated soils. Degradation of different OPs, characterized by different physical and chemical properties, was obtained by different selected representative strains using SPME GC-MS analysis on water and soil microcosms. The results showed that, after the incubation period, the amount of pesticide residues were in the range 20-80%. Some of the isolates bacterial species are currently unknown as OPs degraders.

Antifoam degradation testing

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

Lambert, D. P.; Zamecnik, J. R.; Newell, D. D.

2015-08-20

This report describes the results of testing to quantify the degradation products resulting from the dilution and storage of Antifoam 747. Antifoam degradation is of concern to the Defense Waste Processing Facility (DWPF) due to flammable decomposition products in the vapor phase of the Chemical Process Cell vessels, as well as the collection of flammable and organic species in the offgas condensate. The discovery that hexamethyldisiloxane is formed from the antifoam decomposition was the basis for a Potential Inadequacy in the Safety Analysis declaration by the DWPF.

Evaluation of isoprene degradation in the detailed tropospheric chemical mechanism, MCM v3, using environmental chamber data

NASA Astrophysics Data System (ADS)

Pinho, P. G.; Pio, C. A.; Jenkin, M. E.

The isoprene degradation mechanism included in version 3 of the Master Chemical Mechanism (MCM v3) has been evaluated and refined, using the Statewide Air Pollution Research Center (SAPRC) environmental chamber datasets on the photo-oxidation of isoprene and its degradation products, methacrolein (MACR) and methylvinyl ketone (MVK). Prior to this, the MCM v3 butane degradation chemistry was also evaluated using chamber data on the photo-oxidation of butane, and its degradation products, methylethyl ketone (MEK), acetaldehyde (CH 3CHO) and formaldehyde (HCHO), in conjunction with an initial evaluation of the chamber-dependent auxiliary mechanisms for the series of relevant chambers. The MCM v3 mechanisms for both isoprene and butane generally performed well and were found to provide an acceptable reaction framework for describing the NO x-photo-oxidation experiments on the above systems, although a number of parameter modifications and refinements were identified which resulted in an improved performance. All these relate to the magnitude of sources of free radicals from organic chemical process, such as carbonyl photolysis rates and the yields of radicals from the reactions of O 3 with unsaturated oxygenates, and specific recommendations are made for refinements. In addition to this, it was necessary to include a representation of the reactions of O( 3P) with isoprene, MACR and MVK (which were not previously treated in MCM v3), and conclusions are drawn concerning the required extent of free radical formation from these reactions. Throughout the study, the performance of MCM v3 was also compared with that of the SAPRC-99 mechanism, which was developed and optimized in conjunction with the chamber datasets.

Sorption and degradation of chlorophenols, nitrophenols and organophosphorus pesticides in the subsoil under landfills — laboratory studies

NASA Astrophysics Data System (ADS)

Kjeldsen, Peter; Kjølholt, Jesper; Schultz, Birgit; Christensen, Thomas H.; Tjell, Jens Christian

1990-09-01

Landfills and old industrial plant sites have been identified in an increasing number of cases as point sources of groundwater pollution, dissipating a wide range of industrial chemicals and pesticides. To study the fate of co-disposed chemicals in the subsoil of landfills, anaerobic soil columns loaded with anaerobic leachate from a municipal landfill were set up. The leachate was spiked with eleven compounds representing three groups of chemicals: chlorophenols, nitrophenols and organophosphates. Two subsoils were used in the study. The columns were maintained at Danish groundwater temperature (8-10°C), and were run for a period of 10 months. Analysis of the influent leachate concentrations of the spiked compounds showed that the concentrations were constant during the entire experimental period. Many of the compounds showed delayed breakthrough (compared to chloride breakthrough) in both soils, followed by a constant effluent concentration ratio of less than unity indicating that degradation was occuring. The velocities for the chloro- and nitrophenols were in the range of 10-100% of the water velocity in the two subsoils. The distribution coefficient for the specific phenol, the acidity and the pH of the soil apparently governed the retardation of the phenolic compounds. Degradation of most of the phenols was observed with half-like values of 30-150 days. The four organophosphorus pesticides, Dimethoate ®, Malathion ®, Sulfotep ® and Fenitrothion ®, showed relative velocities from < 10% to ≈ 100%. Malathion ® and Sulfotep ® were degraded with half-life values of 10-20 days, while Dimethoate ® was not significantly degraded in the two soil columns. Fenitrothion ® did not appear in the effluent from the columns within the experimental period of time, probably due to high retardation.

Aging of organochlorine pesticides and polychlorinated biphenyls in muck soil: volatilization, bioaccessibility, and degradation.

PubMed

Wong, Fiona; Bidleman, Terry F

2011-02-01

An organic rich muck soil which is highly contaminated with native organochlorine pesticide (OCs) was spiked with known amounts of (13)C-labeled OCs and nonlabeled polychlorinated biphenyls (PCBs). Spiked soils were aged under indoor, outdoor, and sterile conditions and the change in volatility, surrogate bioaccessibility, and degradation of chemicals was monitored periodically over 730 d. Volatility was measured using a fugacity meter to characterize the soil-air partition coefficient (K(SA) = C(SOIL)/C(AIR)). The fraction of bioaccessible residues was estimated by comparing recoveries of chemical with a mild extractant, hydroxylpropyl-β-cyclodextrin (HPCD) vs a harsh extractant, DCM. K(SA) of the spiked OCs in the nonsterile (Indoor, Outdoor) soils were initially lower and approached the K(SA) of native OCs over time, showing reduction of volatility upon aging. HPCD extractability of spiked OCs and PCBs were negatively correlated with K(SA), which suggests that volatility can be used as a surrogate for bioaccessibility. Degradation of endosulfans, PCB 8 and 28 was observed in the nonsterile soils, and (13)C(6)-α-HCH showed selective degradation of the (+) enantiomer. Enantiomer fractions (EF) in air and HPCD extracts were lower than in nonsterile soils, suggesting greater sequestering of the (+) enantiomer in the soil during microbial degradation.

Prediction of the ageing of commercial lager beer during storage based on the degradation of iso-α-acids.

PubMed

Blanco, Carlos A; Nimubona, Dieudonné; Caballero, Isabel

2014-08-01

Iso-α-acids and their chemically modified variants are responsible for the bitterness of beer and play a disproportionately large role in the final quality of beer. The current study was undertaken to predict the degradation of commercial lager beers related to changes in the concentration of trans-iso-α-acids during storage by using high-pressure liquid chromatography. In the analysed beers the concentration of isohumulone (average concentration 28 mg L(-1)) was greater than that of isocohumulone (20 mg L(-1)) and isoadhumulone (10 mg L(-1)). The kinetic parameters, activation energy and rate constant, of the trans-iso-α-acids were calculated. In the case of dark beers, the activation energy for the degradation of trans-isocohumulones was found to be higher than for trans-isohumulones and trans-isoadhumulones, whereas in pale and alcohol-free beers activation energies for the degradation of the three trans isomers were similar. The loss of iso-α-acids can be calculated using the activation energy of the degradation of trans-iso-α-acids and the temperature profile of the accelerated ageing. The results obtained in the investigation can be used in the beer industry to predict the alteration of the bitterness of beer during storage. © 2013 Society of Chemical Industry.

Evaluation of HDPE and LDPE degradation by fungus, implemented by statistical optimization

NASA Astrophysics Data System (ADS)

Ojha, Nupur; Pradhan, Neha; Singh, Surjit; Barla, Anil; Shrivastava, Anamika; Khatua, Pradip; Rai, Vivek; Bose, Sutapa

2017-01-01

Plastic in any form is a nuisance to the well-being of the environment. The ‘pestilence’ caused by it is mainly due to its non-degradable nature. With the industrial boom and the population explosion, the usage of plastic products has increased. A steady increase has been observed in the use of plastic products, and this has accelerated the pollution. Several attempts have been made to curb the problem at large by resorting to both chemical and biological methods. Chemical methods have only resulted in furthering the pollution by releasing toxic gases into the atmosphere; whereas; biological methods have been found to be eco-friendly however they are not cost effective. This paves the way for the current study where fungal isolates have been used to degrade polyethylene sheets (HDPE, LDPE). Two potential fungal strains, namely, Penicillium oxalicum NS4 (KU559906) and Penicillium chrysogenum NS10 (KU559907) had been isolated and identified to have plastic degrading abilities. Further, the growth medium for the strains was optimized with the help of RSM. The plastic sheets were subjected to treatment with microbial culture for 90 days. The extent of degradation was analyzed by, FE-SEM, AFM and FTIR. Morphological changes in the plastic sheet were determined.

Evaluation of HDPE and LDPE degradation by fungus, implemented by statistical optimization.

PubMed

Ojha, Nupur; Pradhan, Neha; Singh, Surjit; Barla, Anil; Shrivastava, Anamika; Khatua, Pradip; Rai, Vivek; Bose, Sutapa

2017-01-04

Plastic in any form is a nuisance to the well-being of the environment. The 'pestilence' caused by it is mainly due to its non-degradable nature. With the industrial boom and the population explosion, the usage of plastic products has increased. A steady increase has been observed in the use of plastic products, and this has accelerated the pollution. Several attempts have been made to curb the problem at large by resorting to both chemical and biological methods. Chemical methods have only resulted in furthering the pollution by releasing toxic gases into the atmosphere; whereas; biological methods have been found to be eco-friendly however they are not cost effective. This paves the way for the current study where fungal isolates have been used to degrade polyethylene sheets (HDPE, LDPE). Two potential fungal strains, namely, Penicillium oxalicum NS4 (KU559906) and Penicillium chrysogenum NS10 (KU559907) had been isolated and identified to have plastic degrading abilities. Further, the growth medium for the strains was optimized with the help of RSM. The plastic sheets were subjected to treatment with microbial culture for 90 days. The extent of degradation was analyzed by, FE-SEM, AFM and FTIR. Morphological changes in the plastic sheet were determined.

FT-Raman spectroscopy study of organic matrix degradation in nanofilled resin composite.

PubMed

Soares, Luís Eduardo Silva; Nahórny, Sídnei; Martin, Airton Abrahão

2013-04-01

This in vitro study evaluated the effect of light curing unit (LCU) type, mouthwashes, and soft drink on chemical degradation of a nanofilled resin composite. Samples (80) were divided into eight groups: halogen LCU, HS--saliva (control); HPT--Pepsi Twist®; HLC--Listerine®; HCP--Colgate Plax®; LED LCU, LS--saliva (control); LPT--Pepsi Twist®; LLC--Listerine®; LCP--Colgate Plax®. The degree of conversion analysis and the measure of the peak area at 2,930 cm-1 (organic matrix) of resin composite were done by Fourier-transform Raman spectroscopy (baseline, after 7 and 14 days). The data were subjected to multifactor analysis of variance (ANOVA) at a 95% confidence followed by Tukey's HSD post-hoc test. The DC ranged from 58.0% (Halogen) to 59.3% (LED) without significance. Differences in the peak area between LCUs were found after 7 days of storage in S and PT. A marked increase in the peak intensity of HLC and LLC groups was found. The soft-start light-activation may influence the chemical degradation of organic matrix in resin composite. Ethanol contained in Listerine® Cool Mint mouthwash had the most significant degradation effect. Raman spectroscopy is shown to be a useful tool to investigate resin composite degradation.

Long-Term In Vitro Degradation of a High-Strength Brushite Cement in Water, PBS, and Serum Solution

PubMed Central

Ajaxon, Ingrid; Öhman, Caroline; Persson, Cecilia

2015-01-01

Bone loss and fractures may call for the use of bone substituting materials, such as calcium phosphate cements (CPCs). CPCs can be degradable, and, to determine their limitations in terms of applications, their mechanical as well as chemical properties need to be evaluated over longer periods of time, under physiological conditions. However, there is lack of data on how the in vitro degradation affects high-strength brushite CPCs over longer periods of time, that is, longer than it takes for a bone fracture to heal. This study aimed at evaluating the long-term in vitro degradation properties of a high-strength brushite CPC in three different solutions: water, phosphate buffered saline, and a serum solution. Microcomputed tomography was used to evaluate the degradation nondestructively, complemented with gravimetric analysis. The compressive strength, chemical composition, and microstructure were also evaluated. Major changes from 10 weeks onwards were seen, in terms of formation of a porous outer layer of octacalcium phosphate on the specimens with a concomitant change in phase composition, increased porosity, decrease in object volume, and mechanical properties. This study illustrates the importance of long-term evaluation of similar cement compositions to be able to predict the material's physical changes over a relevant time frame. PMID:26587540

Study of the degradation in aqueous solution of a refractory organic compound: avermectin type used as pesticide in agriculture.

PubMed

Boukhrissa, Athir; Ferrag-Siagh, Fatiha; Rouidi, Lina-Mounia; Chemat, Smaïn; Aït-Amar, Hamid

2017-10-01

We examined the removal of abamectin by the electro-Fenton (EF) process and the feasibility of biological treatment after degradation. The effect of the operating parameters showed that abamectin (Aba) degradation was enhanced with increasing temperature. Response surface analysis of the central composite design led to the following optimal conditions for the abatement of chemical oxygen demand: 45.5 °C, 5 mg L -1 , 150 mA, and 0.15 mmol L -1 for the temperature, initial Aba concentration, current intensity, and catalyst concentration, respectively. Under these conditions, 68.01% of the organic matter was removed and 94% of Aba was degraded after 5 h and 20 min of electrolysis, respectively. A biodegradability test, which was performed on a solution electrolyzed at 47 °C, 9 mg L -1 , 150 mA, and 0.15 mmol L -1 , confirms that the ratio of biological oxygen demand/chemical oxygen demand increased appreciably from 0.0584 to 0.64 after 5 h of electrolysis. This increased ratio is slightly above the limit of biodegradability (0.4). These results show the relevance of the EF process and its effectiveness for abamectin degradation. We conclude that biological treatment can be combined with the EF process for total mineralization.

Development of non-thermal plasma jet and its potential application for color degradation of organic pollutant in wastewater treatment

NASA Astrophysics Data System (ADS)

Pirdo Kasih, Tota; Kharisma, Angel; Perdana, Muhammad Kevin; Murphiyanto, Richard Dimas Julian

2017-12-01

This paper presents the development of non-thermal plasma-based AOPs for color degradation in wastewater treatment. The plasma itself was generated by an in-house high voltage power supply (HVPS). Instead of gas-phase plasma system, we applied plasma jet system underwater during wastewater treatment without additional any chemicals (chemical-free processing). The method is thought to maximize the energy transfer and increase the efficient interaction between plasma and solution during the process. Our plasma jet system could proceed either by using helium (He), argon (Ar) and air as the medium in an open air atmosphere. Exploring the developed plasma to be applied in organic wastewater treatment, we demonstrated that the plasma jet could be generated underwater and yields in color degradation of methylene blue (MB) wastewater model. When using Ar gas as a medium, the color degradation of MB could be achieved within 90 minutes. Whereas, by using Ar with an admixing of oxygen (O2) gas, the similar result could be accomplished within 60 minutes. Additional O2 gas in the latter might produce more hydroxyl radicals and oxygen-based species which speed up the oxidative reaction with organic pollutants, and hence accelerate the process of color degradation.

Evaluation of HDPE and LDPE degradation by fungus, implemented by statistical optimization

PubMed Central

Ojha, Nupur; Pradhan, Neha; Singh, Surjit; Barla, Anil; Shrivastava, Anamika; Khatua, Pradip; Rai, Vivek; Bose, Sutapa

2017-01-01

Plastic in any form is a nuisance to the well-being of the environment. The ‘pestilence’ caused by it is mainly due to its non-degradable nature. With the industrial boom and the population explosion, the usage of plastic products has increased. A steady increase has been observed in the use of plastic products, and this has accelerated the pollution. Several attempts have been made to curb the problem at large by resorting to both chemical and biological methods. Chemical methods have only resulted in furthering the pollution by releasing toxic gases into the atmosphere; whereas; biological methods have been found to be eco-friendly however they are not cost effective. This paves the way for the current study where fungal isolates have been used to degrade polyethylene sheets (HDPE, LDPE). Two potential fungal strains, namely, Penicillium oxalicum NS4 (KU559906) and Penicillium chrysogenum NS10 (KU559907) had been isolated and identified to have plastic degrading abilities. Further, the growth medium for the strains was optimized with the help of RSM. The plastic sheets were subjected to treatment with microbial culture for 90 days. The extent of degradation was analyzed by, FE-SEM, AFM and FTIR. Morphological changes in the plastic sheet were determined. PMID:28051105

Tracking Agricultural Land Degradation with Landsat

NASA Astrophysics Data System (ADS)

Lam, K.; Jimenez, U.; Mclean, A.

2013-12-01

Land preservation and in particular, soil preservation, is key to maintaining the stability of wildlife on earth. The necessity to maintain land quality isn't unique to any specific area, it is a global issue. Land degradation can be witnessed across the globe, from the Heihe River Basin, China to the San Joaquin River in Central Valley, California. Large-scale 'traditional' agricultural practices such as widespread monoculture, overuse of chemical fertilizers and pesticides, and over-farming, have been found to cause significant land degradation in many regions. Once the causes of land degradation have been established, it is important to research preventative and rehabilitative measures. This is where the popularization of agricultural sustainability has proven wildly important, manifesting in a world-wide phenomenon. This research used Landsat and ENVI to: (1) identify changes in vegetation, over time, along the Heihe River, in an effort to measure the effectiveness of a new mandate focused on rehabilitating this desertification-prone area; and (2) show changes in the San Joaquin River through three droughts (1986 to present). The sudden spur of interest in agricultural sustainability and land preservation has led to changes in legislation, such as the Heihe River Basin Mandate, increased concern over the use of land degrading techniques, tools, chemicals, and more research on extreme weather events.

Chemicals used in the rubber industry. An overview.

PubMed

Fishbein, L

1983-01-01

Hundreds of chemicals illustrative of many structural and use categories are employed in the rubber industry. The present overview has centered on the structural features of a number of compounds representative of several select use categories, eg, vulcanizing agents, accelerators, antioxidants, antiozonants, and blowing agents, with focus on the nature of their impurities, their chemical degradation, and by-products, as well as on those chemicals that can be converted to N-nitrosamines.

Bacteria-mediated bisphenol A degradation.

PubMed

Zhang, Weiwei; Yin, Kun; Chen, Lingxin

2013-07-01

Bisphenol A (BPA) is an important monomer in the manufacture of polycarbonate plastics, food cans, and other daily used chemicals. Daily and worldwide usage of BPA and BPA-contained products led to its ubiquitous distribution in water, sediment/soil, and atmosphere. Moreover, BPA has been identified as an environmental endocrine disruptor for its estrogenic and genotoxic activity. Thus, BPA contamination in the environment is an increasingly worldwide concern, and methods to efficiently remove BPA from the environment are urgently recommended. Although many factors affect the fate of BPA in the environment, BPA degradation is mainly depended on the metabolism of bacteria. Many BPA-degrading bacteria have been identified from water, sediment/soil, and wastewater treatment plants. Metabolic pathways of BPA degradation in specific bacterial strains were proposed, based on the metabolic intermediates detected during the degradation process. In this review, the BPA-degrading bacteria were summarized, and the (proposed) BPA degradation pathway mediated by bacteria were referred.

Distribution of chemical warfare agent, energetics, and metals in sediments at a deep-water discarded military munitions site

NASA Astrophysics Data System (ADS)

Briggs, Christian; Shjegstad, Sonia M.; Silva, Jeff A. K.; Edwards, Margo H.

2016-06-01

There is a strong need to understand the behavior of chemical warfare agent (CWA) at underwater discarded military munitions (DMM) sites to determine the potential threat to human health or the environment, yet few studies have been conducted at sites in excess of 250 m, the depth at which most U.S. chemical munitions were disposed. As part of the Hawai'i Undersea Military Munitions Assessment (HUMMA), sediments adjacent to chemical and conventional DMM at depths of 400-650 m were sampled using human occupied vehicles (HOVs) in order to quantify the distribution of CWA, energetics, and select metals. Sites in the same general area, with no munitions within 50 m in any direction were sampled as a control. Sulfur mustard (HD) and its degradation product 1,4-dithiane were detected at each CWA DMM site, as well as a single sample with the HD degradation product 1,4-thioxane. An energetic compound was detected in sediment to a limited extent at one CWA DMM site. Metals common in munitions casings (i.e., Fe, Cu, and Pb) showed similar trends at the regional and site-wide scales, likely reflecting changes in marine sediment deposition and composition. This study shows HD and its degradation products can persist in the deep-marine environment for decades following munitions disposal.

The Effect of Specific Surface Area of Chitin-Metal Silicate Coprocessed Excipient on the Chemical Decomposition of Cefotaxime Sodium.

PubMed

Al-Nimry, Suhair S; Alkhamis, Khouloud A; Alzarieni, Kawthar Z

2017-02-01

Chitin-metal silicates are multifunctional excipients used in tablets. Previously, a correlation between the surface acidity of chitin-calcium and chitin-magnesium silicate and the chemical decomposition of cefotaxime sodium was found but not with chitin-aluminum silicate. This lack of correlation could be due to the catalytic effect of silica alumina or the difference in surface area of the excipients. The objective of this study was to investigate the effect of the specific surface area of the excipient on the chemical decomposition of cefotaxime sodium in the solid state. Chitin was purified and coprocessed with different metal silicates to prepare the excipients. The specific surface area was determined using gas adsorption. The chemical decomposition was studied at constant temperature and relative humidity. Also, the degradation in solution was studied. A correlation was found between the degradation rate constant and the surface area of chitin-aluminum and chitin-calcium silicate but not with chitin-magnesium silicate. This was due to the small average pore diameter of this excipient. Also, the degradation in solution was slower than in solid state. In conclusion, the stability of cefotaxime sodium was dependent on the surface area of the excipient in contact with the drug. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product.

PubMed

Leszczyński, Piotr J; Budzianowski, Armand; Dobrzycki, Lukasz; Cyrański, Michał K; Derzsi, Mariana; Grochala, Wojciech

2012-01-14

High purity samples of a [Ag(pyrazine)(2)]S(2)O(8) complex were obtained using modified synthetic pathways. Di(pyrazine)silver(II) peroxydisulfate is sensitive to moisture forming [Ag(pyrazine)(2)](S(2)O(8))(H(2)O) hydrate which degrades over time yielding HSO(4)(-) derivatives and releasing oxygen. One polymorphic form of pyrazinium hydrogensulfate, β-(pyrazineH(+))(HSO(4)(-)), is found among the products of chemical decomposition together with unique [Ag(i)(pyrazine)](5)(H(2)O)(2)(HSO(4))(2)[H(SO(4))(2)]. Chemical degradation of [Ag(pyrazine)(2)]S(2)O(8) in the presence of trace amounts of moisture can explain the very low yield of wet synthesis (11-15%). Attempts have failed to obtain a mixed valence Ag(II)/Ag(I) pyrazine complex via partial chemical reduction of the [Ag(pyrazine)(2)]S(2)O(8) precursor with a variety of inorganic and organic reducing agents, or via controlled thermal decomposition. Thermal degradation of [Ag(pyrazine)(2)]S(2)O(8) containing occluded water proceeds at T > 90 °C via evolution of O(2); simultaneous release of pyrazine and SO(3) is observed during the next stages of thermal decomposition (120-285 °C), while Ag(2)SO(4) and Ag are obtained upon heating to 400-450 °C.

Variation in ruminal in situ degradation of crude protein and starch from maize grains compared to in vitro gas production kinetics and physical and chemical characteristics.

PubMed

Seifried, Natascha; Steingaß, Herbert; Schipprack, Wolfgang; Rodehutscord, Markus

2016-10-01

The objectives of this study were (1) to evaluate in situ ruminal dry matter (DM), crude protein (CP) and starch degradation characteristics and in vitro gas production (GP) kinetics using a set of 20 different maize grain genotypes and (2) to predict the effective degradation (ED) of CP and starch from chemical and physical characteristics alone or in combination with in vitro GP measurements. Maize grains were characterised by different chemical and physical characteristics. Ruminal in situ degradation was measured in three lactating Jersey cows. Ground grains (sieve size: 2 mm) were incubated in bags for 1, 2, 4, 8, 16, 24, 48 and 72 h. Bag residues were analysed for CP and starch content. Degradation kinetics was determined and the ED of DM, CP and starch calculated using a ruminal passage rate of 5%/h and 8%/h. The GP of the grains (sieve size: 1 mm) was recorded after 2, 4, 6, 8, 12, 24, 48 and 72 h incubation in buffered rumen fluid and fitted to an exponential equation to determine GP kinetics. Correlations and stepwise multiple linear regressions were evaluated for the prediction of ED calculated for a passage rate of 5%/h (ED5) for CP (EDCP5) and starch (EDST5). The in situ parameters and ED5 varied widely between genotypes with average values (±SD) of 64% ± 4.2, 62% ± 4.1 and 65% ± 5.2 for ED5 of DM, EDCP5 and EDST5 and were on average 10 percentage points lower for a passage rate of 8%/h. Degradation rates varied between 4.8%/h and 7.4%/h, 4.1%/h and 6.5%/h and 5.3%/h and 8.9%/h for DM, CP and starch, respectively. These rates were in the same range as GP rates (6.0-8.3%/h). The EDCP5 and EDST5 were related to CP concentration and could be evaluated in detail using CP fractions and specific amino acids. In vitro GP measurements and GP rates correlated well with EDCP5 and EDST5 and predicted EDCP5 and EDST5 in combination with the chemical characteristics of the samples. Equations can be used to obtain quick and cost effective information on ruminal degradation of CP and starch from maize grains.

Understanding and improving lithium ion batteries through mathematical modeling and experiments

NASA Astrophysics Data System (ADS)

Deshpande, Rutooj D.

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary. One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result of lithium diffusion during charging and discharging operations. When lithium is inserted in either the positive or negative electrode, there is a volume change associated with insertion or de-insertion. Diffusion-induced stresses (DISs) can therefore cause the nucleation and growth of cracks, leading to mechanical degradation of the batteries. With different mathematical models we studied the behavior of diffusion induces stresses and effects of electrode shape, size, concentration dependent material properties, pre-existing cracks, phase transformations, operating conditions etc. on the diffusion induced stresses. Thus we develop tools to guide the design of the electrode material with better mechanical stability for durable batteries. Along with mechanical degradation, chemical degradation of batteries also plays an important role in deciding battery cycle life. The instability of commonly employed electrolytes results in solid electrolyte interphase (SEI) formation. Although SEI formation contributes to irreversible capacity loss, the SEI layer is necessary, as it passivates the electrode-electrolyte interface from further solvent decomposition. SEI layer and diffusion induced stresses are inter-dependent and affect each-other. We study coupled chemical-mechanical degradation of electrode materials to understand the capacity fading of the battery with cycling. With the understanding of chemical and mechanical degradation, we develop a simple phenomenological model to predict battery life. On the experimental part we come up with a novel concept of using liquid metal alloy as a self-healing battery electrode. We develop a method to prepare thin film liquid gallium electrode on a conductive substrate. This enabled us to perform a series of electrochemical and characterization experiments which certify that liquid electrode undergo liquid-solid-liquid transition and thus self-heals the cracks formed during de-insertion. Thus the mechanical degradation can be avoided. We also perform ab-initio calculations to understand the equilibrium potential of various lithium-gallium phases. KEYWORDS: Lithium ion batteries, diffusion induced stresses, self-healing electrode, coupled chemical and mechanical degradation, life-prediction model.

Observation of the degradation of three types of plastic pellets exposed to UV irradiation in three different environments.

PubMed

Cai, Liqi; Wang, Jundong; Peng, Jinping; Wu, Ziqing; Tan, Xiangling

2018-07-01

Plastic debris represents one of the most prevalent and persistent pollution problems in the marine environment. In particular, microplastics that are mainly degraded from larger plastic debris have become a growing environmental concern. However, studies on the degradation of plastics in the aquatic environment that hydrobios reside in have been limited, while several studies regarding the degradation of plastics have been conducted under outdoor or accelerated weathering conditions. Thus, observation of the degradation of three types of virgin plastic pellets exposed to UV irradiation in three different environments (i.e., simulated seawater, ultrapure water, and a waterless (air) condition) was carried out. Data on the changes in physical and chemical properties were collected. The FTIR spectra showed that hydroxyl groups and carbonyl groups developed in three types of weathered plastic pellets under the air and ultrapure water environmental conditions after 3months of UV irradiation, while only carbonyl groups were found in plastic pellets in the simulated seawater environment. In contrast, the Raman spectra showed no significant changes in the weathered plastic pellets, but there were different intensities of characteristic peaks after exposure to UV irradiation. In addition, SEM images illustrated that granular oxidation, cracks and flakes were common patterns during degradation, and the plastic pellets in the three different environments experienced different levels of chemical weathering. We suggest that further studies on the degradation processes of plastic debris are needed to predict the fate of plastic debris in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Quantitative diagnosis and prognosis framework for concrete degradation due to alkali-silica reaction

NASA Astrophysics Data System (ADS)

Mahadevan, Sankaran; Neal, Kyle; Nath, Paromita; Bao, Yanqing; Cai, Guowei; Orme, Peter; Adams, Douglas; Agarwal, Vivek

2017-02-01

This research is seeking to develop a probabilistic framework for health diagnosis and prognosis of aging concrete structures in nuclear power plants that are subjected to physical, chemical, environment, and mechanical degradation. The proposed framework consists of four elements: monitoring, data analytics, uncertainty quantification, and prognosis. The current work focuses on degradation caused by ASR (alkali-silica reaction). Controlled concrete specimens with reactive aggregate are prepared to develop accelerated ASR degradation. Different monitoring techniques — infrared thermography, digital image correlation (DIC), mechanical deformation measurements, nonlinear impact resonance acoustic spectroscopy (NIRAS), and vibro-acoustic modulation (VAM) — are studied for ASR diagnosis of the specimens. Both DIC and mechanical measurements record the specimen deformation caused by ASR gel expansion. Thermography is used to compare the thermal response of pristine and damaged concrete specimens and generate a 2-D map of the damage (i.e., ASR gel and cracked area), thus facilitating localization and quantification of damage. NIRAS and VAM are two separate vibration-based techniques that detect nonlinear changes in dynamic properties caused by the damage. The diagnosis results from multiple techniques are then fused using a Bayesian network, which also helps to quantify the uncertainty in the diagnosis. Prognosis of ASR degradation is then performed based on the current state of degradation obtained from diagnosis, by using a coupled thermo-hydro-mechanical-chemical (THMC) model for ASR degradation. This comprehensive approach of monitoring, data analytics, and uncertainty-quantified diagnosis and prognosis will facilitate the development of a quantitative, risk informed framework that will support continuous assessment and risk management of structural health and performance.

Intracellular degradation of chemically functionalized carbon nanotubes using a long-term primary microglial culture model

NASA Astrophysics Data System (ADS)

Bussy, Cyrill; Hadad, Caroline; Prato, Maurizio; Bianco, Alberto; Kostarelos, Kostas

2015-12-01

Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study.Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06625e

Pathway-based monitoring of biological effects at Great Lakes sites

EPA Science Inventory

The Great Lakes region suffers from degradation of water and environmental quality due to release of chemicals of emerging concern (CEC) that may threaten near shore health. Critical issues remain in delisting AOC including determining sources of chemicals causing fish health im...

ALKALINE NONCYANIDE ZINC PLATING WITH REFUSE OF RECOVERED CHEMICALS

EPA Science Inventory

A metal finishing process can create environmental problems because it uses chemicals that are not only toxic but also resistant to degradation or decomposition. Study was undertaken at a zinc electroplating operation to achieve zero discharge of wastewater and total recycle of r...

Structural characterization of aquatic humic material. 2. Phenolic content and its relationship to chlorination mechanism in an isolated aquatic fulvi acid

USGS Publications Warehouse

Norwood, D.L.; Christman, R.F.; Hatcher, P.G.

1987-01-01

The complementary techniques of solid-state 13G nuclear magnetic resonance spectroscopy and chemical degradation were utilized to examine the lignin/phenolic substructure of an isolated aquatic fulvic acid capable of producing upon aqueous chlorination a number of organohalides typically found in municipal drinking water. Results indicate that while phenolic moieties are present in the fulvic acid, they account for only a minor fraction of the total carbon. A sequential chemical degradation experiment utilizing aqueous chlorine and CuO demonstrated that the lignin/phenolic substructure was attacked by the chlorine. It is concluded that while phenolic ring rupture mechanisms appear to be important in organohalide generation, other aqueous chlorination mechanisms involving aliphatic and other types of aromatic structures should also be considered. ?? 1987 American Chemical Society.

Plastics and beaches: a degrading relationship.

PubMed

Corcoran, Patricia L; Biesinger, Mark C; Grifi, Meriem

2009-01-01

Plastic debris in Earth's oceans presents a serious environmental issue because breakdown by chemical weathering and mechanical erosion is minimal at sea. Following deposition on beaches, plastic materials are exposed to UV radiation and physical processes controlled by wind, current, wave and tide action. Plastic particles from Kauai's beaches were sampled to determine relationships between composition, surface textures, and plastics degradation. SEM images indicated that beach plastics feature both mechanically eroded and chemically weathered surface textures. Granular oxidation textures were concentrated along mechanically weakened fractures and along the margins of the more rounded plastic particles. Particles with oxidation textures also produced the most intense peaks in the lower wavenumber region of FTIR spectra. The textural results suggest that plastic debris is particularly conducive to both chemical and mechanical breakdown in beach environments, which cannot be said for plastics in other natural settings on Earth.

Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

PubMed

Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

2014-04-15

Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs. Copyright © 2013 Elsevier B.V. All rights reserved.

Production of aromatics from di- and polyoxygenates

DOEpatents

Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy

2016-08-02

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline aluminamore » support.« less

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Group VIII metal and a crystallinemore » alumina support.« less

Citral stabilization and characterization of nanoemulsions stabilized by a mixture of gelatin and Tween 20 in an acidic system.

PubMed

Tian, Huaixiang; Li, Danfeng; Xu, Ting; Hu, Jing; Rong, Yuzhi; Zhao, Bo

2017-07-01

Citral is one of the most important flavor compounds in fresh juice and lemon oil. Unfortunately, citral is chemically unstable and degrades over time in aqueous solutions. Here, citral nanoemulsions including a mixture of gelatin and Tween 20 as emulsifiers were produced in an effort to maintain the stability of citral in an acidic system. The mean droplet size and polydispersity index of the citral nanoemulsion were 467.83 nm and 0.259 respectively when the mass ratio of gelatin/Tween 20 was 3:1 and the total emulsifier concentration of the emulsion system was 10 g kg -1 . The citral nanoemulsion remained stable during storage for 14 days at 30 °C. Therefore this nanoemulsion system effectively protected citral from degradation and decreased the formation of off-flavor compounds (e.g. p-cymene, p-cresol and p-methylacetophenone) relative to a single emulsifier. The mixture of gelatin and Tween 20 enhanced the stability of citral under acidic conditions and could be used as an effective emulsifier to protect citral from degradation under acidic environments in the food industry. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Advanced multivariate analysis to assess remediation of hydrocarbons in soils.

PubMed

Lin, Deborah S; Taylor, Peter; Tibbett, Mark

2014-10-01

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.

Studies of material and process compatibility in developing compact silicon vapor chambers

NASA Astrophysics Data System (ADS)

Cai, Qingjun; Bhunia, Avijit; Tsai, Chialun; Kendig, Martin W.; DeNatale, Jeffrey F.

2013-06-01

The performance and long-term reliability of a silicon vapor chamber (SVC) developed for thermal management of high-power electronics critically depend on compatibility of the component materials. A hermetically sealed SVC presented in this paper is composed of bulk silicon, glass-frit as a bonding agent, lead/tin solder as an interface sealant and a copper charging tube. These materials, in the presence of a water/vapor environment, may chemically react and release noncondensable gas (NCG), which can weaken structural strength and degrade the heat transfer performance with time. The present work reports detailed studies on chemical compatibility of the components and potential solutions to avoid the resulting thermal performance degradation. Silicon surface oxidation and purification of operating liquid are necessary steps to reduce performance degradation in the transient period. A lead-based solder with its low reflow temperature is found to be electrochemically stable in water/vapor environment. High glazing temperature solidifies molecular bonding in glass-frit and mitigates PbO precipitation. Numerous liquid flushes guarantee removal of chemical residual after the charging tube is soldered to SVC. With these improvements on the SVC material and process compatibility, high effective thermal conductivity and steady heat transfer performance are obtained.

Synthesis of azoxystrobin transformation products and selection of monoclonal antibodies for immunoassay development.

PubMed

Parra, Javier; Mercader, Josep V; Agulló, Consuelo; Abad-Somovilla, Antonio; Abad-Fuentes, Antonio

2012-04-25

The use of agrochemicals for crop protection may result in the presence of toxic residues in soils and aquatic environments, besides in foodstuffs. Most often just the parent compound is included in the definition of pesticide residue, even though chemicals resulting from biotransformation and degradation routes might also be of toxicological relevance. Azoxystrobin is a broad-spectrum systemic fungicide widely used worldwide to combat pathogenic fungi affecting plants. We herein report the synthesis and detailed chemical characterization of several of the most relevant metabolites and degradates of azoxystrobin. These compounds were further employed as ligands for screening a collection of monoclonal antibodies to azoxystrobin, which had been previously generated from haptens functionalized at different positions of the target chemical. As a result, an antibody was identified capable of binding, with subnanomolar affinity, not only azoxystrobin but also its main transformation products, such as the so-called acid and enol derivatives, as well as the azoxystrobin (Z)-isomer. The selected binder was demonstrated as a useful immunoreagent for the development of immunochemical assays as novel analytical tools for the qualitative determination of azoxystrobin and its metabolites and degradates. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Fluoxetine and Norfluoxetine Revisited: New Insights into the Electrochemical and Spectroscopic Properties

NASA Astrophysics Data System (ADS)

Garrido, E. Manuela; Garrido, Jorge; Calheiros, Rita; Marques, M. Paula M.; Borges, Fernanda

2009-08-01

The extent to which humans and wildlife are exposed to the vast array of anthropogenic chemicals and their degradation products, along with related naturally occurring compounds, is nowadays an important issue. The study of the physical-chemical properties of the compounds and/or degradation products is an important subject because some of them are intrinsically related to its resistance to degradation and/or bioaccumulation. Accordingly, the study of the electrochemical behavior of the selective serotonin reuptake inhibitor fluoxetine and its main metabolite norfluoxetine was investigated. The identification of the oxidation processes was done via two fluoxetine analogues, 1-(benzyloxy)-4-(trifluoromethyl)benzene and N-methyl-3-phenylpropan-1-amine hydrochloride. The oxidative processes occurring in fluoxetine are pH-dependent and were ascribed to the chemical moieties present in the molecule: the secondary amine group and the substituted aromatic nucleus. To perform an unequivocal ascription, the structural preferences of the drug and metabolite were also determined, by Raman spectroscopy coupled to quantum mechanical calculations (at the DFT level). The analytical data obtained in this work will allow the development of a rapid and unequivocal spectroscopic procedure suitable for fluoxetine identification, as well as to distinguish between the drug and its main metabolite.

Substrate degradation by the proteasome: a single-molecule kinetic analysis

PubMed Central

Lu, Ying; Lee, Byung-hoon; King, Randall W; Finley, Daniel; Kirschner, Marc W

2015-01-01

To address how the configuration of conjugated ubiquitins determines the recognition of substrates by the proteasome, we analyzed the degradation kinetics of substrates with chemically defined ubiquitin configurations. Contrary to the view that a tetraubiquitin chain is the minimal signal for efficient degradation, we find that distributing the ubiquitins as diubiquitin chains provides a more efficient signal. To understand how the proteasome actually discriminates among ubiquitin configurations, we developed single-molecule assays that distinguished intermediate steps of degradation kinetically. The level of ubiquitin on a substrate drives proteasome-substrate interaction, whereas the chain structure of ubiquitin affects translocation into the axial channel on the proteasome. Together these two features largely determine the susceptibility of substrates for proteasomal degradation. PMID:25859050

Effects of Stable Degradation Products of Curcumin on Cancer Cell Proliferation and Inflammation.

PubMed

Sanidad, Katherine Z; Zhu, Julia; Wang, Weicang; Du, Zheyuan; Zhang, Guodong

2016-12-07

Curcumin is among the most promising dietary compounds for cancer prevention. However, curcumin rapidly degrades in aqueous buffer at physiological pH, making it difficult to understand whether the effects of curcumin are from curcumin itself or its degradation products. Here we studied the antiproliferative and anti-inflammatory effects of curcumin degradation products, including its total degradation products (a mixture containing all stable degradation products of curcumin) and bicyclopentadione (a dominant stable degradation compound of curcumin). Curcumin potently modulated cell proliferation, progression of cell cycle, and apoptosis in MC38 colon cancer cells and inhibited lipopolysaccharide (LPS)-induced inflammatory responses and NF-κB signaling in RAW 264.7 macrophage cells. In contrast, neither the total degradation products of curcumin nor bicyclopentadione had such effects. For example, after 24 h of treatment in MC38 colon cancer cells, 5 μg/mL curcumin inhibited 39.2 ± 1.8% of cell proliferation, whereas its degradation products were inactive. Together, these results suggest that the stable chemical degradation products of curcumin are not likely to play a major role in mediating the biological activities of curcumin.

Thermal degradation of aqueous 2-aminoethylethanolamine in CO2 capture; identification of degradation products, reaction mechanisms and computational studies.

PubMed

Saeed, Idris Mohamed; Lee, Vannajan Sanghiran; Mazari, Shaukat Ali; Si Ali, B; Basirun, Wan Jeffrey; Asghar, Anam; Ghalib, Lubna; Jan, Badrul Mohamed

2017-01-01

Amine degradation is the main significant problems in amine-based post-combustion CO 2 capture, causes foaming, increase in viscosity, corrosion, fouling as well as environmental issues. Therefore it is very important to develop the most efficient solvent with high thermal and chemical stability. This study investigated thermal degradation of aqueous 30% 2-aminoethylethanolamine (AEEA) using 316 stainless steel cylinders in the presence and absence of CO 2 for 4 weeks. The degradation products were identified by gas chromatography mass spectrometry (GC/MS) and liquid chromatography-time-of-flight-mass spectrometry (LC-QTOF/MS). The results showed AEEA is stable in the absence of CO 2 , while in the presence of CO 2 AEEA showed to be very unstable and numbers of degradation products were identified. 1-(2-Hydroxyethyl)-2-imidazolidinone (HEIA) was the most abundance degradation product. A possible mechanism for the thermal degradation of AEEA has been developed to explain the formation of degradation products. In addition, the reaction energy of formation of the most abundance degradation product HEIA was calculated using quantum mechanical calculation.

Biodegradation of lignin and nicotine with white rot fungi for the delignification and detoxification of tobacco stalk.

PubMed

Su, Yulong; Xian, He; Shi, Sujuan; Zhang, Chengsheng; Manik, S M Nuruzzaman; Mao, Jingjing; Zhang, Ge; Liao, Weihong; Wang, Qian; Liu, Haobao

2016-11-21

Tobacco stalk is one kind of abundant crop residues in China. The high lignification of tobacco stalk increases its reusing cost and the existing of nicotine will cause serious pollution. The biodegradation of lignocellulosic biomass has been demonstrated to be an environmental and economical approach for the utilization of plant stalk. Meanwhile, many nicotine-degrading microorganisms were found in nature. However, microorganisms which could degraded both nicotine and lignin haven't been reported. Therefore, it's imperative to find some suitable microorganisms to break down lignin and simultaneously remove nicotine in tobacco stalk. The nicotine in tobacco stalk could be degraded effectively by Trametes versicolor, Trametes hirsute and Phanerochaete chrysosporium. The nicotine content in tobacco stalk was lowered to below 500 mg/kg (a safe concentration to environment) after 10 days of fermentation with Phanerochaete chrysosporium and Trametes versicolor, and 15 days with Trametes hirsute. The degradation rate of lignin in the fermented tobacco stalk was 37.70, 51.56 and 53.75% with Trametes versicolor, Trametes hirsute and Phanerochaete chrysosporium, respectively. Meanwhile, 24.28% hemicellulose was degraded by Phanerochaete chrysosporium and 28.19% cellulose was removed by Trametes hirsute. Through the enzyme activity analysis, the main and highest ligninolytic enzymes produced by Phanerochaete chrysosporium, Trametes hirsute and Trametes versicolor were lignin peroxidase (88.62 U · L -1 ), manganese peroxidase (100.95 U · L -1 ) and laccase (745.65 U · L -1 ). Meanwhile, relatively high and stable cellulase activity was also detected during the fermentation with Phanerochaete chrysosporium, and the highest endoglucanase, exoglucanase and filter paper enzyme activities were 0.38 U · mL -1 , 0.45 U · mL -1 and 0.35U · mL -1 , respectively. Moreover, the products in the fermentation of tobacco stalk with P. chrysosporium were identified with GC-MS, besides the chemicals produced in the degradation of lignin and nicotine, some small molecular valuable chemicals and fatty acid were also detected. Our study developed a new method for the degradation and detoxification of tobacco stalk by fermentation with white rot fungi Phanerochaete chrysosporium and Trametes hirsute. The different oxidative enzymes and chemical products detected during the degradation indicated a possible pathway for the utilization of tobacco stalk.

Bacterial extracellular lignin peroxidase

DOEpatents

Crawford, Donald L.; Ramachandra, Muralidhara

1993-01-01

A newly discovered lignin peroxidase enzyme is provided. The enzyme is obtained from a bacterial source and is capable of degrading the lignin portion of lignocellulose in the presence of hydrogen peroxide. The enzyme is extracellular, oxidative, inducible by lignin, larch wood xylan, or related substrates and capable of attacking certain lignin substructure chemical bonds that are not degradable by fungal lignin peroxidases.

Choosing and applying fire-retardant-treated plywood and lumber for roof designs

Treesearch

Susan LeVan; Mary Collet

1989-01-01

Fire-retardant-treated (FRT) plywood used as roof sheathing has exhibited strength degradation in some situations. The cause appears to be certain fire retardant chemicals that are activated under environmental conditions of high temperature and moisture content. This report describes how fire retardants are made, how they work, and what causes strength degradation of...

Using kinetic models to predict thermal degradation of fire-retardant-treated plywood roof sheathing

Treesearch

Patricia Lebow; Jerrold E. Winandy; Patricia K. Lebow

2003-01-01

Between 1985-1995 a substantial number of multifamily housing units in the Eastern and Southern U.S. experienced problems with thermally degraded fire-retardant-treated (FRT) plywood roof sheathing. A series of studies conducted at the USDA Forest Service, Forest Products Laboratory (FPL), examined the materials, chemical mechanisms, and process implications and has...

Environmental risk assessment of selected organic chemicals based on TOC test and QSAR estimation models.

PubMed

Chi, Yulang; Zhang, Huanteng; Huang, Qiansheng; Lin, Yi; Ye, Guozhu; Zhu, Huimin; Dong, Sijun

2018-02-01

Environmental risks of organic chemicals have been greatly determined by their persistence, bioaccumulation, and toxicity (PBT) and physicochemical properties. Major regulations in different countries and regions identify chemicals according to their bioconcentration factor (BCF) and octanol-water partition coefficient (Kow), which frequently displays a substantial correlation with the sediment sorption coefficient (Koc). Half-life or degradability is crucial for the persistence evaluation of chemicals. Quantitative structure activity relationship (QSAR) estimation models are indispensable for predicting environmental fate and health effects in the absence of field- or laboratory-based data. In this study, 39 chemicals of high concern were chosen for half-life testing based on total organic carbon (TOC) degradation, and two widely accepted and highly used QSAR estimation models (i.e., EPI Suite and PBT Profiler) were adopted for environmental risk evaluation. The experimental results and estimated data, as well as the two model-based results were compared, based on the water solubility, Kow, Koc, BCF and half-life. Environmental risk assessment of the selected compounds was achieved by combining experimental data and estimation models. It was concluded that both EPI Suite and PBT Profiler were fairly accurate in measuring the physicochemical properties and degradation half-lives for water, soil, and sediment. However, the half-lives between the experimental and the estimated results were still not absolutely consistent. This suggests deficiencies of the prediction models in some ways, and the necessity to combine the experimental data and predicted results for the evaluation of environmental fate and risks of pollutants. Copyright © 2016. Published by Elsevier B.V.

Biodegradation of toxic chemicals by Pleurotus eryngii in submerged fermentation and solid-state fermentation.

PubMed

Chang, Bea-Ven; Chang, Yi-Ming

2016-04-01

The toxic chemicals bisphenol A (BPA), bisphenol F (BPF), nonylphenol (NP), and tetrabromobisphenol A (TBBPA) are endocrine-disrupting chemicals that have consequently drawn much concern regarding their effect on the environment. The objectives of this study were to investigate the degradation of BPA, BPF, NP, and TBBPA by enzymes from Pleurotus eryngii in submerged fermentation (SmF) and solid-state fermentation (SSF), and also to assess the removal of toxic chemicals in spent mushroom compost (SMC). BPA and BPF were analyzed by high-performance liquid chromatography; NP and TBBPA were analyzed by gas chromatography. NP degradation was enhanced by adding CuSO4 (1 mM), MnSO4 (0.5 mM), gallic acid (1 mM), tartaric acid (20 mM), citric acid (20 mM), guaiacol (1 mM), or 2,2'-azino-bis- (3-ethylbenzothiazoline-6-sulfonic acid; 1 mM), with the last yielding a higher NP degradation rate than the other additives from SmF. The optimal conditions for enzyme activity from SSF were a sawdust/wheat bran ratio of 1:4 and a moisture content of 5 mL/g. The enzyme activities were higher with sawdust/wheat bran than with sawdust/rice bran. The optimal conditions for the extraction of enzyme from SMC required using sodium acetate buffer (pH 5.0, solid/solution ratio 1:5), and extraction over 3 hours. The removal rates of toxic chemicals by P. eryngii, in descending order of magnitude, were SSF > SmF > SMC. The removal rates were BPF > BPA > NP > TBBPA. Copyright © 2014. Published by Elsevier B.V.

Doping control container for urine stabilization: a pilot study.

PubMed

Tsivou, Maria; Giannadaki, Evangelia; Hooghe, Fiona; Roels, Kris; Van Gansbeke, Wim; Garribba, Flaminia; Lyris, Emmanouil; Deventer, Koen; Mazzarino, Monica; Donati, Francesco; Georgakopoulos, Dimitrios G; Van Eenoo, Peter; Georgakopoulos, Costas G; de la Torre, Xavier; Botrè, Francesco

2017-05-01

Urine collection containers used in the doping control collection procedure do not provide a protective environment for urine, against degradation by microorganisms and proteolytic enzymes. An in-house chemical stabilization mixture was developed to tackle urine degradation problems encountered in human sport samples, in cases of microbial contamination or proteolytic activity. The mixture consists of antimicrobial substances and protease inhibitors for the simultaneous inactivation of a wide range of proteolytic enzymes. It has already been tested in lab-scale, as part of World Anti-Doping Agency's (WADA) funded research project, in terms of efficiency against microbial and proteolytic activity. The present work, funded also by WADA, is a follow-up study on the improvement of chemical stabilization mixture composition, application mode and limitation of interferences, using pilot urine collection containers, spray-coated in their internal surface with the chemical stabilization mixture. Urine in plastic stabilized collection containers have been gone through various incubation cycles to test for stabilization efficiency and analytical matrix interferences by three WADA accredited Laboratories (Athens, Ghent, and Rome). The spray-coated chemical stabilization mixture was tested against microorganism elimination and steroid glucuronide degradation, as well as enzymatic breakdown of proteins, such as intact hCG, recombinant erythropoietin and small peptides (GHRPs, ipamorelin), induced by proteolytic enzymes. Potential analytical interferences, observed in the presence of spray-coated chemical stabilization mixture, were recorded using routine screening procedures. The results of the current study support the application of the spray-coated plastic urine container, in the doping control collection procedure. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Thermolytic Degradation of Synthetic Cannabinoids: Chemical Exposures and Pharmacological Consequences.

PubMed

Thomas, Brian F; Lefever, Timothy W; Cortes, Ricardo A; Grabenauer, Megan; Kovach, Alexander L; Cox, Anderson O; Patel, Purvi R; Pollard, Gerald T; Marusich, Julie A; Kevin, Richard C; Gamage, Thomas F; Wiley, Jenny L

2017-04-01

Synthetic cannabinoids are manufactured clandestinely with little quality control and are distributed as herbal "spice" for smoking or as bulk compound for mixing with a solvent and inhalation via electronic vaporizers. Intoxication with synthetic cannabinoids has been associated with seizure, excited delirium, coma, kidney damage, and other disorders. The chemical alterations produced by heating these structurally novel compounds for consumption are largely unknown. Here, we show that heating synthetic cannabinoids containing tetramethylcyclopropyl-ring substituents produced thermal degradants with pharmacological activity that varied considerably from their parent compounds. Moreover, these degradants were formed under conditions simulating smoking. Some products of combustion retained high affinity at the cannabinoid 1 (CB 1 ) and CB 2 receptors, were more efficacious than (-)-cis-3-[2-hydroxy-4-(1,1-dimethylheptyl)phenyl]-trans-4-(3-hydroxypropyl)cyclohexanol (CP55,940) in stimulating CB 1 receptor-mediated guanosine 5'-O-(3-thiotriphosphate) (GTPγS) binding, and were potent in producing Δ 9 -tetrahydrocannabinol-like effects in laboratory animals, whereas other compounds had low affinity and efficacy and were devoid of cannabimimetic activity. Degradants that retained affinity and efficacy also substituted in drug discrimination tests for the prototypical synthetic cannabinoid 1-pentyl-3-(1-naphthoyl)indole (JWH-018), and are likely to produce psychotropic effects in humans. Hence, it is important to take into consideration the actual chemical exposures that occur during use of synthetic cannabinoid formulations to better comprehend the relationships between dose and effect. Copyright © 2017 by The American Society for Pharmacology and Experimental Therapeutics.

Chemical and biological studies of β-carotene after exposure to Cannabis sativa smoke.

PubMed

do Monte, Dulciana S; Bezerra Tenório, Jonh A; Bastos, Isla V G A; de S Mendonça, Fábio; Neto, Joaquim E; da Silva, Teresinha G; Ramos, Clécio S

2016-01-01

Considering the increase in consumption of Cannabis sativa and the use of the compound β- carotene (BC) as supplement, we investigated potential changes in the chemical and biological proprieties of BC after exposure to C. sativa smoke (CSS). Our results showed that the BC exposed to CSS underwent 98.8% degradation and suffered loss of its antiradical activity. The major degradation products identified were 3-hydroxy-2,4,4-trimethylpentyl)2-methylpropanoate and (2-ethyl-3-hydroxyhexyl)2-methylpropanoate compounds. These are found in higher levels in the exhalations of colorectal cancer patients and are similar to the toxic products associated with lipid peroxidation of polyunsaturated fatty acids. In toxicological assays using micro-crustacean Artemia salina the BC was non-toxic, while the BC degraded by CSS had a toxicity of LC 50  = 397.35 μg/mL. In Wistar rats, females treated with BC degraded by CSS (BCCSS) showed whitish liver spots, alterations in liver weight and in bilirubin and alkaline phosphatase levels, and decrease in the number of leukocytes associated with atypical lymphocytosis. In male rats, there was an increase in the number of leukocytes when compared to the control group. In the histopathological analysis, the cortical region of the kidneys showed the presence of discrete amorphous eosinophilic material (cylinders) in the lumen of the proximate and distal convoluted tubules. In general, the BC in contact with CSS undergoes chemical changes and exhibits toxicity to rats and Artemia salina .

Magnetic multi-metal co-doped magnesium ferrite nanoparticles: An efficient visible light-assisted heterogeneous Fenton-like catalyst synthesized from saprolite laterite ore.

PubMed

Diao, Yifei; Yan, Zhikai; Guo, Min; Wang, Xidong

2018-02-15

Magnetic nanoparticles of multi-metal co-doped magnesium ferrite (MgFe 2 O 4 ) were synthesized from saprolite laterite ore by a hydrothermal method, and firstly proposed as a heterogeneous photon-Fenton-like catalyst for degradation of Rhodamine B (RhB). The factors that influence the degradation reaction including pH value, the concentration of H 2 O 2 and the amount of catalyst, were systematically investigated. The doped MgFe 2 O 4 exhibited a degradation efficiency up to 96.8%, and the chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiencies about 85.6% and 68.3%, respectively, under visible light illumination for 180min. The high activity is mainly attributed to the high specific surface area of the catalyst and the synergistic interaction between photo-catalytic oxidation and Fenton-like oxidation. Moreover, the catalyst also showed good stability and recycling performance for degrading RhB. After five consecutive degradation cycles, the activity decayed no more than 10%. Compared to other catalysts prepared from pure chemical agents, the multi-metal co-doped MgFe 2 O 4 is more competitive due to its high activity, good stability, ease of recollection, and especially the use of saprolite laterite ore as precursor. This work may provide a new avenue to synthesize efficient ferrite catalysts for degrading organic pollutants in wastewater by using natural minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of chemical cues on the foraging and tunneling behavior of Formosan subterranean termites (Isoptera: Rhinotermitidae)

USDA-ARS?s Scientific Manuscript database

Wood rot fungi can cause directional tunneling, aggregation behavior and increased wood consumption by subterranean termites. Because vanillin and guaiacol are byproducts of lignin degradation, these chemicals were tested as potential attractants to Formosan subterranean termites, Coptotermes formo...

Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination.

PubMed

Gravett, M R; Hopkins, F B; Self, A J; Webb, A J; Timperley, C M; Riches, J R

2014-08-01

In the event of alleged use of organophosphorus nerve agents, all kinds of environmental samples can be received for analysis. These might include decontaminated and charred matter collected from the site of a suspected chemical attack. In other scenarios, such matter might be sampled to confirm the site of a chemical weapon test or clandestine laboratory decontaminated and burned to prevent discovery. To provide an analytical capability for these contingencies, we present a preliminary investigation of the effect of accelerant-based fire and liquid decontamination on soil contaminated with the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). The objectives were (a) to determine if VX or its degradation products were detectable in soil after an accelerant-based fire promoted by aviation fuel, including following decontamination with Decontamination Solution 2 (DS2) or aqueous sodium hypochlorite, (b) to develop analytical methods to support forensic analysis of accelerant-soaked, decontaminated and charred soil and (c) to inform the design of future experiments of this type to improve analytical fidelity. Our results show for the first time that modern analytical techniques can be used to identify residual VX and its degradation products in contaminated soil after an accelerant-based fire and after chemical decontamination and then fire. Comparison of the gas chromatography-mass spectrometry (GC-MS) profiles of VX and its impurities/degradation products from contaminated burnt soil, and burnt soil spiked with VX, indicated that the fire resulted in the production of diethyl methylphosphonate and O,S-diethyl methylphosphonothiolate (by an unknown mechanism). Other products identified were indicative of chemical decontamination, and some of these provided evidence of the decontaminant used, for example, ethyl 2-methoxyethyl methylphosphonate and bis(2-methoxyethyl) methylphosphonate following decontamination with DS2. Sample preparation procedures and analytical methods suitable for investigating accelerant and decontaminant-soaked soil samples are presented. VX and its degradation products and/or impurities were detected under all the conditions studied, demonstrating that accelerant-based fire and liquid-based decontamination and then fire are unlikely to prevent the retrieval of evidence of chemical warfare agent (CWA) testing. This is the first published study of the effects of an accelerant-based fire on a CWA in environmental samples. The results will inform defence and security-based organisations worldwide and support the verification activities of the Organisation for the Prohibition of Chemical Weapons (OPCW), winner of the 2013 Nobel Peace Prize for its extensive efforts to eliminate chemical weapons.

New Technologies for Repairing Aging Cables in Nuclear Power Plants

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

Simmons, Kevin L.; Fifield, Leonard S.; Westman, Matthew P.

The goal of this project is to demonstrate a proof-of-concept for a technique to repair aging cables that have been subjected to degradation associated with long-term thermal and radiation exposure in nuclear power plants. The physical degradation of the aging cables manifests itself primarily as cracking and increased brittleness of the polymeric electrical insulation. Therefore, the proposed cable-repair concept comprises development of techniques to impart a softening agent within the deteriorated polymer insulation jacket so as to regain the ability of the insulation to stretch without failing and possibly to heal existing cracks in the insulation. Our approach is tomore » use commercially available ethylene-propylene rubber (EPR) as the relevant test material, demonstrate the adsorption of chemical treatments in the EPR and quantify changes in resulting physical and mechanical properties. EPR cable samples have been thermally treated in air to produce specimens corresponding to the full range of cable age-performance points from new (>350% elongation at break) to end-of-life (<50% elongation at break). The current focus is on two chemical treatments selected as candidates for restoring age-related cable elasticity loss: a rubber plasticizer and a reactive silane molecule. EPR specimens of 200, 150, 100, and 50% elongation at break have been soaked in the candidate chemical treatments and the kinetics of chemical uptake, measured by change in mass of the samples, has been determined. Mechanical properties as a function of aging and chemical treatment have been measured including ultimate tensile strength, tensile modulus at 50% strain, elongation at break, and storage modulus. Dimensional changes with treatment and changes in glass transition temperature were also investigated. These ongoing experiments are expected to provide insight into the physical-chemical nature of the effect of thermal degradation on EPR rejuvenation limits and to advance novel methods for restoring the ability of degraded EPR to be compliant and resist fracture. The results of this research reveal that absorption of chemical treatments can lower the glass transition temperature and modulus of EPR. Chemical treatments pursued thus far have proven ineffective at restoring EPR strength and elongation at break. Future work will combine the plasticizer modalities found to successfully increase the volume of the EPR, reduce EPR glass transition temperature and reduce EPR modulus with promising chemistries that will repair the damage of the polymer, potentially using the plasticizer as a host for the new chemistry.« less

The degradation behaviour of nine diverse contaminants in urban surface water and wastewater prior to water treatment.

PubMed

Cormier, Guillaume; Barbeau, Benoit; Arp, Hans Peter H; Sauvé, Sébastien

2015-12-01

An increasing diversity of emerging contaminants are entering urban surface water and wastewater, posing unknown risks for the environment. One of the main contemporary challenges in ensuring water quality is to design efficient strategies for minimizing such risks. As a first step in such strategies, it is important to establish the fate and degradation behavior of contaminants prior to any engineered secondary water treatment. Such information is relevant for assessing treatment solutions by simple storage, or to assess the impacts of contaminant spreading in the absence of water treatment, such as during times of flooding or in areas of poor infrastructure. Therefore in this study we examined the degradation behavior of a broad array of water contaminants in actual urban surface water and wastewater, in the presence and absence of naturally occurring bacteria and at two temperatures. The chemicals included caffeine, sulfamethoxazole, carbamazepine, atrazine, 17β-estradiol, ethinylestradiol, diclofenac, desethylatrazine and norethindrone. Little information on the degradation behavior of these pollutants in actual influent wastewater exist, nor in general in water for desethylatrazine (a transformation product of atrazine) and the synthetic hormone norethindrone. Investigations were done in aerobic conditions, in the absence of sunlight. The results suggest that all chemicals except estradiol are stable in urban surface water, and in waste water neither abiotic nor biological degradation in the absence of sunlight contribute significantly to the disappearance of desethylatrazine, atrazine, carbamazepine and diclofenac. Biological degradation in wastewater was effective at transforming norethindrone, 17β-estradiol, ethinylestradiol, caffeine and sulfamethoxazole, with measured degradation rate constants k and half-lives ranging respectively from 0.0082-0.52 d(-1) and 1.3-85 days. The obtained degradation data generally followed a pseudo-first-order-kinetic model. This information can be used to model degradation prior to water treatment.

Current State of Knowledge in Microbial Degradation of Polycyclic Aromatic Hydrocarbons (PAHs): A Review

PubMed Central

Ghosal, Debajyoti; Ghosh, Shreya; Dutta, Tapan K.; Ahn, Youngho

2016-01-01

Polycyclic aromatic hydrocarbons (PAHs) include a group of organic priority pollutants of critical environmental and public health concern due to their toxic, genotoxic, mutagenic and/or carcinogenic properties and their ubiquitous occurrence as well as recalcitrance. The increased awareness of their various adverse effects on ecosystem and human health has led to a dramatic increase in research aimed toward removing PAHs from the environment. PAHs may undergo adsorption, volatilization, photolysis, and chemical oxidation, although transformation by microorganisms is the major neutralization process of PAH-contaminated sites in an ecologically accepted manner. Microbial degradation of PAHs depends on various environmental conditions, such as nutrients, number and kind of the microorganisms, nature as well as chemical property of the PAH being degraded. A wide variety of bacterial, fungal and algal species have the potential to degrade/transform PAHs, among which bacteria and fungi mediated degradation has been studied most extensively. In last few decades microbial community analysis, biochemical pathway for PAHs degradation, gene organization, enzyme system, genetic regulation for PAH degradation have been explored in great detail. Although, xenobiotic-degrading microorganisms have incredible potential to restore contaminated environments inexpensively yet effectively, but new advancements are required to make such microbes effective and more powerful in removing those compounds, which were once thought to be recalcitrant. Recent analytical chemistry and genetic engineering tools might help to improve the efficiency of degradation of PAHs by microorganisms, and minimize uncertainties of successful bioremediation. However, appropriate implementation of the potential of naturally occurring microorganisms for field bioremediation could be considerably enhanced by optimizing certain factors such as bioavailability, adsorption and mass transfer of PAHs. The main purpose of this review is to provide an overview of current knowledge of bacteria, halophilic archaea, fungi and algae mediated degradation/transformation of PAHs. In addition, factors affecting PAHs degradation in the environment, recent advancement in genetic, genomic, proteomic and metabolomic techniques are also highlighted with an aim to facilitate the development of a new insight into the bioremediation of PAH in the environment. PMID:27630626

DESIGNING PESTICIDE METABOLIC PATHWAY/DEGRADATE DATABASES FOR REGISTRANT SUBMITTED HEALTH EFFECTS/ECOLOGICAL EFFECTS DATA

EPA Science Inventory

OPPTS requires information on the toxic effects of pesticide metabolites as well as the parent chemical. Currently, OPP receives metabolic maps with registrant study data submissions, but there is no efficient way to access previously submitted maps on similar chemicals to help w...

CHEMICAL DESTRUCTION OF MTBE USING FENTON'S REAGENT: EFFECT OF FERROUS IRON/HYDROGEN PEROXIDE RATIO

EPA Science Inventory

In previous laboratory experiments Fenton's Reagent (FR) was successfully used as the source of hydroxyl radicals (OH*) for chemical treatment of low concentrations of methyl tert-butyl ether (MTBE) in water. Although under certain conditions MTBE degradation levels as high as 99...

76 FR 27636 - Notice of Intent To Grant Partially Exclusive License of the United States Patent Application No...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-12

... water remediation within the environmental remediation services industry. DATES: Written objections must... method of manufacturing a remediation material by providing a biogentic material as a substrate... chemical species or sorption and degradation of chemical species. The remediation material may be placed...

The GSTome Reflects the Chemical Environment of White-Rot Fungi

PubMed Central

Deroy, Aurélie; Saiag, Fanny; Kebbi-Benkeder, Zineb; Touahri, Nassim; Hecker, Arnaud; Morel-Rouhier, Mélanie; Colin, Francis; Dumarcay, Stephane; Gérardin, Philippe; Gelhaye, Eric

2015-01-01

White-rot fungi possess the unique ability to degrade and mineralize all the different components of wood. In other respects, wood durability, among other factors, is due to the presence of extractives that are potential antimicrobial molecules. To cope with these molecules, wood decay fungi have developed a complex detoxification network including glutathione transferases (GST). The interactions between GSTs from two white-rot fungi, Trametes versicolor and Phanerochaete chrysosporium, and an environmental library of wood extracts have been studied. The results demonstrate that the specificity of these interactions is closely related to the chemical composition of the extracts in accordance with the tree species and their localization inside the wood (sapwood vs heartwood vs knotwood). These data suggest that the fungal GSTome could reflect the chemical environment encountered by these fungi during wood degradation and could be a way to study their adaptation to their way of life. PMID:26426695

Recent Advances in Synthetic Bioelastomers

PubMed Central

Shi, Rui; Chen, Dafu; Liu, Quanyong; Wu, Yan; Xu, Xiaochuan; Zhang, Liqun; Tian, Wei

2009-01-01

This article reviews the degradability of chemically synthesized bioelastomers, mainly designed for soft tissue repair. These bioelastomers involve biodegradable polyurethanes, polyphosphazenes, linear and crosslinked poly(ether/ester)s, poly(ε-caprolactone) copolymers, poly(1,3-trimethylene carbonate) and their copolymers, poly(polyol sebacate)s, poly(diol-citrates) and poly(ester amide)s. The in vitro and in vivo degradation mechanisms and impact factors influencing degradation behaviors are discussed. In addition, the molecular designs, synthesis methods, structure properties, mechanical properties, biocompatibility and potential applications of these bioelastomers were also presented. PMID:20057942

Discovery and Testing of Ricin Therapeutics

DTIC Science & Technology

2012-06-01

variants lung disease ER degradation Fabri disease α -D-galactosidase neurological disease ER degradation Oculocutaneous albinism tyrosinase...against other pathogens and human diseases . 15. SUBJECT TERMS Ricin toxin, dislocation, small weight compounds, chemical inhibitors, high-content screen...the U.S. Departments of Health and Human Services (HHS) and Centers for Disease Control and Prevention (CDC). The toxin’s ability to kill cells and

The chemical structure of macromolecular fractions of a sulfur-rich oil

NASA Astrophysics Data System (ADS)

Richnow, Hans H.; Jenisch, Angela; Michaelis, Walter

1993-06-01

A selective stepwise chemical degradation has been developed for structural studies of highmolecularweight (HMW) fractions of sulfur-rich oils. The degradation steps are: (i) desulfurization (ii) cleavage of oxygen-carbon bonds (iii) oxidation of aromatic structural units. After each step, the remaining macromolecular matter was subjected to the subsequent reaction. This degradation scheme was applied to the asphaltene, the resin and a macromolecular fraction of low polarity (LPMF) of the Rozel Point oil. Total amounts of degraded low-molecular-weight compounds increased progressively in the order asphaltene < resin < LPMF. Desulfurization yielded mainly phytane, steranes and triterpanes. Oxygen-carbon bond cleavage resulted in hydrocarbon fractions predominated by n-alkanes and acyclic isoprenoids. The oxidation step afforded high amounts of linear carboxylic acids in the range of C 11 to C 33. The released compounds provide a more complete picture of the molecular structure of the oil fractions than previously available. Labelling experiments with deuterium atoms allowed to characterize the site of bonding and the type of linkage for the released compounds. Evidence is presented that subunits of the macromolecular network are attached simultaneously by oxygen and sulfur (n-alkanes, hopanes) or by sulfur and aromatic units ( n-alkanes, steranes).

Chemical intervention in bacterial lignin degradation pathways: Development of selective inhibitors for intradiol and extradiol catechol dioxygenases.

PubMed

Sainsbury, Paul D; Mineyeva, Yelena; Mycroft, Zoe; Bugg, Timothy D H

2015-06-01

Bacterial lignin degradation could be used to generate aromatic chemicals from the renewable resource lignin, provided that the breakdown pathways can be manipulated. In this study, selective inhibitors of enzymatic steps in bacterial degradation pathways were developed and tested for their effects upon lignin degradation. Screening of a collection of hydroxamic acid metallo-oxygenase inhibitors against two catechol dioxygenase enzymes, protocatechuate 3,4-dioxygenase (3,4-PCD) and 2,3-dihydroxyphenylpropionate 1,2-dioxygenase (MhpB), resulted in the identification of selective inhibitors D13 for 3,4-PCD (IC50 15μM) and D3 for MhpB (IC50 110μM). Application of D13 to Rhodococcus jostii RHA1 in minimal media containing ferulic acid led to the appearance of metabolic precursor protocatechuic acid at low concentration. Application of 1mM disulfiram, an inhibitor of mammalian aldehyde dehydrogenase, to R. jostii RHA1, gave rise to 4-carboxymuconolactone on the β-ketoadipate pathway, whereas in Pseudomonas fluorescens Pf-5 disulfiram treatment gave rise to a metabolite found to be glycine betaine aldehyde. Copyright © 2015 Elsevier Inc. All rights reserved.

Physical and Chemical Properties of Some Imported Woods and their Degradation by Termites

PubMed Central

Shanbhag, Rashmi R.; Sundararaj, R.

2013-01-01

The influence of physical and chemical properties of 20 species of imported wood on degradation of the wood by termites under field conditions was studied. The wood species studied were: Sycamore maple, Acer pseudoplatanus L. (Sapindales: Sapindaceae) (from two countries), Camphor, Dryobalanops aromatic C.F.Gaertner (Malvales: Dipterocarpaceae), Beech, Fagus grandifolia Ehrhart (Fagales: Fagaceae), F. sylvatica L. (from two countries), Oak, Quercus robur L., Ash, Fraxinus angustifolia Vahl (Lamiales: Oleaceae), F. excelsior L., Padauk, Pterocarpus soyauxii Taubert (Fabales: Fabaceae), (from two countries), Jamba, Xylia dolabrifiormis Roxburgh, Shorea laevis Ridley (Malvales: Dipterocarpaceae), S. macoptera Dyer, S. robusta Roth, Teak, Tectona grandis L.f. (Lamiales: Lamiaceae) (from five countries), and rubber tree, Hevea brasiliensis Müller Argoviensis (Malpighiales: Euphorbiaceae) from India. The termites present were: Odontotermes horni (Wasmann) (Isoptera: Termitidae), O. feae, O. wallonensis, and O. obeus (Rambur). A significant conelation was found between density, cellulose, lignin, and total phenolic contents of the wood and degradation by termites. The higher the density of the wood, the lower the degradation. Similarly, higher amount of lignin and total phenolic contents ensured higher resistance, whereas cellulose drives the termites towards the wood. PMID:23906349

Ecotoxicity by the biodegradation of alkylphenol polyethoxylates depends on the effect of trace elements.

PubMed

Hotta, Yudai; Hosoda, Akifumi; Sano, Fumihiko; Wakayama, Manabu; Niwa, Katsuki; Yoshikawa, Hiromichi; Tamura, Hiroto

2010-01-27

The bacteria Sphingomonas sp. strain BSN22, isolated from bean fields, degraded octylphenol polyethoxylates (OPEO(n)) to octylphenol (OP) under aerobic conditions. This biodegradation mechanism proceeded by the following two-step degradation process: (1) degradation of OPEO(n) to octylphenol triethoxylate (OPEO(3)), (2) degradation from OPEO(3) to OP via octylphenoxy acetic acid (OPEC(1)). The chemical structure of OPEC(1) was confirmed by analysis using (18)O-labeled water. Quantitative studies revealed that magnesium (Mg(2+)) and calcium (Ca(2+)) ions were essential for the biodegradation of OPEO(n). Furthermore, the rate of biodegradation was especially accelerated by ferric ions (Fe(3+)), and the accumulated amounts of endocrine active chemicals, such as OP, OPEO(1), and OPEC(1), significantly increased to the concentration of 22.8, 221.7, and 961.1 microM in the presence of 37.0 microM Fe(3+), respectively. This suggests that environmental elements significantly influence the resultant ecotoxicity as well as the rate of their biodegradation in the environment. This study on the mechanism of OPEO(n) biodegradation may play an important role in understanding and managing environmental safety, including drinking water safety.

Investigation of the Persistence of Nerve Agent Degradation ...

EPA Pesticide Factsheets

Journal Article The persistence of chemical warfare nerve agent degradation analytes on surfaces is important for reasons ranging from indicating the presence of nerve agent on that surface to environmental restoration of a site after nerve agent release. This study investigates the persistence of several chemical warfare nerve agent degradation analytes on a number of indoor surfaces and presents an approach for wipe sampling of surfaces, followed by wipe extraction and liquid chromatography-tandem mass spectrometry detection. Multiple commercially available wipe materials were investigated to determine optimal wipe recoveries. Tested surfaces, including several porous/permeable and largely nonporous/impermeable surfaces, were investigated to determine recoveries from these indoor surface materials. Wipe extracts were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and compared with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) results. UPLC provides a sensitive separation of targeted degradation analytes in addition to being nearly four times faster than HPLC, allowing for greater throughput during a widespread release concerning large-scale contamination and subsequent remediation events. Percent recoveries from nonporous/impermeable surfaces were 60-103% for isopropyl methylphosphonate (IMPA), 61-91 % for ethyl methylphosphonate (EMPA), and 60-98% for pinacolyl methylphosphona

Thermal degradation of the tensile strength of unidirectional boron/aluminum composites

NASA Technical Reports Server (NTRS)

Grimes, H. H.; Lad, R. A.; Maisel, J. E.

1977-01-01

The variation of ultimate tensile strength with thermal treatment of B-Al composite materials and of boron fibers chemically removed from these composites in an attempt to determine the mechanism of the resulting strength degradation was studied. Findings indicate that thermally cycling B-Al represents a more severe condition than equivalent time at temperature. Degradation of composite tensile strength from about 1.3 GN/m squared to as low as 0.34 GN/m squared was observed after 3,000 cycles to 420 C for 203 micrometers B-1100 Al composite. In general, the 1100 Al matrix composites degraded somewhat more than the 6061 matrix material studied. Measurement of fiber strengths confirmed a composite strength loss due to the degradation of fiber strength. Microscopy indicated a highly flawed fiber surface.

Long Term Degradation of Resin for High Temperature Composites

NASA Technical Reports Server (NTRS)

Patekar, Kaustubh A.

2000-01-01

The durability of polymer matrix composites exposed to harsh environments is a major concern. Surface degradation and damage are observed in polyimide composites used in air at 125 to 300 C. It is believed that diffusion of oxygen into the material and oxidative chemical reactions in the matrix are responsible. Previous work has characterized and modeled diffusion behavior, and thermogravimetric analyses (TGAs) have been carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. However, the model developed using these data was not able to capture behavior seen in isothermal tests, especially those of long duration. A test program that focuses on lower temperatures and makes use of isothermal tests was undertaken to achieve a better understanding of the degradation reactions under use conditions. A new low-cost technique was developed to collect chemical degradation data for isothermal tests lasting over 200 hr in the temperature range 125 to 300 C. Results indicate complex behavior not captured by the previous TGA tests, including the presence of weight-adding reactions. Weight gain reactions dominated in the 125 to 225 C temperature range, while weight loss reactions dominated beyond 225 C. The data obtained from isothermal tests was used to develop a new model of the material behavior. This model was able to fully capture the behavior seen in the tests up to 275 C. Correlation of the current model with both isothermal data at 300 C and high rate TGA test data is mediocre. At 300 C and above, the reaction mechanisms appear to change. Attempts (which failed) to measure non-oxidative degradation indicate that oxidative reactions dominate the degradation at low temperatures. Based on this work, long term isothermal testing in an oxidative atmosphere is recommended for studying the degradation behavior of this class of materials.

Degradation of Histamine by Lactobacillus plantarum Isolated from Miso Products.

PubMed

Kung, Hsien-Feng; Lee, Yi-Chen; Huang, Ya-Ling; Huang, Yu-Ru; Su, Yi-Cheng; Tsai, Yung-Hsiang

2017-10-01

Histamine is a toxic chemical and is the causative agent of food poisoning. This foodborne toxin may be degraded by the oxidative deamination activity of certain microorganisms. In this study, we isolated four histamine-degrading Lactobacillus plantarum bacteria from miso products. Among them, L. plantarum D-103 exhibited 100% degradation of histamine in de Man Rogosa Sharpe (MRS) broth containing 50 ppm of histamine after 24 h of incubation at 30°C. The optimal growth, histamine oxidase, and histamine-degrading activity of L. plantarum D-103 were observed in histamine MRS broth at pH 7.0, 3% NaCl, and 30°C. It also exhibited tolerance to broad ranges of pH (4 to 10) and salt concentrations (0 to 12%) in histamine MRS broth. Therefore, the histamine-degrading L. plantarum D-103 might be used as an additive culture to prevent histamine accumulation in miso products during fermentation.

Treatment of oily port wastewater effluents using the ultraviolet/hydrogen peroxide photodecomposition system.

PubMed

Siedlecka, Ewa Maria; Stepnowski, Piotr

2006-08-01

This paper presents the nonselective degradation of mechanically pretreated oily wastewater by hydrogen peroxide (H2O2) in the presence and absence of UV irradiation. The effect of chemical oxidation on wastewater biodegradability was also examined. The exclusive use of H2O2 photolyzed by daylight results in quite efficient degradation rates for the low peroxide concentrations used. Higher hydrogen peroxide concentrations inhibit degradation of organic contaminants in the wastewater. The degradation rates of all contaminants are relatively high with an advanced oxidation system (UV/H2O2), but degradation efficiencies are not distinguishably different when 20 or 45 minutes of UV irradiation is used. The excess of H2O2 used in the process can inhibit phenolic degradation and may lead to the formation of a new phenolic fraction. The biodegradability of port wastewater did not increase significantly following the application of the advanced oxidation process.

Mechanistic insights into lithium ion battery electrolyte degradation - a quantitative NMR study.

PubMed

Wiemers-Meyer, S; Winter, M; Nowak, S

2016-09-29

The changes in electrolyte composition on the molecular level and the reaction mechanisms of electrolyte degradation upon thermal aging are monitored by quantitative NMR spectroscopy, revealing similar rates of degradation for pristine and already aged electrolytes. The data analysis is not in favor of an autocatalytic reaction mechanism based on OPF 3 but rather indicates that the degradation of LiPF 6 in carbonate based solvents proceeds via a complex sequence of "linear" reactions rather than a cyclic reaction pattern which is determined by the amount of water present in the samples. All investigated electrolytes are reasonably stable at temperatures of up to 60 °C in the presence of minor amounts or absence of water hence indicating that chemical instability of electrolyte components against water is decisive for degradation and an increase in temperature ("thermal aging") just accelerates the degradation impact of water.

The kinetic of key phytochemical compounds of non-heading and heading leafy Brassica oleracea landraces as affected by traditional cooking methods.

PubMed

Giambanelli, Elisa; Verkerk, Ruud; D'Antuono, L Filippo; Oliviero, Teresa

2016-11-01

Kales are often a key ingredient of traditional foods, containing high amounts of indolic glucosinolates (precursors of indole-3-carbinol and ascorbigen), carotenoids and phenolics. The present trend to associate traditional foods crops with health-promoting properties suggested to investigate the degradation kinetic of three Brassica oleracea landraces' phytochemicals subjected to boiling, steaming and stir-frying. Boiling led to substantial losses due to leaching. Glucosinolates followed a second-order degradation kinetic (20% of their initial values after 10 min in Nero di Toscana). Phenolic content in leaves + cooking water remained unchanged, whereas their antioxidant capacity was reduced. Carotenoid content increased during the first minutes of boiling. Steaming showed the highest retention of phytochemicals, with often zero-order degradation kinetic, having however a strong effect on colour. Stir-frying produced high losses for all measured compounds; also, β-carotene reduced its content to 10-23% independently of variety. Conversion values for indole-derived compounds ranged from non-detectable to 23.5%. Variety strongly affected observed degradation rates because of a different glucosinolate composition and leaf structure. With this research, more information has been gained on the degradation kinetic of B. oleracea landraces' phytochemical compounds upon cooking, highlighting the possibility of improving bioactive component retention. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Biochars change the sorption and degradation of thiacloprid in soil: Insights into chemical and biological mechanisms.

PubMed

Zhang, Peng; Sun, Hongwen; Min, Lujuan; Ren, Chao

2018-05-01

One interest of using biochar as soil amendment is to reduce pesticide adverse effects. In this paper, the sorption and degradation of thiacloprid (THI) in a black soil amended by various biochars were systematically investigated, and the mechanisms therein were explored by analyzing the changes in soil physicochemical properties, degrading enzymes and genes and microorganism community. Biochar amendment increased THI sorption in soil, which was associated with an increase in organic carbon and surface area and a decrease in H/C. Amendments of 300-PT (pyrolyzing temperature) biochar promoted the biodegradation of THI by increasing the microbe abundance and improving nitrile hydratase (NHase) activity. In contrast, 500- and 700-PT biochar amendments inhibited biodegradation by reducing THI availability and changing NHase activity and THI-degradative nth gene abundance, and instead promoted chemical degradation mainly through elevated pH, active groups on mineral surface and generation of •OH and other free radicals. Furthermore, THI shifted the soil microbial community, stimulated the NHase activity and elevated nth gene abundance. Biochar amendments also changed soil bacterial community by modulating soil pH, dissolved organic matter and nitrogen and phosphorus levels, which further influenced THI biodegradation. Therefore, the impact of biochars on the fate of a pesticide in soil depends greatly on their type and properties, which should be comprehensively examined when applying biochar to soil. Copyright © 2018 Elsevier Ltd. All rights reserved.

Photochemical removal of aniline in aqueous solutions: switching from photocatalytic degradation to photo-enhanced polymerization recovery.

PubMed

Tang, Heqing; Li, Jing; Bie, Yeqiang; Zhu, Lihua; Zou, Jing

2010-03-15

Organic pollutants may be treated by either a degradation process or a recovery process in the view point of sustainable chemistry. Photocatalytic removal of aniline was investigated in aqueous solutions. It was found that the photocatalytic oxidation of aniline resulted in its degradation or polymerization, depending on its concentration. Hence a new treatment strategy was proposed in combination of photocatalytic degradation and polymerization, where the polymerization was in fact a recovery process. When aniline concentration was as low as 0.1 mmol L(-1), it was possible to photocatalytically degrade aniline, which could be further enhanced by increasing solution pH, modifying TiO(2) surface with the addition of anions, or coupling with the photoreduction of added oxidants. When aniline concentration was increased to about 1 mmol L(-1), the photocatalytic oxidation was observed to yield the polymerization of aniline, leading to nanocomposites of polyaniline (PAN) and TiO(2). Alternatively, the photo-enhanced chemical polymerization of aniline at higher concentrations (>or=50 mmol L(-1)) in the presence of chemical oxidants produced PAN nanostructures. The conversion of pollutant aniline to valuable PAN nanostructures or nano-PAN/TiO(2) composites is suggestive for possible applications in the treatment of aniline wastewaters as a sustainable environmental protection measure. (c) 2009 Elsevier B.V. All rights reserved.

Biomolecular Effects of Cold Plasma Exposure

NASA Technical Reports Server (NTRS)

Mogul, Rakesh; Bolshakov, Alexander A.; Chan, Suzanne L.; Stevens, Ramsey D.; Khare, Bishun N.; Meyyappan, M.; Trent, Jonathan D.; DeVincenzi, D. (Technical Monitor)

2002-01-01

The effects of cold plasma exposure on Deinococcus radiodurans, plasmid DNA and model proteins were assessed using microbiological, spectrometric and biochemical techniques. Exposure of D. radiodurans, an extremely radiation resistant microbe, to O2 plasma (less than or equal to 25 W, approx. 45 mTorr, 90 min) yielded a approx. 99.999 % sterilization and the sterilization rate was increased approx. 10-fold at 100 W and 500 mTorr. AFM images shows that the exposed cells are significantly deformed and possess 50-70 nm concavities. IR analysis indicates the chemical degradation of lipids, proteins and carotenoids of the cell wall and membrane. Intracellular damage was indicated by major absorbance loss at 1245, 1651 and 1538/cm corresponding to degradation of DNA and proteins, respectively. Biochemical experiments demonstrate that plasmas induce strand scissions and crosslinking of plasmid DNA, and reduction of enzyme activity; the degradation is power dependent with total sample loss occurring in 60 s at 200 W and 500 mTorr. Emission spectroscopy shows that D. radiodurans is volatilized into CO2, CO, N2 and H2O confirming the removal of biological matter from contaminated surfaces. The O2 plasma impacts several cellular components predominantly through chemical degradation by atomic oxygen. A CO2, plasma, however, was not effective at degrading D. radiodurans, revealing the importance of plasma composition, which has implications for planetary protection and the contamination of Mars.

Biodegradation of the Allelopathic Chemical m-Tyrosine by Bacillus aquimaris SSC5 Involves the Homogentisate Central Pathway

PubMed Central

Khan, Fazlurrahman; Kumari, Munesh; Cameotra, Swaranjit Singh

2013-01-01

m-Tyrosine is an amino acid analogue, exuded from the roots of fescue grasses, which acts as a potent allelopathic and a broad spectrum herbicidal chemical. Although the production and toxic effects of m-tyrosine are known, its microbial degradation has not been documented yet. A soil microcosm study showed efficient degradation of m-tyrosine by the inhabitant microorganisms. A bacterial strain designated SSC5, that was able to utilize m-tyrosine as the sole source of carbon, nitrogen, and energy, was isolated from the soil microcosm and was characterized as Bacillus aquimaris. Analytical methods such as HPLC, GC-MS, and 1H-NMR performed on the resting cell samples identified the formation of 3-hydroxyphenylpyruvate (3-OH-PPA), 3-hydroxyphenylacetate (3-OH-PhAc), and homogentisate (HMG) as major intermediates in the m-tyrosine degradation pathway. Enzymatic assays carried out on cell-free lysates of m-tyrosine-induced cells confirmed transamination reaction as the first step of m-tyrosine degradation. The intermediate 3-OH-PhAc thus obtained was further funneled into the HMG central pathway as revealed by a hydroxylase enzyme assay. Subsequent degradation of HMG occurred by ring cleavage catalyzed by the enzyme homogentisate 1, 2-dioxygenase. This study has significant implications in terms of understanding the environmental fate of m-tyrosine as well as regulation of its phytotoxic effect by soil microorganisms. PMID:24098407

Comparison of tissue deterioration of ripening banana fruit (Musa spp., AAA group, Cavendish subgroup) under chilling and non-chilling temperatures.

PubMed

Ramírez-Sánchez, Maricruz; Huber, Donald J; Vallejos, Carlos E

2018-03-08

In fleshy fruits, induced programmed cell death (PCD) has been observed in heat-treated tomato, and in ethylene-treated and low-temperature exposure in immature cucumber. No other fleshy fruit has been evaluated for chilling-injury-induced PCD, especially mature fruit with full ripening capacity. The purpose of this research was to identify and evaluate the presence of PCD processes during the development of low-temperature-induced physiopathy of banana fruit. Exposure of fruit to 5 °C for 4 days induced degradative processes similar to those occurring during ripening and overripening of non-chilled fruit. Nuclease from banana peel showed activity in both DNA substrates and RNA substrates. No exclusive low-temperature-induced proteases and nucleases were observed. DNA of chilled peel showed earlier signs of degradation and higher levels of DNA tailing during overripening. This study shows that exposure to low temperatures did not induce a pattern of degradative processes that differed from that occurring during ripening and overripening of non-chilled fruit. DNA showed earlier signs of degradation and higher levels of DNA tailing. Nuclease activity analysis showed bifunctionality in both chilled and non-chilled tissue and no chilling-exclusive protease and nuclease. Fleshy fruit might use their available resources on degradative processes and adjust them depending on environmental conditions. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

2-chloroethanol formation as evidence for a 2-chloroethyl alkylating intermediate during chemical degradation of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea and 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea.

PubMed

Reed, D J; May, H E; Boose, R B; Gregory, K M; Beilstein, M A

1975-03-01

Chemical degradation of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea or 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea in buffer under physiological conditions resulted in the formation of a significant quantity of 2-chlorethanol (18 to 25% of the initial nitrosourea concentration). Other degradation products observed included acetaldehyde (5 to 10%), vinyl chloride (1 to 2%), ethylene (1 to 2%), and cyclohexylamine (32%), but not 1,3-dicyclohexylurea. The 2-chlorethyl moiety of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea was trapped with halide ions, CI-, BR-, and I-, to form the corresponding dihaloethanes which were identified by gas chromatography-mass spectrometry techniques. High-pressure liquid chromatographic procedures were developed for the separation and quantiation of the nitrosoureas and many of their degradation products. It is postulated that a new mode of 1(2-chloreoethyl)-3-cyclohexyl-1-nitrosourea and 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea degradation can occur that is not the loss of the chloro group as chloride ion, but the loss of the N-3 hydrogen as a proton. Then the corresponding isocyanate and 2-chloroethyidiazene hydroxide are formed, with the latter intermidiate becoming an alkylating species, possibly in part as a 2-chloroethyl carbonium ion.

Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

NASA Astrophysics Data System (ADS)

DeVisscher, A.; Dewulf, J.; Van Durme, J.; Leys, C.; Morent, R.; Van Langenhove, H.

2008-02-01

Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation.

Solubilization and spore recovery from silicone polymers. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Hsiao, Y. C.

1974-01-01

A non-sporicidal technique for solvent degradation of cured silicone polymers was developed which involves chemical degradation of cured silicone polymers by amine solvents at room temperature. Substantial improvements were obtained in the recovery of seeded spores from room temperature cured polymers as compared to the standard recovery procedures, which indicates that the curing process is not sufficiently exothermic to reduce spore viability. The dissolution reaction of cured silicone polymers whith amine solvents is proposed to occur by bimolecular nucleophilic displacement. The chemical structure of silicone polymers was determined by spectroscopic methods. The phenyl to methyl ratio, R/Si ratio, molecular weight, and hydroxyl content of the silicone resins were determined.

Development of A Flexible System for the Simultaneous Conversion of Biomass to Industrial Chemicals and the Production of Industrial Biocatalysts

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

Gao, Johnway; Hooker, Brian S.; Skeen, R S.

2002-01-01

A flexible system was developed for the simultaneous conversion of biomass to industrial chemicals and the production of industrial biocatalysts. In particular, the expression of a bacterial enzyme, beta-glucuronidase (GUS), was investigated using a genetically modified starch-degrading Saccharomyces strain in suspension cultures in starch media. Different sources of starch including corn and waste potato starch were used for yeast biomass accumulation and GUS expression studies under controls of inducible and constitutive promoters. A thermostable bacterial cellulase, Acidothermus cellulolyticus E1 endoglucanase gene was also cloned into an episomal plasmid expression vector and expressed in the starch-degrading Saccharomyces strain.

Photostability of 2D Organic-Inorganic Hybrid Perovskites

PubMed Central

Wei, Yi; Audebert, Pierre; Galmiche, Laurent; Lauret, Jean-Sébastien; Deleporte, Emmanuelle

2014-01-01

We analyze the behavior of a series of newly synthesized (R-NH3)2PbX4 perovskites and, in particular, discuss the possible reasons which cause their degradation under UV illumination. Experimental results show that the degradation process depends a lot on their molecular components: not only the inorganic part, but also the chemical structure of the organic moieties play an important role in bleaching and photo-chemical reaction processes which tend to destroy perovskites luminescent framework. In addition, we find the spatial arrangement in crystal also influences the photostability course. Following these trends, we propose a plausible mechanism for the photodegradation of the films, and also introduced options for optimized stability. PMID:28788706

Nutrient content and nutrient availability of sorghum wet distiller's grain in comparison with the parental grain for ruminants.

PubMed

Trujillo, Ana I; Bruni, María; Chilibroste, Pablo

2017-06-01

The present study aimed to compare wet sorghum distiller's grain (WSDG) with sorghum grain (SG) in terms of: (i) chemical composition; (ii) in situ rumen degradation kinetics of organic matter (OM) and neutral detergent fiber (NDF); (iii) crude protein (CP) sub-fractions; (iv) in situ disappearance at 12 and 48 h; and (v) energy values. The WSDG intestinal digestibility (ID) of undegradable crude protein (UCP) was compared to soybean meal (SBM). Compared to SG, WSDG exhibited: (i) lower (P < 0.01) dry matter and non-fiber carbohydrate content, whereas the other chemical components were higher (P < 0.01); (ii) higher (P < 0.01) degradation rates of OM and NDF and lower (P < 0.01) degradable fraction of OM and NDF; (iii) lower (P < 0.05) contents of CP sub-fractions A, B1 and B2, and higher (P < 0.05) contents of B3 and C; (iv) lower (P < 0.05) protein disappearance at 12 and 48 h and higher UCP; and (v) lower (P < 0.05) energy content. The ID of UCP for WSDG was lower (P < 0.05) compared to SBM. The WSDG as a supplement provides a good source of energy. To enable its use as a protein supplement, further studies should be performed. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Assessment of the use of red mud as a catalyst for photodegradation of bisphenol A in wastewater treatment.

PubMed

Busto, Raquel Vieira; Gonçalves, Maraisa; Coelho, Lúcia Helena Gomes

2016-09-01

This study aimed to investigate the use of red mud (RM) - a byproduct of aluminum production, as a photocatalyst, which was characterized physical-chemically and used in the photodegradation of the target compound bisphenol A (BPA). Chemical processing was performed in the RM (acid treatment, chemical reduction and calcination) to verify the most active catalyst. From the results obtained, a complete degradation kinetics of BPA was carried out using a synthetic matrix (BPA in deionized water) and a real matrix (BPA in wastewater) using natural RM/calcined and TiO 2 for comparison. The results indicated the potential use of the RM/calcined, which was able to degrade between 88 and 100% of the pollutant in a synthetic sample. Tests on a real effluent sample resulted in degradation rates that ranged from 59 to 100% with chemical oxygen demand reductions of up to 23% using natural RM/calcined in comparison to TiO 2 . The blank system (irradiation of the solution without the use of a photocatalyst) and the natural RM/calcined one, resulted in reductions of the toxicity in the effluent sample (measured by EC 20 using the marine bacteria Vibrio fischeri) of about 12 times, whereas the same treatment using TiO 2 resulted in a toxicity reduction of only seven times. Within these results, the RM/calcined showed potential to be used in wastewater treatment in polishing processes.

Fate and transport of TNT, RDX, and HMX in streambed sediments: Implications for riverbank filtration.

PubMed

Zheng, Weixi; Lichwa, Joseph; D'Alessio, Matteo; Ray, Chittaranjan

2009-08-01

Riverbank filtration (RBF) refers to the process of capturing surface water passing through the river-sediment-aquifer system by using a collection technique such as a well or an infiltration gallery. RBF removes nearly all suspended and a large number of dissolved contaminants from the surface water. Therefore, it can function as an effective pretreatment process in drinking-water production. TNT (2,4,6-trinitrotoluene), RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) are three military explosive chemicals that are considered of concern to human health when present in source waters. This study is to evaluate the ability of the filtration media in RBF systems to remove these chemicals. The results from an anoxic batch test showed that all three chemicals will degrade while passing through streambed sediments. The pseudo first-order degradation-rate constants for TNT, RDX, and HMX were measured to be 0.33, 0.055, and 0.033d(-1), respectively. Under aerobic conditions only TNT showed significant degradation. Results from a model RBF system showed that the mobility of the three chemical contaminants in streambed sediments was in the order: HMX>RDX>TNT. The results suggest that RBF is capable of removing TNT and RDX but HMX levels may continue to be of concern-especially when collector wells use laterals running directly beneath the stream or riverbed.

Accelerated Testing of UH-60 Viscous Bearings for Degraded Grease Fault

NASA Technical Reports Server (NTRS)

Dykas, Brian; Hood, Adrian; Krantz, Timothy; Klemmer, Marko

2015-01-01

An accelerated aging investigation of critical aviation bearings lubricated with MIL-PRF- 81322 grease was conducted to derive an understanding of the mechanisms of grease degradation and loss of lubrication over time. The current study focuses on UH-60 Black Hawk viscous damper bearings supporting the tail rotor driveshaft, which were subjected to more than 5800 hours of testing in a heated environment to accelerate the deterioration of the grease. The mechanism of grease degradation is a reduction in the oil/thickener ratio rather than the expected chemical degradation of grease constituents. Over the course of testing, vibration and temperature monitoring of bearings was conducted and trends for failing bearings are presented.

Polymer scaffold degradation control via chemical control

DOEpatents

Hedberg-Dirk, Elizabeth L.; Dirk, Shawn; Cicotte, Kirsten

2016-01-05

A variety of polymers and copolymers suitable for use as biologically compatible constructs and, as a non-limiting specific example, in the formation of degradable tissue scaffolds as well methods for synthesizing these polymers and copolymers are described. The polymers and copolymers have degradation rates that are substantially faster than those of previously described polymers suitable for the same uses. Copolymers having a synthesis route which enables one to fine tune the degradation rate by selecting the specific stoichiometry of the monomers in the resulting copolymer are also described. The disclosure also provides a novel synthesis route for maleoyl chloride which yields monomers suitable for use in the copolymer synthesis methods described herein.

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

PubMed

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

2015-05-15

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

Synthesis and Characterization of Carboxymethylcellulose-Methacrylate Hydrogel Cell Scaffolds

PubMed Central

Reeves, Robert; Ribeiro, Andreia; Lombardo, Leonard; Boyer, Richard; Leach, Jennie B.

2012-01-01

Many carbohydrates pose advantages for tissue engineering applications due to their hydrophilicity, degradability, and availability of chemical groups for modification. For example, carboxymethylcellulose (CMC) is a water-soluble cellulose derivative that is degradable by cellulase. Though this enzyme is not synthesized by mammalian cells, cellulase and the fragments derived from CMC degradation are biocompatible. With this in mind, we created biocompatible, selectively degradable CMC-based hydrogels that are stable in routine culture, but degrade when exposed to exogenous cellulase. Solutions of CMC-methacrylate and polyethylene glycol dimethacrylate (PEG-DM) were co-crosslinked to form stable hydrogels; we found that greater CMC-methacrylate content resulted in increased gel swelling, protein diffusion and rates of degradation by cellulase, as well as decreased gel shear modulus. CMC-methacrylate/PEG-DM gels modified with the adhesive peptide RGD supported fibroblast adhesion and viability. We conclude that hydrogels based on CMC-methacrylate are suitable for bioengineering applications where selective degradability may be favorable, such as cell scaffolds or controlled release devices. PMID:22708058

Investigating the Photocatalytic Degradation of Oil Paint using ATR-IR and AFM-IR.

PubMed

Morsch, Suzanne; van Driel, Birgit A; van den Berg, Klaas Jan; Dik, Joris

2017-03-22

As linseed oil has a longstanding and continuing history of use as a binder in artistic paints, developing an understanding of its degradation mechanism is critical to conservation efforts. At present, little can be done to detect the early stages of oil paint deterioration due to the complex chemical composition of degrading paints. In this work, we use advanced infrared analysis techniques to investigate the UV-induced deterioration of model linseed oil paints in detail. Subdiffraction limit infrared analysis (AFM-IR) is applied to identify and map accelerated degradation in the presence of two different grades of titanium white pigment particles (rutile or anatase TiO 2 ). Differentiation between the degradation of these two formulations demonstrates the sensitivity of this approach. The identification of characteristic peaks and transient species residing at the paint surface allows infrared absorbance peaks related to degradation deeper in the film to be extricated from conventional ATR-FTIR spectra, potentially opening up a new approach to degradation monitoring.

Degradation and decolorization of monosodium glutamate wastewater with Coriolus versicolor.

PubMed

Jia, Cuiying; Kang, Ruijuan; Zhang, Yuhui; Zhang, Yong; Cong, Wei

2007-10-01

Degradation and decolorization of monosodium glutamate wastewater (MSGW) with Coriolus versicolor were firstly carried out. The effects of various operation parameters namely wastewater concentrations, pH, culture time and incidence of sterilization on maximum percentage of degradation and decolorization of wastewater were investigated. Studies of mycelium and enzyme for C. versicolor degradation and decolorization were estimated in this study. Ten percentage of wastewater concentration and pH = 5.0 were found to be the most suitable ones among the other experiments. The highest degradation and decolorization efficiency of wastewater was obtained at the fifth day of cultivation, which was displayed with more than 70% chemical oxygen demand removal, 83% total sugar removal and 55% color removal, respectively. Sterile operation had no remarkable effect on the degradation and decolorization efficiency for C. versicolor. Mycelium and the extra cellular fungal enzyme were both necessary for the degradation and decolorization of MSGW. C. versicolor possesses great potential and economic advantages in MSGW treatment.

Coupling model of aerobic waste degradation considering temperature, initial moisture content and air injection volume.

PubMed

Ma, Jun; Liu, Lei; Ge, Sai; Xue, Qiang; Li, Jiangshan; Wan, Yong; Hui, Xinminnan

2018-03-01

A quantitative description of aerobic waste degradation is important in evaluating landfill waste stability and economic management. This research aimed to develop a coupling model to predict the degree of aerobic waste degradation. On the basis of the first-order kinetic equation and the law of conservation of mass, we first developed the coupling model of aerobic waste degradation that considered temperature, initial moisture content and air injection volume to simulate and predict the chemical oxygen demand in the leachate. Three different laboratory experiments on aerobic waste degradation were simulated to test the model applicability. Parameter sensitivity analyses were conducted to evaluate the reliability of parameters. The coupling model can simulate aerobic waste degradation, and the obtained simulation agreed with the corresponding results of the experiment. Comparison of the experiment and simulation demonstrated that the coupling model is a new approach to predict aerobic waste degradation and can be considered as the basis for selecting the economic air injection volume and appropriate management in the future.

Physiology, biochemistry and possible applications of microbial caffeine degradation.

PubMed

Gummadi, Sathyanarayana N; Bhavya, B; Ashok, Nandhini

2012-01-01

Caffeine, a purine alkaloid is a constituent of widely consumed beverages. The scientific evidence which has proved the harm of this alkaloid has paved the way for innumerable research in the area of caffeine degradation. In addition to this, the fact that the by-products of the coffee and tea industry pollute the environment has called for the need of decaffeinating coffee and tea industry's by-products. Though physical and chemical methods for decaffeination are available, the lack of specificity for removal of caffeine in these techniques and their non-eco-friendly nature has opened the area of microbial and enzymatic degradation of caffeine. Another important application of microbial caffeine degradation apart from its advantages like specificity, eco-friendliness and cost-effectiveness is the fact that this process will enable the production of industrially and medically useful components of the caffeine degradation pathway like theobromine and theophylline. This is a comprehensive review which mainly focuses on caffeine degradation, large-scale degradation of the same and its applications in the industrial world.

SERDP ER-1376 Enhancement of In Situ Bioremediation of Energetic Compounds by Coupled Abiotic/Biotic Processes:Final Report for 2004 - 2006

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

Szecsody, James E.; Comfort, Steve; Fredrickson, Herbert L.

2007-08-07

This project was initiated by SERDP to quantify processes and determine the effectiveness of abiotic/biotic mineralization of energetics (RDX, HMX, TNT) in aquifer sediments by combinations of biostimulation (carbon, trace nutrient additions) and chemical reduction of sediment to create a reducing environment. Initially it was hypothesized that a balance of chemical reduction of sediment and biostimulation would increase the RDX, HMX, and TNT mineralization rate significantly (by a combination of abiotic and biotic processes) so that this abiotic/biotic treatment may be a more efficient for remediation than biotic treatment alone in some cases. Because both abiotic and biotic processes aremore » involved in energetic mineralization in sediments, it was further hypothesized that consideration for both abiotic reduction and microbial growth was need to optimize the sediment system for the most rapid mineralization rate. Results show that there are separate optimal abiotic/biostimulation aquifer sediment treatments for RDX/HMX and for TNT. Optimal sediment treatment for RDX and HMX (which have chemical similarities and similar degradation pathways) is mainly chemical reduction of sediment, which increased the RDX/HMX mineralization rate 100 to150 times (relative to untreated sediment), with additional carbon or trace nutrient addition, which increased the RDX/HMX mineralization rate an additional 3 to 4 times. In contrast, the optimal aquifer sediment treatment for TNT involves mainly biostimulation (glucose addition), which stimulates a TNT/glucose cometabolic degradation pathway (6.8 times more rapid than untreated sediment), degrading TNT to amino-intermediates that irreversibly sorb (i.e., end product is not CO2). The TNT mass migration risk is minimized by these transformation reactions, as the triaminotoluene and 2,4- and 2,6-diaminonitrotoluene products that irreversibly sorb are no longer mobile in the subsurface environment. These transformation rates are increased 13 times further by chemical reduction of sediment. Dithionite reduction alone is not an effective treatment for TNT (intermediates that irreversibly sorb are not produced), even though the TNT degradation rate (to 2- or 4-aminodinitrotoluene) increases.« less

Feasibility of silica-hybridized collagen hydrogels as three-dimensional cell matrices for hard tissue engineering.

PubMed

Yu, Hye-Sun; Lee, Eun-Jung; Seo, Seog-Jin; Knowles, Jonathan C; Kim, Hae-Won

2015-09-01

Exploiting hydrogels for the cultivation of stem cells, aiming to provide them with physico-chemical cues suitable for osteogenesis, is a critical demand for bone engineering. Here, we developed hybrid compositions of collagen and silica into hydrogels via a simple sol-gel process. The physico-chemical and mechanical properties, degradation behavior, and bone-bioactivity were characterized in-depth; furthermore, the in vitro mesenchymal stem cell growth and osteogenic differentiation behaviors within the 3D hybrid gel matrices were communicated for the first time. The hydrolyzed and condensed silica phase enabled chemical links with the collagen fibrils to form networked hybrid gels. The hybrid gels showed improved chemical stability and greater resistance to enzymatic degradation. The in vitro apatite-forming ability was enhanced by the hybrid composition. The viscoelastic mechanical properties of the hybrid gels were significantly improved in terms of the deformation resistance to an applied load and the modulus values under a dynamic oscillation. Mesenchymal stem cells adhered well to the hybrid networks and proliferated actively with substantial cytoskeletal extensions within the gel matrices. Of note, the hybrid gels substantially reduced the cell-mediated gel contraction behaviors, possibly due to the stiffer networks and higher resistance to cell-mediated degradation. Furthermore, the osteogenic differentiation of cells, including the expression of bone-associated genes and protein, was significantly upregulated within the hybrid gel matrices. Together with the physico-chemical and mechanical properties, the cellular behaviors observed within 3D gel matrices, being different from the previous approaches reported on 2D substrates, provide new information on the feasibility and usefulness of the silica-collagen system for stem cell culture and tissue engineering of hard tissues. © The Author(s) 2015.

[Degradation characteristics of swamps in Zoige Plateau induced by drainage based on quantitative classification of vegetation].

PubMed

Li, Ke; Yang, Yong-Xing; Yang, Yang; Han, Da-Yong

2012-07-01

Based on the field survey of swamp ecological characteristics and environmental quality and the ecological investigation of drained swamp transects in Zoige Plateau of Tibet in 2009, twenty typical swamp plots in the Plateau were classified into three types by TWINSPAN, i. e., primary swamp, long-term drained degraded swamp, and short-term drained degraded swamp, and each type of the degraded swamps was divided into three degradation grades, i. e., light degradation, moderate degradation, and severe degradation, with the degradation characteristics of vegetation and soil along the swamp degraded gradient studied. The swamp degradation in the Plateau was mainly driven by drainage pattern, drainage intensity, and soil moisture gradient, and the vegetation degradation was more obvious than the soil degradation. In the vegetation degradation, the structural change of hydro-type functional assemblage was most obvious, e. g., the importance value of helophytes under the stress of long-term drainage and short-term drainage decreased from 0.920 to 0.183 and 0.053, while that of mesophytes increased from 0.029 to 0.613 and 0.686, respectively. The soil response to the swamp degradation was in hysteresis, i. e., the soil physical and chemical properties presented definite variations but the differences were not significant among the swamps with different grades of degradation. The results of CCA indicated that soil moisture and nitrogen and potassium contents were the most important factors affecting the plant species distribution in drained degraded swamps in Zoige Plateau.

Determination of minimum enzymatic decolorization time of reactive dye solution by spectroscopic & mathematical approach.

PubMed

Celebi, Mithat; Ozdemir, Zafer Omer; Eroglu, Emre; Altikatoglu, Melda; Guney, Ibrahim

2015-02-01

Synthetic dyes are very important for textile dyeing, paper printing, color photography and petroleum products. Traditional methods of dye removal include biodegradation, precipitation, adsorption, chemical degradation, photo degradation, and chemical coagulation. Dye decolorization with enzymatic reaction is an important issue for several research field (chemistry, environment) In this study, minimum decolorization time of Remazol Brilliant Blue R dye with Horseradish peroxidase enzyme was calculated using with mathematical equation depending on experimental data. Dye decolorization was determined by monitoring the absorbance decrease at the specific maximum wavelength for dye. All experiments were carried out with different initial dye concentrations of Remazol Brilliant Blue R at 25 degrees C constant temperature for 30 minutes. The development of the least squares estimators for a nonlinear model brings about complications not encountered in the case of the linear model. Decolorization times for completely removal of dye were calculated according to equation. It was shown that mathematical equation was conformed exponential curve for dye degradation.

Retardation of biodegradation of linear alkyl benzene sulphonate by a sublethal concentration of mercuric chloride

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

Misra, V.; Pandey, S.D.; Viswanathan, P.N.

1991-10-01

Environmental xenobiotics are usually classified into persistent and biodegradable ones. However, this may not be universally true, since biochemical capacity of ecosystems species may vary with species diversity and versatility. This may differ in different locations decided by geoclimatic factors. Prolonged exposure of organisms causing primary degradation to the toxic xenobiotics may lead to metabolic adaptation to survive the chemical stress. Also under multiple toxicant stress, the normal biodegrading capacity may be impaired by the effect of one toxicant on the organisms per se or on the enzymes causing degradation. If such inhibition of biodegradation occurs in ecosystems, even normallymore » biodegradable chemicals may tend to accumulate. To test this view, model experiments were conducted with LAS (Linear alkyl benzene sulphonate) a biodegradable surfactant and mercuric chloride. Since the purpose of the study was to test the degradation under natural conditions, no attempt was made to identify the micro-organisms involved.« less

Effect of thermo-tolerant actinomycetes inoculation on cellulose degradation and the formation of humic substances during composting.

PubMed

Zhao, Yi; Zhao, Yue; Zhang, Zhechao; Wei, Yuquan; Wang, Huan; Lu, Qian; Li, Yanjie; Wei, Zimin

2017-10-01

The inoculum containing four cellulolytic thermophilic actinomycetes was screened from compost samples, and was inoculated into co-composting during different inoculation phases. The effect of different inoculation phases on cellulose degradation, humic substances formation and the relationship between inoculation and physical-chemical parameters was determined. The results revealed that inoculation at different phases of composting improved cellulase activities, accelerated the degradation of cellulose, increased the content of humic substances and influenced the structure of actinomycetic community, but there were significant differences between different inoculation phases. Redundancy analysis showed that the different inoculation phases had different impacts on the relationship between exogenous actinobacteria and physical-chemical parameters. Therefore, based on the promoting effort of inoculation in thermophilic phase of composting for the formation of humic substances, we suggested an optimized inoculation strategy to increase the content of humic substances, alleviate CO 2 emission during composting. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics of alkali-based photocathode degradation

DOE PAGES

Pavlenko, Vitaly; Liu, Fangze; Hoffbauer, Mark A.; ...

2016-11-02

Here, we report on a kinetic model that describes the degradation of the quantum efficiency (QE) of Cs 3Sb and negative electron affinity (NEA) GaAs photocathodes under UHV conditions. Additionally, the generally accepted irreversible chemical change of a photocathode’s surface due to reactions with residual gases, such as O 2, CO 2, and H 2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. Moreover, this intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes –surface-activated and “bulk,” indicating that in both systems the QE degradationmore » results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface) comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.« less

Chemically modified amino porphyrin/TiO2 for the degradation of Acid Black 1 under day light illumination

NASA Astrophysics Data System (ADS)

Krishnakumar, Balu; Balakrishna, Avula; Arranja, Cláudia T.; Dias, Carlos M. F.; Sobral, Abilio J. F. N.

2017-04-01

In this paper, for the first time, chemically modified 5,10,15,20-meso-tetra-(para-amino)-phenyl-porphyrin/TiO2 (TPAPP/TiO2) was prepared and used for the degradation of an azo dye Acid Black 1 (AB 1) under direct sunlight. Initially, TiO2 was prepared by sol-gel method. Before making a TPAPP/TiO2 composite, the surface modification of TiO2 was carried out with glycidoxypropyltrimethoxy silane (GPTMS) which acts as a coupling agent. This is an epoxy terminated silane and could easily bond to the amino group of TPAPP through epoxy cleavage. The formation of TPAPP/TiO2 was confirmed by different characterization techniques such as FT-IR, XRD, SEM and DRS. The photocatalytic activity of TiO2 was highly influenced by TPAPP. A mechanism was proposed for AB 1 degradation by TPAPP/TiO2 under sun light.

Chemically modified amino porphyrin/TiO2 for the degradation of Acid Black 1 under day light illumination.

PubMed

Krishnakumar, Balu; Balakrishna, Avula; Arranja, Cláudia T; Dias, Carlos M F; Sobral, Abilio J F N

2017-04-05

In this paper, for the first time, chemically modified 5,10,15,20-meso-tetra-(para-amino)-phenyl-porphyrin/TiO 2 (TPAPP/TiO 2 ) was prepared and used for the degradation of an azo dye Acid Black 1 (AB 1) under direct sunlight. Initially, TiO 2 was prepared by sol-gel method. Before making a TPAPP/TiO 2 composite, the surface modification of TiO 2 was carried out with glycidoxypropyltrimethoxy silane (GPTMS) which acts as a coupling agent. This is an epoxy terminated silane and could easily bond to the amino group of TPAPP through epoxy cleavage. The formation of TPAPP/TiO 2 was confirmed by different characterization techniques such as FT-IR, XRD, SEM and DRS. The photocatalytic activity of TiO 2 was highly influenced by TPAPP. A mechanism was proposed for AB 1 degradation by TPAPP/TiO 2 under sun light. Copyright © 2017 Elsevier B.V. All rights reserved.

Coformer selection based on degradation pathway of drugs: a case study of adefovir dipivoxil-saccharin and adefovir dipivoxil-nicotinamide cocrystals.

PubMed

Gao, Yuan; Gao, Jing; Liu, Ziling; Kan, Hongliang; Zu, Hui; Sun, Wanjin; Zhang, Jianjun; Qian, Shuai

2012-11-15

Adefovir dipivoxil (AD) is a bis(pivaloyloxymethyl) prodrug of adefovir with chemical stability problem. It undergoes two degradation pathways including hydrolysis and dimerization during storage. Pharmaceutical cocrystallization exhibits a promising approach to enhance aqueous solubility as well as physicochemical stability. In this study we attempted to prepare and investigate the physiochemical properties of AD cocrystals, which were formed with two coformers having different acidity and alkalinity (weakly acidic saccharin (SAC) and weakly basic nicotinamide (NCT)). The presence of different coformer molecules along with AD resulted in altered physicochemical properties. AD-SAC cocrystal showed great improvement in solubility and chemical stability, while AD-NCT did not. Several potential factors giving rise to different solid-state properties were summarized. Different coformers resulted in different cocrystal formation, packing style and hydrogen bond formation. This study could provide the coformer selection strategy based on degradation pathways for some unstable drugs in pharmaceutical cocrystal design. Copyright © 2012 Elsevier B.V. All rights reserved.

Toxicological Profile of Chlorophenols and Their Derivatives in the Environment: The Public Health Perspective

PubMed Central

Igbinosa, Etinosa O.; Odjadjare, Emmanuel E.; Chigor, Vincent N.; Igbinosa, Isoken H.; Emoghene, Alexander O.; Ekhaise, Fredrick O.; Igiehon, Nicholas O.; Idemudia, Omoruyi G.

2013-01-01

Chlorophenol compounds and their derivatives are ubiquitous contaminants in the environment. These compounds are used as intermediates in manufacturing agricultural chemicals, pharmaceuticals, biocides, and dyes. Chlorophenols gets into the environment from a variety of sources such as industrial waste, pesticides, and insecticides, or by degradation of complex chlorinated hydrocarbons. Thermal and chemical degradation of chlorophenols leads to the formation of harmful substances which constitute public health problems. These compounds may cause histopathological alterations, genotoxicity, mutagenicity, and carcinogenicity amongst other abnormalities in humans and animals. Furthermore, the recalcitrant nature of chlorophenolic compounds to degradation constitutes an environmental nuisance, and a good understanding of the fate and transport of these compounds and their derivatives is needed for a clearer view of the associated risks and mechanisms of pathogenicity to humans and animals. This review looks at chlorophenols and their derivatives, explores current research on their effects on public health, and proffers measures for mitigation. PMID:23690744

Metabolism and biotransformation of azo dye by bacterial consortium studied in a bioreaction calorimeter.

PubMed

Shanmugam, Bhuvanesh Kumar; Mahadevan, Surianarayanan

2015-11-01

Effluents from leather and textile industries are difficult for treatment owing to its recalcitrant nature. Since the volume of effluent generated are high, a robust and active microbial consortia is required for effective treatment. The focus in the present study is the calorimetric traceability of the metabolic behaviors of mixed microbial consortia, while it grows and degrades recalcitrant substance such as an azo dye acid blue 113. The consortium exhibited a syntrophic division of substrate and was effective in degrading dye up to 0.8g/l. Notably, it was able to degrade 93.7% of the azo dye in 12-16h whereas its monocultures required 48-72h to reach 82.1%. The products of biodegradation were analyzed and the chemical pathway substantiated using chemical thermodynamic and energy release patterns. MTT assay confirmed that emanates are eco-friendly. Heat profile pattern and bioenergetics provide fundamental data for a feasible application in commercial level. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biodegradation of sulfosulphuron in agricultural soil by Trichoderma sp.

PubMed

Yadav, U; Choudhury, P P

2014-11-01

Sulfosulphuron-degrading fungus was isolated by enrichment technique from the sulfosulphuron-contaminated soil of wheat rhizosphere. To assess the biodegradation potential of isolated Trichoderma sp., minimal potato dextrose agar broth with different levels of sulfosulphuron (up to 2 g l(-1) ) was evaluated in the growth and biotransformation experiments. ESI LC-MS/MS analysis revealed the presence of degradation products 2-amino-4,6-dimethoxypyrimidine (I) and 2-ethylsulfonyl imidazo{1,2-a} pyridine-3-sulfonamide-2-ethylsulfonyl imidazo{1,2-a} pyridine-3-sulfonamide (II) indicating the cleavage of the urea bridge and the presence of the by-product N-(4,6-dimethoxypyrimidin-2-yl)urea (III) indicating the degradation of sulfonylamide linkage. Two other metabolites, N-(4,6-dimethoxypyrimidin-2-yl)-N'-hydroxyurea (IV) and N, N'-bis(4,6-dimethoxypyrimidin-2-yl)urea (V), were also identified. From the previous reports, it was found that the degradation of sulfonyl urea herbicides took place through the chemical degradation of the sulfonylurea bridge followed by microbial degradation. During this investigation, Trichoderma sp. grew well with and degraded sulfosulphuron via both the decarboxylation on the sulphonyl urea bridge and the hydrolytic cleavage of the sulfonylamide linkage as demonstrated by the formation of metabolites. Trichoderma is nonphytopathogenic in nature, and some species of it restrict the growth of soil-dwelling phytopathogens. Therefore, it is a promising candidate for the decontamination of soil from sulfosulphuron residues. The degradation of sulfosulphuron by any individual fungus is being reported for the first time. Trichoderma sp. isolated from wheat-rhizospheric soil could survive in minimal broth rich in sulfosulphuron. Previous reports have described the complete degradation of any sulfonyl urea herbicides by micro-organisms only after the pH-dependent chemical hydrolysis of the sulfonyl urea bridge of the herbicide. This study demonstrates the novel result that the Trichoderma sp. utilized the sulfosulphuron as a sole carbon source and degraded it by cleaving sulfonyl urea bridge and sulfonylamide linkage. Thus, the application of Trichoderma sp., which is nonphytopathogenic, has the potential to decontaminate agricultural soil from sulfosulphuron load. © 2014 The Society for Applied Microbiology.

Chemical and spectroscopic analyses of organic matter transformation in warming tundra soils

NASA Astrophysics Data System (ADS)

Herndon, E.; Roy Chowdhury, T.; Mann, B. F.; Graham, D. E.; Bargar, J.; Gu, B.; Liang, L.

2013-12-01

Many tundra soils are currently major carbon sinks; however, an increase in temperature may shift these systems to C sources and create a positive feedback for warming. In order to predict future C release from tundra soils, it is necessary to quantify rates of SOM degradation and to identify the reactants and products of microbial decomposition reactions. In this study, multiple spectroscopic techniques are used to investigate SOM during laboratory incubations of tundra soils. We aim to characterize the chemical transformation of organic matter during decomposition as a function of temperature and geochemistry. Frozen soil cores were obtained from the Barrow Environmental Observatory (BEO) in northern Alaska as part of the Next Generation Ecosystem Experiment Arctic project. To investigate the influence of temperature on organic matter degradation and compositional changes, soil horizons from each core were homogenized and soil material was incubated at -2°C, +4°C, or +8°C. Samples were sacrificed periodically over 100 days, and chemical and physical extractions were used to separate SOM into operationally-defined pools, including light (density < 1.6 g cm-2) and mineral-bound, and water-, acid-, base-, and non-soluble fractions. A suite of wet-chemical and spectroscopic analyses was used to measure CO2 and CH4 formation and soil C compositional changes, including techniques such as Fourier transform infrared spectroscopy, high performance liquid chromatography (HPLC), high resolution mass spectrometry, and X-ray absorption spectroscopy. Detailed chemical and spectroscopic analyses reveal significant differences amongst extracts and with depth in the soil. In general, more organic C was extracted in the base than in the acid and water fractions, and mineral-bound organic C increased with depth. The water-soluble C fraction showed the lowest molar absorptivity of the three extracts and consisted of mostly lower-molecular weight organics. Acid-soluble C increased with increasing mineral content of the soil, likely due to the presence of labile organics bound to Fe-oxide minerals. In addition, 13-80% of the total C remained in soil following sequential chemical extractions, suggesting resistance to degradation and strong association with minerals. Soil incubations showed temperature-dependent production of CO2 and CH4, indicating microbial C degradation. The masses of CO2 and CH4 released represent only a small fraction of the total soil organic C, and little change in was observed in bulk SOM. However, the water-soluble C exhibited significant vulnerability to degradation, as revealed by HPLC and spectroscopic analyses, and these results suggest potential pathways for chemical transformation of soil C during decomposition. The results of this study will contribute to a computational modeling framework for understanding sources and rates of C fluxes from soils to the atmosphere and will help elucidate potential changes to Arctic tundra systems subject to warming.

BLT-EC (Breach, Leach and Transport-Equilibrium Chemistry) data input guide. A computer model for simulating release and coupled geochemical transport of contaminants from a subsurface disposal facility

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

MacKinnon, R.J.; Sullivan, T.M.; Kinsey, R.R.

1997-05-01

The BLT-EC computer code has been developed, implemented, and tested. BLT-EC is a two-dimensional finite element computer code capable of simulating the time-dependent release and reactive transport of aqueous phase species in a subsurface soil system. BLT-EC contains models to simulate the processes (container degradation, waste-form performance, transport, chemical reactions, and radioactive production and decay) most relevant to estimating the release and transport of contaminants from a subsurface disposal system. Water flow is provided through tabular input or auxiliary files. Container degradation considers localized failure due to pitting corrosion and general failure due to uniform surface degradation processes. Waste-form performancemore » considers release to be limited by one of four mechanisms: rinse with partitioning, diffusion, uniform surface degradation, and solubility. Transport considers the processes of advection, dispersion, diffusion, chemical reaction, radioactive production and decay, and sources (waste form releases). Chemical reactions accounted for include complexation, sorption, dissolution-precipitation, oxidation-reduction, and ion exchange. Radioactive production and decay in the waste form is simulated. To improve the usefulness of BLT-EC, a pre-processor, ECIN, which assists in the creation of chemistry input files, and a post-processor, BLTPLOT, which provides a visual display of the data have been developed. BLT-EC also includes an extensive database of thermodynamic data that is also accessible to ECIN. This document reviews the models implemented in BLT-EC and serves as a guide to creating input files and applying BLT-EC.« less

Phenols as chemical fossils in coals. [Book chapter

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

Bimer, J.; Given, P.H.; Raj, S.

It is generally considered that vitrinite, the principal maceral in most coals, represents coalified, partly decayed wood. Hence lignin should be one of the important precursors to the vitrinites in coals. Accordingly, it would be interesting to know whether any chemical fossils related to lignin could be found in coals. The purpose of this paper is to report what we believe to be a successful search for such fossils. The experimental approach exploited a degradation reaction developed in a study of soil humic acids by Burges et al. This reaction involves a reductive degradation with sodium amalgam and hot water.more » Thin layer chromatography of the ether soluble part of the product (yield, about 20%) showed the presence of a number of phenols and phenolic acids, most of whose structures bore obvious relationships to known microbial and chemical degradation products of lignin but some to the A ring of flavonoids. Humic acids can be extracted from peats and lignites but not from bituminous coals. However, oxidation of bituminous coals with aqueous performic acid generates in high yield (80 to 110% by weight) materials that closely resemble humic acids. The Burges reductive degradation was applied to humic acids extracted from some peats and lignites, and produced by oxidation of a number of bituminous coals. A number of identifications of products were made originally by gas chromatography with co-injection of standards. In this preliminary publication the experimental procedures are described and a sufficient selection of the data are given to show what was found by co-injection and later confirmed by mass spectrometry.« less

Lignin composition is more important than content for maize stem cell wall degradation.

PubMed

He, Yuan; Mouthier, Thibaut Mb; Kabel, Mirjam A; Dijkstra, Jan; Hendriks, Wouter H; Struik, Paul C; Cone, John W

2018-01-01

The relationship between the chemical and molecular properties - in particular the (acid detergent) lignin (ADL) content and composition expressed as the ratio between syringyl and guaiacyl compounds (S:G ratio) - of maize stems and in vitro gas production was studied in order to determine which is more important in the degradability of maize stem cell walls in the rumen of ruminants. Different internodes from two contrasting maize cultivars (Ambrosini and Aastar) were harvested during the growing season. The ADL content decreased with greater internode number within the stem, whereas the ADL content fluctuated during the season for both cultivars. The S:G ratio was lower in younger tissue (greater internode number or earlier harvest date) in both cultivars. For the gas produced between 3 and 20 h, representing the fermentation of cell walls in rumen fluid, a stronger correlation (R 2 = 0.80) was found with the S:G ratio than with the ADL content (R 2 = 0.68). The relationship between ADL content or S:G ratio and 72-h gas production, representing total organic matter degradation, was weaker than that with gas produced between 3 and 20 h. The S:G ratio plays a more dominant role than ADL content in maize stem cell wall degradation. © 2017 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. © 2017 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Extending shikimate pathway for the production of muconic acid and its precursor salicylic acid in Escherichia coli.

PubMed

Lin, Yuheng; Sun, Xinxiao; Yuan, Qipeng; Yan, Yajun

2014-05-01

cis,cis-Muconic acid (MA) and salicylic acid (SA) are naturally-occurring organic acids having great commercial value. MA is a potential platform chemical for the manufacture of several widely-used consumer plastics; while SA is mainly used for producing pharmaceuticals (for example, aspirin and lamivudine) and skincare and haircare products. At present, MA and SA are commercially produced by organic chemical synthesis using petro-derived aromatic chemicals, such as benzene, as starting materials, which is not environmentally friendly. Here, we report a novel approach for efficient microbial production of MA via extending shikimate pathway by introducing the hybrid of an SA biosynthetic pathway with its partial degradation pathway. First, we engineered a well-developed phenylalanine producing Escherichia coli strain into an SA overproducer by introducing isochorismate synthase and isochorismate pyruvate lyase. The engineered strain is able to produce 1.2g/L of SA from simple carbon sources, which is the highest titer reported so far. Further, the partial SA degradation pathway involving salicylate 1-monoxygenase and catechol 1,2-dioxygenase is established to achieve the conversion of SA to MA. Finally, a de novo MA biosynthetic pathway is assembled by integrating the established SA biosynthesis and degradation modules. Modular optimization enables the production of up to 1.5g/L MA within 48h in shake flasks. This study not only establishes an efficient microbial platform for the production of SA and MA, but also demonstrates a generalizable pathway design strategy for the de novo biosynthesis of valuable degradation metabolites. Copyright © 2014. Published by Elsevier Inc.

Identification of chemical warfare agents using a portable microchip-based detection device

NASA Astrophysics Data System (ADS)

Petkovic-Duran, K.; Swallow, A.; Sexton, B. A.; Glenn, F.; Zhu, Y.

2011-12-01

Analysis of chemical warfare agents (CWAs) and their degradation products is an important verification component in support of the Chemical Weapons Convention and urgently demanding rapid and reliable analytical methods. A portable microchip electrophoresis (ME) device with contactless conductivity (CCD) detection was developed for the in situ identification of CWA and their degradation products. A 10mM MES/His, 0.4mM CTAB - based separation electrolyte accomplished the analysis of Sarin (GB), Tabun( GA) and Soman (GD) in less than 1 min, which is the fastest screening of nerve agents achieved with portable ME and CCD based detection methods to date. Reproducibility of detection was successfully demonstrated on simultaneous detection of GB (200ppm) and GA (278ppm). Reasonable agreement for the four consecutive runs was achieved with the mean peak time for Sarin of 29.15s, and the standard error of 0.58s or 2%. GD and GA were simultaneously detected with their degradation products methylphosphonic acid (MPA), pinacolyl methylphosphonic acid (PMPA) and O-Ethyl Phosphorocyanidate (GAHP and GAHP1) respectively. The detection limit for Sarin was around 35ppb. To the best of our knowledge this is the best result achieved in microchip electrophoresis and contactless conductivity based detection to date.

Economical Treatment of Dredged Material to Facilitate Beneficial Use

DTIC Science & Technology

2014-08-01

Mifflin DM stabilization results . ............................................................................................. 54 ERDC/EL TR-14-11 vii...deficits resulting from chemical reactions taking place in reduced sediments during disposal. Direct injection of chemical oxidants into the...usually the meta- and para-chlorines on the biphenyl structure. Aerobic conditions usually degrade the resulting lightly chlorinated PCBs with the

Biodegradation pathway of an anionic surfactant (Igepon TC-42) during recycling waste water through plant hydroponics for advanced life support during long-duration space missions

NASA Astrophysics Data System (ADS)

Levine, L. H.; Kagie, H. R.; Garland, J. L.

The degradation of an anionic surfactant (Igepon TC-42) was investigated as part of an integrated study of direct recycling of human hygiene water through hydroponic plant growth systems. Several chemical approaches were developed to characterize the degradation of Igepon and to measure the accumulation of intermediates such as fatty acids and methyl taurine. Igepon was rapidly degraded as indicated by the reduction of methylene blue active substances (MBAS) and component fatty acids. The Igepon degradation rate continued to increase over a period of several weeks following repeated daily exposure to 18 μg/l Igepon. The accumulation of free fatty acids and methyl taurine was also observed during decomposition of Igepon. The concentration of methyl taurine was below detection limit (0.2 nmol/ml) during the slow phase of Igepon degradation, and increased to 1-2 nmol/ml during the phase of rapid degradation. These findings support a degradation pathway involving initial hydrolysis of amide to release fatty acids and methyl taurine, and subsequent degradation of these intermediates.

Determination of an Effective Perfluorinated Compounds (PFCs) Oxidation Method

NASA Astrophysics Data System (ADS)

Siriwardena, D. P.; Crimi, M.; Holsen, T.; Bellona, C.

2014-12-01

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a stable synthetic class of chemicals ubiquitously spread in environmental media (i.e. air, soil, biota, surface water and groundwater). The substances' strong polar carbon-fluorine bonds and their high thermal and chemical stability make them resistant to biological, chemical, and physical degradation. The purpose of this research is to identify the most effective oxidation method to treat perfluorinated compounds (PFCs) and their by-products that is suitable for in situ application. The laboratory oxidation study focuses on the more commonly detected and studied long-chain (C-8) PFAS; perfluorooctanoic acids (PFOA) and perfluorooctane sulfonic acid (PFOS). Existing research evaluating oxidizing treatment effectiveness on perfluoroalkyl sulfoinoic acids (PFSAs) is limited. A review of the literature and results from preliminary studies indicate that activated persulfate and catalyzed hydrogen peroxide propagation (CHP) reactions appear to be promising oxidants for PFOA. It has been demonstrated that the reactivity of superoxide in water increases in the presence of hydrogen peroxide (H2O2) and solids. Superoxide generated in CHP reactions degrades PFOA seemingly similar to superoxide-mediated destruction of the perhalogenated compounds.The goal of this study is to look at conditions that promote generation of superoxide and look at PFASs treatment effectiveness and byproduct generation. CHP reactions are conducted with varying amount of H2O2 and Fe(III) to determine the optimum conditions for PFC degradation. Results will be compared to those of another experiment using manganese dioxide as a CHP catalyst with varied H2O2 concentration to generate superoxide to degrade PFASs. Activated persulfate conditions to be compared include alkaline pH activation, heat activation, and dual oxidation (combined H2O2 and persulfate ). This presentation will focus on a comparison of oxidation effectiveness under the varied reaction conditions as well as on the oxidation intermediates and byproducts generated toward improved understanding of the potential for and limitations of in situ chemical oxidation (ISCO) for treatment of PFCs.

78 FR 63938 - Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or on Various...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-25

...]-(2-fluorophenyl)-[alpha]- (4-fluorophenyl)-1 H-1,2,4-triazole-1-ethanol], including its metabolites...-fluorophenyl)-1 H-1,2,4-triazole-1-ethanol], including its metabolites and degradates, in or on African tree... saflufenacil, including its metabolites and degradates, in or on grass, forage at 15 ppm; grass, hay at 20 ppm...

Occurrence, degradation, and effect of polymer-based materials in the environment.

PubMed

Lambert, Scott; Sinclair, Chris; Boxall, Alistair

2014-01-01

There is now a plethora of polymer-based materials (PBMs) on the market, because of the increasing demand for cheaper consumable goods, and light-weight industrial materials. Each PBM constitutes a mixture of their representative polymer/sand their various chemical additives. The major polymer types are polyethylene, polypropylene,and polyvinyl chloride, with natural rubber and biodegradable polymers becoming increasingly more important. The most important additives are those that are biologically active, because to be effective such chemicals often have properties that make them resistant to photo-degradation and biodegradation. During their lifecycle,PBMs can be released into the environment form a variety of sources. The principal introduction routes being general littering, dumping of unwanted waste materials,migration from landfills and emission during refuse collection. Once in the environment,PBMs are primarily broken down by photo-degradation processes, but due to the complex chemical makeup of PBMs, receiving environments are potentially exposed to a mixture of macro-, meso-, and micro-size polymer fragments, leached additives, and subsequent degradation products. In environments where sunlight is absent (i.e., soils and the deep sea) degradation for most PBMs is minimal .The majority of literature to date that has addressed the environmental contamination or disposition of PBMs has focused on the marine environment. This is because the oceans are identified as the major sink for macro PBMs, where they are known to present a hazard to wildlife via entanglement and ingestion. The published literature has established the occurrence of microplastics in marine environment and beach sediments, but is inadequate as regards contamination of soils and freshwater sediments. The uptake of microplastics for a limited range of aquatic organisms has also been established, but there is a lack of information regarding soil organisms, and the long-term effects of microplastic uptake are also less well understood.There is currently a need to establish appropriate degradation test strategies consistent with realistic environmental conditions, because the complexity of environmental systems is lost when only one process (e.g., hydrolysis) is assessed in isolation. Enhanced methodologies are also needed to evaluate the impact of PBMs to soil and freshwater environments.

Spectroscopic investigation of oxygen- and water-induced electron trapping and charge transport instabilities in n-type polymer semiconductors.

PubMed

Di Pietro, Riccardo; Fazzi, Daniele; Kehoe, Tom B; Sirringhaus, Henning

2012-09-12

We present an optical spectroscopy study on the role of oxygen and water in electron trapping and storage/bias-stress degradation of n-type polymer field-effect transistors based on one of the most widely studied electron transporting conjugated polymers, poly{[N,N9-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bisthiophene)} (P(NDI2OD-T2)). We combine results obtained from charge accumulation spectroscopy, which allow optical quantification of the concentration of mobile and trapped charges in the polymer film, with electrical characterization of P(NDI2OD-T2) organic field-effect transistors to study the mechanism for storage and bias-stress degradation upon exposure to dry air/oxygen and humid nitrogen/water environments, thus separating the effect of the two molecules and determining the nature of their interaction with the polymer. We find that the stability upon oxygen exposure is limited by an interaction between the neutral polymer and molecular oxygen leading to a reduction in electron mobility in the bulk of the semiconductor. We use density functional theory quantum chemical calculations to ascribe the drop in mobility to the formation of a shallow, localized, oxygen-induced trap level, 0.34 eV below the delocalized lowest unoccupied molecular orbital of P(NDI2OD-T2). In contrast, the stability of the polymer anion against water is limited by two competing reactions, one involving the electrochemical oxidation of the polymer anion by water without degradation of the polymer and the other involving a radical anion-catalyzed chemical reaction of the polymer with water, in which the electron can be recycled and lead to further degradation reactions, such that a significant portion of the film is degraded after prolonged bias stressing. Using Raman spectroscopy, we have been able to ascribe this to a chemical interaction of water with the naphthalene diimide unit of the polymer. The degradation mechanisms identified here should be considered to explain electron trapping in other rylene diimides and possibly in other classes of conjugated polymers as well.

Local impact of humidification on degradation in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Sanchez, Daniel G.; Ruiu, Tiziana; Biswas, Indro; Schulze, Mathias; Helmly, Stefan; Friedrich, K. Andreas

2017-06-01

The water level in a polymer electrolyte membrane fuel cell (PEMFC) affects the durability as is seen from the degradation processes during operation a PEMFC with fully- and nonhumidified gas streams as analyzed using an in-situ segmented cell for local current density measurements during a 300 h test operating under constant conditions and using ex situ SEM/EDX and XPS post-test analysis of specific regions. The impact of the RH on spatial distribution of the degradation process results from different water distribution giving different chemical environments. Under nonhumidified gas streams, the cathode inlet region exhibits increased degradation, whereas with fully humidified gases the bottom of the cell had the higher performance losses. The degradation and the degree of reversibility produced by Pt dissolution, PTFE defluorination, and contaminants such as silicon (Si) and nickel (Ni) were locally evaluated.

Chemical degradation of proteins in the solid state with a focus on photochemical reactions.

PubMed

Mozziconacci, Olivier; Schöneich, Christian

2015-10-01

Protein pharmaceuticals comprise an increasing fraction of marketed products but the limited solution stability of proteins requires considerable research effort to prepare stable formulations. An alternative is solid formulation, as proteins in the solid state are thermodynamically less susceptible to degradation. Nevertheless, within the time of storage a large panel of kinetically controlled degradation reactions can occur such as, e.g., hydrolysis reactions, the formation of diketopiperazine, condensation and aggregation reactions. These mechanisms of degradation in protein solids are relatively well covered by the literature. Considerably less is known about oxidative and photochemical reactions of solid proteins. This review will provide an overview over photolytic and non-photolytic degradation reactions, and specially emphasize mechanistic details on how solid structure may affect the interaction of protein solids with light. Copyright © 2014 Elsevier B.V. All rights reserved.

Estimated Chemical Warfare Agent Surface Clearance Goals for Remediation Pre-Planning

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

Dolislager, Frederick; Bansleben, Dr. Donald; Watson, Annetta Paule

2010-01-01

Health-based surface clearance goals, in units of mg/cm2, have been developed for the persistent chemical warfare agents sulfur mustard (HD) and nerve agent VX as well as their principal degradation products. Selection of model parameters and critical receptor (toddler child) allow calculation of surface residue estimates protective for the toddler child, the general population and adult employees of a facilty that has undergone chemical warfare agent attack.

Biologically Active Zone Enhancement (BAZE) for In Situ RDX Degradation in Ground Water

DTIC Science & Technology

2010-01-01

geotechnical laboratory testing, will be performed in Level D protection with the addition of chemical resistant gloves. The level of protection for...splash hazards), • Chemical- resistant boots (PVC, Neoprene, Rubber) or work boots with covers ( steel-toed as appropriate), • Inner gloves (latex or...vinyl), • Outer, chemical- resistant gloves (nitrile, PVC, Neoprene), • Safety glasses or goggles, • Hard hat (as required by OSHA), and • Splash

Towards Thermal Wavelength Scale Two- and Three-Dimensional Photonic Crystals

DTIC Science & Technology

2016-04-01

this now. We studied the anisotropic thermal conductivity of nanoscale graphite layers deposited by chemical vapor deposition on Ni substrates at...Braun, and David G. Cahill, “Thermal conductivity of graphite thin films grown by low temperature chemical vapor deposition on Ni (111),” submitted...that there is no degradation in the power factor. In the carbon work, we studied the deposited by chemical vapor deposition on Ni substrates at

Insights into lignin degradation and its potential industrial applications.

PubMed

Abdel-Hamid, Ahmed M; Solbiati, Jose O; Cann, Isaac K O

2013-01-01

Lignocellulose is an abundant biomass that provides an alternative source for the production of renewable fuels and chemicals. The depolymerization of the carbohydrate polymers in lignocellulosic biomass is hindered by lignin, which is recalcitrant to chemical and biological degradation due to its complex chemical structure and linkage heterogeneity. The role of fungi in delignification due to the production of extracellular oxidative enzymes has been studied more extensively than that of bacteria. The two major groups of enzymes that are involved in lignin degradation are heme peroxidases and laccases. Lignin-degrading peroxidases include lignin peroxidase (LiP), manganese peroxidase (MnP), versatile peroxidase (VP), and dye-decolorizing peroxidase (DyP). LiP, MnP, and VP are class II extracellular fungal peroxidases that belong to the plant and microbial peroxidases superfamily. LiPs are strong oxidants with high-redox potential that oxidize the major non-phenolic structures of lignin. MnP is an Mn-dependent enzyme that catalyzes the oxidation of various phenolic substrates but is not capable of oxidizing the more recalcitrant non-phenolic lignin. VP enzymes combine the catalytic activities of both MnP and LiP and are able to oxidize Mn(2+) like MnP, and non-phenolic compounds like LiP. DyPs occur in both fungi and bacteria and are members of a new superfamily of heme peroxidases called DyPs. DyP enzymes oxidize high-redox potential anthraquinone dyes and were recently reported to oxidize lignin model compounds. The second major group of lignin-degrading enzymes, laccases, are found in plants, fungi, and bacteria and belong to the multicopper oxidase superfamily. They catalyze a one-electron oxidation with the concomitant four-electron reduction of molecular oxygen to water. Fungal laccases can oxidize phenolic lignin model compounds and have higher redox potential than bacterial laccases. In the presence of redox mediators, fungal laccases can oxidize non-phenolic lignin model compounds. In addition to the peroxidases and laccases, fungi produce other accessory oxidases such as aryl-alcohol oxidase and the glyoxal oxidase that generate the hydrogen peroxide required by the peroxidases. Lignin-degrading enzymes have attracted the attention for their valuable biotechnological applications especially in the pretreatment of recalcitrant lignocellulosic biomass for biofuel production. The use of lignin-degrading enzymes has been studied in various applications such as paper industry, textile industry, wastewater treatment and the degradation of herbicides. Copyright © 2013 Elsevier Inc. All rights reserved.

Chemical Characterization of the Degradation of Necromass from Four Ascomycota Fungi: Implications for Soil Organic Carbon Turnover and Storage

NASA Astrophysics Data System (ADS)

Bruner, V. J.; Schreiner, K. M.; Blair, N. E.; Egerton, L.

2016-12-01

Terrestrial soils store vast amounts of organic carbon, approximately twice as much carbon as is currently in the atmospheric CO2 pool. Despite its importance in the global carbon cycle, much is still unknown about the source, turnover, and stability of this soil organic carbon (SOC) pool. For example, fungi are known to play an important role in shaping the chemistry of SOC by degrading common biopolymers, and fungal biomass has been found to be a significant portion of living microbial SOC, dominating over bacteria in some soils by as much as 90%. And yet, despite growing evidence that microbial necromass may be larger contributors to SOC than previously thought, very little is known about the specific degradation patterns of fungal necromass and subsequently its potential chemical contributions to long-lived SOC pools. This study addresses these knowledge gaps through a time-series analysis of the degradation patterns of fungal tissue from four different saprotrophic Ascomyota species in temperate restored prairie soils. Fungal tissue was buried in soils both within a temperature- and light-controlled laboratory environment, and in a field environment, and harvested at intervals from 1 day to two months. After harvest, chemical analysis of the dried tissue by thermochemolysis pyrolysis-GCMS was used for relative quantitation of a variety of common biomolecules and biopolymers within the fungal tissue that may be long lived in soils, including chitin, glucan, mannan, ergosterol, and melanin. The degradation of these specific molecules, bulk fungal tissue, and bulk C and N within the tissue, is modeled to (1) show that a small portion of fungal necromass persists in the environment even after the period of the experiment and could serve as a contributor to long-lived SOC, and (2) provide quantitative information on the contribution of fungal tissue to global SOC pools.

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

PubMed

Zhao, Xueheng; Hwang, Huey-Min

2009-05-01

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

Benzene degradation in a denitrifying biofilm reactor: activity and microbial community composition.

PubMed

van der Waals, Marcelle J; Atashgahi, Siavash; da Rocha, Ulisses Nunes; van der Zaan, Bas M; Smidt, Hauke; Gerritse, Jan

2017-06-01

Benzene is an aromatic compound and harmful for the environment. Biodegradation of benzene can reduce the toxicological risk after accidental or controlled release of this chemical in the environment. In this study, we further characterized an anaerobic continuous biofilm culture grown for more than 14 years on benzene with nitrate as electron acceptor. We determined steady state degradation rates, microbial community composition dynamics in the biofilm, and the initial anaerobic benzene degradation reactions. Benzene was degraded at a rate of 0.15 μmol/mg protein/day and a first-order rate constant of 3.04/day which was fourfold higher than rates reported previously. Bacteria belonging to the Peptococcaceae were found to play an important role in this anaerobic benzene-degrading biofilm culture, but also members of the Anaerolineaceae were predicted to be involved in benzene degradation or benzene metabolite degradation based on Illumina MiSeq analysis of 16S ribosomal RNA genes. Biomass retention in the reactor using a filtration finger resulted in reduction of benzene degradation capacity. Detection of the benzene carboxylase encoding gene, abcA, and benzoic acid in the culture vessel indicated that benzene degradation proceeds through an initial carboxylation step.

Effects of ionizing radiations on a pharmaceutical compound, chloramphenicol

NASA Astrophysics Data System (ADS)

Varshney, L.; Patel, K. M.

1994-05-01

Chloramphenicol, a broad spectrum antibiotic, has been irradiated using Cobalt-60 γ radiation and electron beam at graded radiation doses upto 100 kGy. Several degradation products and free radicals are formed on irradiation. Purity, degradation products, free radicals, discolouration, crystallinity, solubility and entropy of radiation processing have been investigated. Aqueous solutions undergo extensive radiolysis even at low doses. Physico-chemical, microbiological and toxicological tests do not show significant degradation at sterilization dose. High performance liquid chromatography (HPLC), differential scanning calorimetry (DSC), UV-spectrophotometry, diffuse reflectance spectroscopy (DRS) and electron spin resonance spectroscopy (ESR) techniques were employed for the investigations.

Degradation of curcumin: From mechanism to biological implications

PubMed Central

Schneider, Claus; Gordon, Odaine N.; Edwards, Rebecca L.; Luis, Paula B.

2016-01-01

Curcumin is the main bioactive ingredient in turmeric extract and widely consumed as part of the spice mix curry or as dietary supplement. Turmeric has a long history of therapeutic application in traditional Asian medicine. Biomedical studies conducted in the past two decades have identified a large number of cellular targets and effects of curcumin. In vitro curcumin rapidly degrades in an autoxidative transformation to diverse chemical species, formation of which has only recently been appreciated. We discuss how degradation and metabolism of curcumin, through products and their mechanism of formation, provide a basis for the interpretation of preclinical data and clinical studies. We suggest that the previously unrecognized diversity of its degradation products could be an important factor in explaining the polypharmacology of curcumin. PMID:25817068

The emerging role for bacteria in lignin degradation and bio-product formation.

PubMed

Bugg, Timothy D H; Ahmad, Mark; Hardiman, Elizabeth M; Singh, Rahul

2011-06-01

The microbial degradation of lignin has been well studied in white-rot and brown-rot fungi, but is much less well studied in bacteria. Recent published work suggests that a range of soil bacteria, often aromatic-degrading bacteria, are able to break down lignin. The enzymology of bacterial lignin breakdown is currently not well understood, but extracellular peroxidase and laccase enzymes appear to be involved. There are also reports of aromatic-degrading bacteria isolated from termite guts, though there are conflicting reports on the ability of termite gut micro-organisms to break down lignin. If biocatalytic routes for lignin breakdown could be developed, then lignin represents a potentially rich source of renewable aromatic chemicals. Copyright © 2010 Elsevier Ltd. All rights reserved.

Physical-chemical quality of onion analyzed under drying temperature

NASA Astrophysics Data System (ADS)

Djaeni, M.; Arifin, U. F.; Sasongko, S. B.

2017-03-01

Drying is one of conventional processes to enhance shelf life of onion. However, the active compounds such as vitamin and anthocyanin (represented in red color), degraded due to the introduction of heat during the process. The objective of this research was to evaluate thiamine content as well as color in onion drying under different temperature. As an indicator, the thiamine and color was observed every 30 minutes for 2 hours. Results showed that thiamine content and color were sensitvely influenced by the temperature change. For example, at 50°C for 2 hours drying process, the thiamine degradation was 55.37 %, whereas, at 60°C with same drying time, the degradation was 74.01%. The quality degradation also increased by prolonging drying time.

Degradation of 4-Chlorophenol Under Sunlight Using ZnO Nanoparticles as Catalysts

NASA Astrophysics Data System (ADS)

Rajar, Kausar; Sirajuddin; Balouch, Aamna; Bhanger, M. I.; Sherazi, Tufail H.; Kumar, Raj

2018-03-01

Herein we demonstrate a simplistic microwave assisted chemical precipitation approach regarding the synthesis of zinc oxide nanoparticles. As-prepared ZnO nanoparticles (NPs) were characterized by UV-visible spectroscopy, Fourier transform infra-red spectroscopy, atomic force microscopy and x-ray diffractometry and scrutinized as photo-catalysts for degradation of 4-chlorophenol (4-CP) under sunlight. The study substantiated that 98.5% of 4-CP was degraded within 20 min in the absence of initiator like H2O2 which reflects an outstanding prospective use for ZnO NPs as photo-catalysts. The nanocatalysts were recycled four times and still showed catalytic efficiency up to 95.5% for degradation of 4-CP in the specified 20 min.

Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

PubMed

Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

2016-01-01

Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

The influence of fire exposure on austenitic stainless steel for pressure vessel fitness-for-service assessment: Experimental research

NASA Astrophysics Data System (ADS)

Li, Bo; Shu, Wenhua; Zuo, Yantian

2017-04-01

The austenitic stainless steels are widely applied to pressure vessel manufacturing. The fire accident risk exists in almost all the industrial chemical plants. It is necessary to make safety evaluation on the chemical equipment including pressure vessels after fire. Therefore, the present research was conducted on the influences of fire exposure testing under different thermal conditions on the mechanical performance evolution of S30408 austenitic stainless steel for pressure vessel equipment. The metallurgical analysis described typical appearances in micro-structure observed in the material suffered by fire exposure. Moreover, the quantitative degradation of mechanical properties was investigated. The material thermal degradation mechanism and fitness-for-service assessment process of fire damage were further discussed.

Stabilization of S-adenosyl-L-methionine promoted by trehalose.

PubMed

Morana, Alessandra; Stiuso, Paola; Colonna, Giovanni; Lamberti, Monica; Cartenì, Maria; De Rosa, Mario

2002-11-14

S-adenosyl-L-methionine (SAM), an important metabolic intermediate of mammals, is a well-known therapeutic agent. The molecule is chemically unstable, both in solution and in dry state, and forms different degradation products. Because the chemical instability represents a real problem during the preparation of therapeutic formulations, we investigated the capacity of some sugars to improve the SAM stability over time. In the present work, we demonstrated that the disaccharide trehalose exercises a protective effect towards the lyophilized SAM slackening its degradation (65% of SAM was detected after 50 days at 37 degrees C). A parallel study, performed to stabilize the SAM into lyophilized yeast cells enriched in the sulfonium compound, assessed the positive effect of trehalose also in whole cells, but in lesser measure.

Role of P450 monooxygenases in the degradation of the endocrine-disrupting chemical nonylphenol by the white rot fungus Phanerochaete chrysosporium.

PubMed

Subramanian, Venkataramanan; Yadav, Jagjit S

2009-09-01

The white rot fungus Phanerochaete chrysosporium extensively degraded the endocrine disruptor chemical nonylphenol (NP; 100% of 100 ppm) in both nutrient-limited cultures and nutrient-sufficient cultures. The P450 enzyme inhibitor piperonyl butoxide caused significant inhibition (approximately 75%) of the degradation activity in nutrient-rich malt extract (ME) cultures but no inhibition in defined low-nitrogen (LN) cultures, indicating an essential role of P450 monooxygenase(s) in NP degradation under nutrient-rich conditions. A genome-wide analysis using our custom-designed P450 microarray revealed significant induction of multiple P450 monooxygenase genes by NP: 18 genes were induced (2- to 195-fold) under nutrient-rich conditions, 17 genes were induced (2- to 6-fold) in LN cultures, and 3 were induced under both nutrient-rich and LN conditions. The P450 genes Pff 311b (corresponding to protein identification number [ID] 5852) and Pff 4a (protein ID 5001) showed extraordinarily high levels of induction (195- and 167-fold, respectively) in ME cultures. The P450 oxidoreductase (POR), glutathione S-transferase (gst), and cellulose metabolism genes were also induced in ME cultures. In contrast, certain metabolic genes, such as five of the peroxidase genes, showed partial downregulation by NP. This study provides the first evidence for the involvement of P450 enzymes in NP degradation by a white rot fungus and the first genome-wide identification of specific P450 genes responsive to an environmentally significant toxicant.

Decomposition of the polycyclic nitramine explosive, CL-20, by Fe(0).

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Halasz, Annamaria; Corbeanu, Aurelian; Hawari, Jalal

2004-12-15

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), C6H6N12O12, is an emerging energetic chemical that may replace RDX, but its degradation pathways are not well-known. In the present study, zerovalent iron was used to degrade CL-20 with the aim of determining its products and degradation pathways. In the absence of O2, CL-20 underwent a rapid decomposition with the concurrent formation of nitrite to ultimately produce nitrous oxide, ammonium, formate, glyoxal, and glycolate. LC/MS (ES-) showed the presence of several key products carrying important information on the initial reactions involved in the degradation of CL-20. For instance, a doubly denitrated intermediate of CL-20 was detected together with the mono- and dinitroso derivatives of the energetic chemical. Two other intermediates with [M-H]- at 392 and 376 Da, matching empirical formulas of C6H7N11O10 and C6H7N11O9, respectively, were detected. Using 15N-labeled CL-20, the two intermediates were tentatively identified as the denitrohydrogenated products of CL-20 and its mononitroso derivative, respectively. The present experimental findings suggest that CL-20 degraded via at least two initial routes: one involving denitration and the second involving sequential reduction of the N-NO2 to the corresponding nitroso (N-NO) derivatives prior to denitration and ring cleavage.

Combined biodegradation and ozonation for removal of tannins and dyes for the reduction of pollution loads.

PubMed

Kanagaraj, James; Mandal, Asit Baran

2012-01-01

Tannins and dyes pose major threat to the environment by generating huge pollution problem. Biodegradation of wattle extract, chrome tannin and dye compounds using suitable fungal culture namely Aspergillus niger, Penicillium sp. were carried out. In addition to these, ozone treatment was carried out to get higher degradation rate. The results were monitored by carrying out chemical oxygen demand (COD), total organic carbon (TOC), and UV-Vis analysis. The results showed that wattle extract (vegetable tannin) gave better biodegradation rate than dye and chromium compounds. Biodegradation plus ozone showed degradation rates of 92-95%, 94-95%, and 85-87% for the wattle extract, dyes, chromium compounds, respectively. UV-Vis showed that there were no peaks observed for biodegraded samples indicating better degradation rates as compared to the control samples. FT-IR spectra analysis suggested that the formation of flavanoid derivatives, chromic oxide and NH(2) compounds during degradation of wattle extract, chromium and dye compounds, respectively, at the peaks of 1,601-1,629 cm(-1), 1,647 cm(-1), and 1,610-1,680 cm(-1). The present investigation shows that combination of biodegradation with ozone is the effective method for the removal of dyes and tannins. The biodegradation of the said compounds in combination with ozonation showed better rate of degradation than by chemical methods. The combination of biodegradation with ozone helps to reduce pollution problems in terms of COD, TOC, total dissolved solids and total suspended solids.

Characterization of Volatile Nylon 6.6 Thermal-Oxidative Degradation Products by Selective Isotopic Labeling and Cryo-GC/MS

NASA Astrophysics Data System (ADS)

Smith, Jonell N.; V. White, Gregory; White, Michael I.; Bernstein, Robert; Hochrein, James M.

2012-09-01

Aged materials, such as polymers, can exhibit modifications to their chemical structure and physical properties, which may render the material ineffective for its intended purpose. Isotopic labeling was used to characterize low-molecular weight volatile thermal-oxidative degradation products of nylon 6.6 in an effort to better understand and predict changes in the aged polymer. Headspace gas from aged (up to 243 d at 138 °C) nylon 6.6 monomers (adipic acid and 1,6-hexanediamine) and polymer were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). Observations regarding the relative concentrations observed in each chromatographic peak with respect to aging time were used in conjunction with mass spectra for samples aged under ambient air to determine the presence and identity of 18 degradation products. A comparison of the National Institute of Standards and Technology (NIST) library, unlabeled, and isotopically labeled mass spectra (C-13 or N-15) and expected fragmentation pathways of each degradation product were used to identify the location of isotopically labeled atoms within the product's chemical structure, which can later be used to determine the exact origin of the species. In addition, observations for unlabeled nylon 6.6 aged in an O-18 enriched atmosphere were used to determine if the source of oxygen in the applicable degradation products was from the gaseous environment or the polymer. Approximations for relative isotopic ratios of unlabeled to labeled products are reported, where appropriate.

Role of P450 Monooxygenases in the Degradation of the Endocrine-Disrupting Chemical Nonylphenol by the White Rot Fungus Phanerochaete chrysosporium▿

PubMed Central

Subramanian, Venkataramanan; Yadav, Jagjit S.

2009-01-01

The white rot fungus Phanerochaete chrysosporium extensively degraded the endocrine disruptor chemical nonylphenol (NP; 100% of 100 ppm) in both nutrient-limited cultures and nutrient-sufficient cultures. The P450 enzyme inhibitor piperonyl butoxide caused significant inhibition (∼75%) of the degradation activity in nutrient-rich malt extract (ME) cultures but no inhibition in defined low-nitrogen (LN) cultures, indicating an essential role of P450 monooxygenase(s) in NP degradation under nutrient-rich conditions. A genome-wide analysis using our custom-designed P450 microarray revealed significant induction of multiple P450 monooxygenase genes by NP: 18 genes were induced (2- to 195-fold) under nutrient-rich conditions, 17 genes were induced (2- to 6-fold) in LN cultures, and 3 were induced under both nutrient-rich and LN conditions. The P450 genes Pff 311b (corresponding to protein identification number [ID] 5852) and Pff 4a (protein ID 5001) showed extraordinarily high levels of induction (195- and 167-fold, respectively) in ME cultures. The P450 oxidoreductase (POR), glutathione S-transferase (gst), and cellulose metabolism genes were also induced in ME cultures. In contrast, certain metabolic genes, such as five of the peroxidase genes, showed partial downregulation by NP. This study provides the first evidence for the involvement of P450 enzymes in NP degradation by a white rot fungus and the first genome-wide identification of specific P450 genes responsive to an environmentally significant toxicant. PMID:19542331

Ruminal degradation of cell wall associated nitrogenous compounds of several (15) N-labelled feeds.

PubMed

Vanegas, Jorge L; Arroyo, José M; González, Javier

2016-09-01

Ruminal in situ effective degradability (ED) of dry matter (DM), neutral (NDF) and acid (ADF) detergent fibres, total-N and NDF (NDIN) and ADF (ADIN) bound-N in sunflower seed (SS), wheat grain (WG) and wheat straw (WS) were measured in three ruminally cannulated sheep, correcting microbial N-contamination using the (15) N dilution technique modified to consider the (15) N supply to adherent bacteria. The lack of correction for N-contamination under-evaluated ED estimates in 1.52% (total-N), 28.0% (NDIN) and 33.3% (ADIN) in SS and in 1.02% (total-N) and 4.43% (NDIN) in WG. In the remaining cases, this contamination prevented establishing apparent degradation kinetics and, therefore, errors were not measured. Microbial corrected ED estimates in SS were higher in total-N (0.917) than in NDIN (0.559) and ADIN (0.520), which showed similar values. This behaviour was also shown in WS (0.670, 0.386 and 0.426, respectively), whereas decreasing values were shown from total-N (0.917) to NDIN (0.830) and ADIN (0.482) in WG. Results confirm that NDF and ADF procedures failed to remove large fractions of particle adherent microorganisms, under-evaluating the ED of NDIN and ADIN. Degradation of NDIN represented a significant part of the degraded N, whereas ADIN contribution was only negligible in WG. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Effect of cellulosic sugar degradation products (furfural and hydroxymethylfurfural) on acetone-butanol-ethanol (ABE) fermentation using Clostridium beijerinckii P260

USDA-ARS?s Scientific Manuscript database

Studies were performed to identify chemicals present in wheat straw hydrolysate (WSH) that enhance acetone butanol ethanol (ABE) productivity. These chemicals were identified as furfural and hydroxymethyl furfural (HMF). Control experiment resulted in the production of 21.09-21.66 gL**-1 ABE with a ...

Chemical modification of wood

Treesearch

Roger M. Rowell

2007-01-01

After millions of years of evolution, wood was designed to perform in a wet environment, and nature is programmed to recycle it, in a timely way, back to the basic building blocks of carbon dioxide and water through biological, thermal, aqueous, photochemical, chemical, and mechanical degradation. The properties of wood are, for the most part, a result of the chemistry...

Development of an Exchange Format for the European Environmental Chemical Data and Information Network (ECDIN).

ERIC Educational Resources Information Center

And Others; Proctor, David, J.

1978-01-01

Uses collection and storage of data in an environmental chemicals data bank to develop an exchange format of hierarchical tree structure between network partners. Rules identify and process the nodes in the tree in such a way that information is neither lost nor degraded upon transfer between network partners. (CWM)

Effects of chemically modified wood on bond durability

Treesearch

Rishawn Brandon; Rebecca E. Ibach; Charles R. Frihart

2005-01-01

Chemical modification of wood can improve its dimensional stability and resistance to biological degradation and moisture, but modification can also create a new surface for bonding. Acetylation of wood results in the loss of hydroxyl groups, making the wood more hydrophobic and reduces its ability to hydrogen-bond with the adhesive. In contrast, reacting wood with...

Determination of pharmaceutical residues and assessment of their removal efficiency at the Daugavgriva municipal wastewater treatment plant in Riga, Latvia.

PubMed

Reinholds, I; Muter, O; Pugajeva, I; Rusko, J; Perkons, I; Bartkevics, V

2017-01-01

Pharmaceutical products (PPs) belong to emerging contaminants that may accumulate along with other chemical pollutants in wastewaters (WWs) entering industrial and/or urban wastewater treatment plants (WWTPs). In the present study, the technique of ultra-high-performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (Orbitrap-HRMS) was applied for the analysis of 24 multi-class PPs in WW samples collected at different technological stages of Daugavgriva WWTP located in Riga, Latvia. Caffeine and acetaminophen levels in the range of 7,570-11,403 ng/L and 810-1,883 ng/L, respectively, were the predominant compounds among 19 PPs determined in the WW. The results indicate that aerobic digestion in biological ponds was insufficiently effective to degrade most of the PPs (reduction efficiency <0-50.0%) with the exception of four PPs that showed degradation efficiency varying from 55.0 to 99.9%. Tests of short-term chemical and enzymatic hydrolysis for PP degradation in WW samples were performed, and the results reflected the complexity of different degradation mechanisms and physicochemical transformations of PPs. The toxicological studies of WW impact on Daphnia magna indicated gradual reduction of the total toxicity through the treatment stages at the WWTP.

Material degradation due to moisture and temperature. Part 1: mathematical model, analysis, and analytical solutions

NASA Astrophysics Data System (ADS)

Xu, C.; Mudunuru, M. K.; Nakshatrala, K. B.

2016-11-01

The mechanical response, serviceability, and load-bearing capacity of materials and structural components can be adversely affected due to external stimuli, which include exposure to a corrosive chemical species, high temperatures, temperature fluctuations (i.e., freezing-thawing), cyclic mechanical loading, just to name a few. It is, therefore, of paramount importance in several branches of engineering—ranging from aerospace engineering, civil engineering to biomedical engineering—to have a fundamental understanding of degradation of materials, as the materials in these applications are often subjected to adverse environments. As a result of recent advancements in material science, new materials such as fiber-reinforced polymers and multi-functional materials that exhibit high ductility have been developed and widely used, for example, as infrastructural materials or in medical devices (e.g., stents). The traditional small-strain approaches of modeling these materials will not be adequate. In this paper, we study degradation of materials due to an exposure to chemical species and temperature under large strain and large deformations. In the first part of our research work, we present a consistent mathematical model with firm thermodynamic underpinning. We then obtain semi-analytical solutions of several canonical problems to illustrate the nature of the quasi-static and unsteady behaviors of degrading hyperelastic solids.

Thermal sterilization of heat-sensitive products using high-temperature short-time sterilization.

PubMed

Mann, A; Kiefer, M; Leuenberger, H

2001-03-01

High-temperature short-time (HTST) sterilization with a continuous-flow sterilizer, developed for this study, was evaluated. The evaluation was performed with respect to (a) the chemical degradation of two heat-sensitive drugs in HTST range (140-160 degrees C) and (b) the microbiological effect of HTST sterilization. Degradation kinetics of two heat-sensitive drugs showed that a high peak temperature sterilization process resulted in less chemical degradation for the same microbiological effect than a low peak temperature process. Both drugs investigated could be sterilized with acceptable degradation at HTST conditions. For the evaluation of the microbiological effect, Bacillus stearothermophilus ATCC 7953 spores were used as indicator bacteria. Indicator spore kinetics (D(T), z value, k, and E(a)), were determined in the HTST range. A comparison between the Bigelow model (z value concept) and the Arrhenius model, used to describe the temperature coefficient of the microbial inactivation, demonstrated that the Bigelow model is more accurate in prediction of D(T) values in the HTST range. The temperature coefficient decreased with increasing temperature. The influence of Ca(2+) ions and pH value on the heat resistance of the indicator spores, which is known under typical sterilization conditions, did not change under HTST conditions.

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water.

PubMed

Hao, Xiao Long; Zhou, Ming Hua; Lei, Le Cheng

2007-03-22

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.

Space Environment Effects on Stability of Medications Flown on Space Shuttles and the International Space Station (ISS)

NASA Technical Reports Server (NTRS)

Daniels, Vernie; Du, Jianping; Crady, Camille; Satterfield, Rick; Putcha, Lakshmi

2007-01-01

The purpose is to assess physical and chemical degradation of select pharmaceutical formulations from the Shuttle and ISS medical kits. Eleven pharmaceuticals dispensed as different dosage forms were selected based on their physical / chemical characteristics and susceptibility to environmental factors such as, temperature, humidity and light sensitivity. When available, ground-controls of the study medications with matching brand and lot numbers were used for comparison. Samples retrieved from flight were stored along with their matching controls in a temperature and humidity controlled environmental chamber. Temperature, humidity, and radiation data from the Shuttle and ISS were retrieved from onboard HOBO U12 Temp/RH Data Loggers, and from passive dosimeters. Physical and chemical analyses of the pharmaceuticals were conducted using validated United States Pharmacopeia (USP) methods. Results indicated degradation of 6 of the 11 formulations returned from space flights. Four formulations, Amoxicillin / Clavulanate, promethazine, sulfamethoxazole / trimethoprim, and ciprofloxacin tablets depicted discoloration after flight. Chemical content analyses using High or Ultra Performance Liquid Chromatography (HPLC / UPLC) methods revealed that dosage forms of Amoxicillin / Clavulanate, promethazine, sulfamethoxazole / trimethoprim, lidocaine, ciprofloxacin and mupirocin contained less than 95% of manufacturer s labeled claim of active drug compound. Shuttle and ISS environments affect stability and shelf life of certain mediations flown on these missions. Data analysis is in progress to examine the effect of specific space flight environmental factors on pharmaceutical stability. The degradation profiles generated from ground studies in analog environments will be useful in establishing predictive shelf-life profiles for medications intended for use during long-term space exploration missions.

Designing degradable hydrogels for orthogonal control of cell microenvironments

PubMed Central

Kharkar, Prathamesh M.

2013-01-01

Degradable and cell-compatible hydrogels can be designed to mimic the physical and biochemical characteristics of native extracellular matrices and provide tunability of degradation rates and related properties under physiological conditions. Hence, such hydrogels are finding widespread application in many bioengineering fields, including controlled bioactive molecule delivery, cell encapsulation for controlled three-dimensional culture, and tissue engineering. Cellular processes, such as adhesion, proliferation, spreading, migration, and differentiation, can be controlled within degradable, cell-compatible hydrogels with temporal tuning of biochemical or biophysical cues, such as growth factor presentation or hydrogel stiffness. However, thoughtful selection of hydrogel base materials, formation chemistries, and degradable moieties is necessary to achieve the appropriate level of property control and desired cellular response. In this review, hydrogel design considerations and materials for hydrogel preparation, ranging from natural polymers to synthetic polymers, are overviewed. Recent advances in chemical and physical methods to crosslink hydrogels are highlighted, as well as recent developments in controlling hydrogel degradation rates and modes of degradation. Special attention is given to spatial or temporal presentation of various biochemical and biophysical cues to modulate cell response in static (i.e., non-degradable) or dynamic (i.e., degradable) microenvironments. This review provides insight into the design of new cell-compatible, degradable hydrogels to understand and modulate cellular processes for various biomedical applications. PMID:23609001

Detection of toxic industrial chemicals in water supplies using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Spencer, Kevin M.; Sylvia, James M.; Spencer, Sarah A.; Clauson, Susan L.

2010-04-01

An effective method to create fear in the populace is to endanger the water supply. Homeland Security places significant importance on ensuring drinking water integrity. Beyond terrorism, accidental supply contamination from a spill or chemical residual increases is a concern. A prominent class of toxic industrial chemicals (TICs) is pesticides, which are prevalent in agricultural use and can be very toxic in minute concentrations. Detection of TICs or warfare agents must be aggressive; the contaminant needs to be rapidly detected and identified to enable isolation and remediation of the contaminated water while continuing a clean water supply for the population. Awaiting laboratory analysis is unacceptable as delay in identification and remediation increases the likelihood of infection. Therefore, a portable or online water quality sensor is required that can produce rapid results. In this presentation, Surface-Enhanced Raman Spectroscopy (SERS) is discussed as a viable fieldable sensor that can be immersed directly into the water supply and can provide results in <5 minutes from the time the instrument is turned on until analysis is complete. The ability of SERS to detect several chemical warfare agent degradation products, simulants and toxic industrial chemicals in distilled water, tap water and untreated water will be shown. In addition, results for chemical warfare agent degradation products and simulants will be presented. Receiver operator characteristic (ROC) curves will also be presented.

Biodegradable Polymeric Materials in Degradable Electronic Devices

PubMed Central

2018-01-01

Biodegradable electronics have great potential to reduce the environmental footprint of devices and enable advanced health monitoring and therapeutic technologies. Complex biodegradable electronics require biodegradable substrates, insulators, conductors, and semiconductors, all of which comprise the fundamental building blocks of devices. This review will survey recent trends in the strategies used to fabricate biodegradable forms of each of these components. Polymers that can disintegrate without full chemical breakdown (type I), as well as those that can be recycled into monomeric and oligomeric building blocks (type II), will be discussed. Type I degradation is typically achieved with engineering and material science based strategies, whereas type II degradation often requires deliberate synthetic approaches. Notably, unconventional degradable linkages capable of maintaining long-range conjugation have been relatively unexplored, yet may enable fully biodegradable conductors and semiconductors with uncompromised electrical properties. While substantial progress has been made in developing degradable device components, the electrical and mechanical properties of these materials must be improved before fully degradable complex electronics can be realized. PMID:29632879

Cathode Degradation in Thallium Bromide Devices

NASA Astrophysics Data System (ADS)

Datta, Amlan; Motakef, Shariar

2015-06-01

Thallium bromide (TlBr) is a wide bandgap, compound semiconductor with high gamma-ray stopping power and promising physical properties. However, performance degradation and the eventual irreversible failure of TlBr devices can occur rapidly at room temperature, due to “polarization”, caused by the electromigration of Tl+ and Br- ions to the electrical contacts across the device. Using the Accelerated Device Degradation (ADD) experiment, the degradation phenomena in TlBr devices have been visualized and recorded. This paper focuses on “ageing” of the device cathode at various temperatures. ADD is a fast and reliable direct characterization technique that can be used to identify the effects of various growth and post-growth process modifications on device degradation. Using this technique we have identified cathode degradation with the migration of Br- ions and an associated generation and growth of Thallium-rich fractal “ferns” from the cathode. Its effect on the radiation response of the device has also been discussed in this paper. The chemical changes in the cathode were characterized using Energy-dispersive X-ray spectroscopy.

Progress and obstacles in the production and application of recombinant lignin-degrading peroxidases

PubMed Central

Lambertz, Camilla; Ece, Selin; Fischer, Rainer; Commandeur, Ulrich

2016-01-01

ABSTRACT Lignin is 1 of the 3 major components of lignocellulose. Its polymeric structure includes aromatic subunits that can be converted into high-value-added products, but this potential cannot yet been fully exploited because lignin is highly recalcitrant to degradation. Different approaches for the depolymerization of lignin have been tested, including pyrolysis, chemical oxidation, and hydrolysis under supercritical conditions. An additional strategy is the use of lignin-degrading enzymes, which imitates the natural degradation process. A versatile set of enzymes for lignin degradation has been identified, and research has focused on the production of recombinant enzymes in sufficient amounts to characterize their structure and reaction mechanisms. Enzymes have been analyzed individually and in combinations using artificial substrates, lignin model compounds, lignin and lignocellulose. Here we consider progress in the production of recombinant lignin-degrading peroxidases, the advantages and disadvantages of different expression hosts, and obstacles that must be overcome before such enzymes can be characterized and used for the industrial processing of lignin. PMID:27295524

The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

PubMed

Chen, Q; Song, J M; Pan, F; Xia, F L; Yuan, J Y

2009-10-01

Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

Predicting chemical degradation during storage from two successive concentration ratios: Theoretical investigation.

PubMed

Peleg, Micha; Normand, Mark D

2015-09-01

When a vitamin's, pigment's or other food component's chemical degradation follows a known fixed order kinetics, and its rate constant's temperature-dependence follows a two parameter model, then, at least theoretically, it is possible to extract these two parameters from two successive experimental concentration ratios determined during the food's non-isothermal storage. This requires numerical solution of two simultaneous equations, themselves the numerical solutions of two differential rate equations, with a program especially developed for the purpose. Once calculated, these parameters can be used to reconstruct the entire degradation curve for the particular temperature history and predict the degradation curves for other temperature histories. The concept and computation method were tested with simulated degradation under rising and/or falling oscillating temperature conditions, employing the exponential model to characterize the rate constant's temperature-dependence. In computer simulations, the method's predictions were robust against minor errors in the two concentration ratios. The program to do the calculations was posted as freeware on the Internet. The temperature profile can be entered as an algebraic expression that can include 'If' statements, or as an imported digitized time-temperature data file, to be converted into an Interpolating Function by the program. The numerical solution of the two simultaneous equations requires close initial guesses of the exponential model's parameters. Programs were devised to obtain these initial values by matching the two experimental concentration ratios with a generated degradation curve whose parameters can be varied manually with sliders on the screen. These programs too were made available as freeware on the Internet and were tested with published data on vitamin A. Copyright © 2015 Elsevier Ltd. All rights reserved.

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study.

PubMed

Liang, Chenju; Lee, I-Ling

2008-09-10

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.

Stability studies of lincomycin hydrochloride in aqueous solution and intravenous infusion fluids.

PubMed

Czarniak, Petra; Boddy, Michael; Sunderland, Bruce; Hughes, Jeff D

2016-01-01

The purpose of this study was to evaluate the chemical stability of Lincocin(®) (lincomycin hydrochloride) in commonly used intravenous fluids at room temperature (25°C), at accelerated-degradation temperatures and in selected buffer solutions. The stability of Lincocin(®) injection (containing lincomycin 600 mg/2 mL as the hydrochloride) stored at 25°C±0.1°C in sodium lactate (Hartmann's), 0.9% sodium chloride, 5% glucose, and 10% glucose solutions was investigated over 31 days. Forced degradation of Lincocin(®) in hydrochloric acid, sodium hydroxide, and hydrogen peroxide was performed at 60°C. The effect of pH on the degradation rate of lincomycin hydrochloride stored at 80°C was determined. Lincomycin hydrochloride w as found to maintain its shelf life at 25°C in sodium lactate (Hartmann's) solution, 0.9% sodium chloride solution, 5% glucose solution, and 10% glucose solution, with less than 5% lincomycin degradation occurring in all intravenous solutions over a 31-day period. Lincomycin hydrochloride showed less rapid degradation at 60°C in acid than in basic solution, but degraded rapidly in hydrogen peroxide. At all pH values tested, lincomycin followed first-order kinetics. It had the greatest stability near pH 4 when stored at 80°C (calculated shelf life of 4.59 days), and was least stable at pH 2 (calculated shelf life of 0.38 days). Lincocin(®) injection was chemically found to have a shelf life of at least 31 days at 25°C when added to sodium lactate (Hartmann's) solution, 0.9% sodium chloride solution, 5% glucose solution, and 10% glucose solution. Solutions prepared at approximately pH 4 are likely to have optimum stability.

Furfural and 5-hydroxymethyl-furfural degradation using recombinant manganese peroxidase.

PubMed

Yee, Kelsey L; Jansen, Lauren E; Lajoie, Curtis A; Penner, Michael H; Morse, Lettie; Kelly, Christine J

2018-01-01

Biomass pretreatment-derived degradation compounds, such as furfural and 5-hydroxymethyl-furfural (HMF), inhibit the growth of fermentation microorganisms that utilize biomass to produce fuels and chemicals. Here we report that recombinant manganese peroxidase (rMnP) produced from the yeast Pichia pastoris can degrade furfural and HMF making them less toxic to microorganisms. Treatment with rMnP or manganese(III) acetate reduced furfural and HMF concentrations in a dose-dependent manner. Furfural disappearance was accompanied by malonate disappearance and accumulation of four distinct degradation products. Furfural was more readily degraded by rMnP and manganese(III) acetate than HMF. Growth assays using Saccharomyces cerevisiae indicated that rMnP treatment reduced the toxicity of furfural and HMF. This work provides an avenue to use rMnP to increase the growth of fermentation microorganisms that are inhibited by toxic compounds derived from pretreatment of biomass. Copyright © 2017 Elsevier Inc. All rights reserved.

Performance and diversity of polyvinyl alcohol-degrading bacteria under aerobic and anaerobic conditions.

PubMed

Huang, Jianping; Yang, Shisu; Zhang, Siqi

2016-11-01

To compare the degradation performance and biodiversity of a polyvinyl alcohol-degrading microbial community under aerobic and anaerobic conditions. An anaerobic-aerobic bioreactor was operated to degrade polyvinyl alcohol (PVA) in simulated wastewater. The degradation performance of the bioreactor during sludge cultivation and the microbial communities in each reactor were compared. Both anaerobic and aerobic bioreactors demonstrated high chemical oxygen demand removal efficiencies of 87.5 and 83.6 %, respectively. Results of 16S rDNA sequencing indicated that Proteobacteria dominated in both reactors and that the microbial community structures varied significantly under different operating conditions. Both reactors obviously differed in bacterial diversity from the phyla Planctomycetes, Chlamydiae, Bacteroidetes, and Chloroflexi. Betaproteobacteria and Alphaproteobacteria dominated, respectively, in the anaerobic and aerobic reactors. The anaerobic-aerobic system is suitable for PVA wastewater treatment, and the microbial genetic analysis may serve as a reference for PVA biodegradation.

[Degradation and transformation of engineering carbon nanomaterials in the environment: A review].

PubMed

Yue, Fang-Ning; Luo, Shui-Ming; Zhang, Cheng-Dong

2013-02-01

With the large amount production and application of engineering carbon nanomaterials, their potential ecological risk has attracted extensive attention. The degradation and transformation of the carbon nanomaterials in the environment directly affect the fates and eco-toxicity of the nanomaterials in the environment, and the research of the degradation and transformation processes of the nanomaterials in the environment is the key link for the determination of the environmental capacity of the nanomaterials and for the evaluation of the nanomaterials life cycle in the environment. This paper briefly introduced the chemical transformation, microbial degradation, and photodegradation of the major engineering carbon nanomaterials (carbon nanotubes and fullerene) in the environment, and summarized the environmental and structural factors affecting the degradation of the nanomaterials and the related intrinsic mechanisms. The shortcomings of the related researches and the directions of the future research were also put forward.

Thin metal film and multilayers experiment (A0138-3)

NASA Technical Reports Server (NTRS)

Delaboudiniere, J. P.; Berset, J. M.

1984-01-01

The sources of degradation of in state of the art and newly developed components and testing the usefulness of the concept of storing experiment samples in dry nitrogen under launch and space vacuum conditions during reentry mission phase were investigated. Ultraviolet (UV) and extreme ultraviolet (EUV) experiments suffer degradations during space missions of even 1 month duration. It is suggested that the degradation is due to condensation of outgassing products, followed by solar induced polymerization, however, penetrating charged particles are also known to produce volume effects. Degradation may also start immediately after manufacturing of the component due to oxidation, moisture, or chemical corrosion by atmospheric constituents such as CO2 and SO2. When the filters are used as windows for gas absorption cells or gas filters, or when they define the instrumental bandwidth by themselves. The effects of mechanical degradation by thermal cycling and/or dust may cause a dramatic impact.

Carrier mounted bacterial consortium facilitates oil remediation in the marine environment.

PubMed

Simons, Keryn L; Sheppard, Petra J; Adetutu, Eric M; Kadali, Krishna; Juhasz, Albert L; Manefield, Mike; Sarma, Priyangshu M; Lal, Banwari; Ball, Andrew S

2013-04-01

Marine oil pollution can result in the persistent presence of weathered oil. Currently, removal of weathered oil is reliant on chemical dispersants and physical removal, causing further disruption. In contrast few studies have examined the potential of an environmentally sustainable method using a hydrocarbon degrading microbial community attached to a carrier. Here, we used a tank mesocosm system (50 l) to follow the degradation of weathered oil (10 g l(-1)) using a bacterial consortium mobilised onto different carrier materials (alginate or shell grit). GCMS analysis demonstrated that the extent of hydrocarbon degradation was dependent upon the carrier material. Augmentation of shell grit with nutrients and exogenous hydrocarbon degraders resulted in 75±14% removal of >C32 hydrocarbons after 12 weeks compared to 20±14% for the alginate carrier. This study demonstrated the effectiveness of a biostimulated and bioaugmented carrier material to degrade marine weathered oil. Copyright © 2013 Elsevier Ltd. All rights reserved.

Advances in Degradable Embolic Microspheres: A State of the Art Review

PubMed Central

Doucet, Jensen; Kiri, Lauren; O’Connell, Kathleen; Kehoe, Sharon; Lewandowski, Robert J.; Liu, David M.; Abraham, Robert J.; Boyd, Daniel

2018-01-01

Considerable efforts have been placed on the development of degradable microspheres for use in transarterial embolization indications. Using the guidance of the U.S. Food and Drug Administration (FDA) special controls document for the preclinical evaluation of vascular embolization devices, this review consolidates all relevant data pertaining to novel degradable microsphere technologies for bland embolization into a single reference. This review emphasizes intended use, chemical composition, degradative mechanisms, and pre-clinical safety, efficacy, and performance, while summarizing the key advantages and disadvantages for each degradable technology that is currently under development for transarterial embolization. This review is intended to provide an inclusive reference for clinicians that may facilitate an understanding of clinical and technical concepts related to this field of interventional radiology. For materials scientists, this review highlights innovative devices and current evaluation methodologies (i.e., preclinical models), and is designed to be instructive in the development of innovative/new technologies and evaluation methodologies. PMID:29373510

Degradation of some representative polycyclic aromatic hydrocarbons by the water-soluble protein extracts from Zea mays L. cv PR32-B10.

PubMed

Barone, Roberto; de Biasi, Margherita-Gabriella; Piccialli, Vincenzo; de Napoli, Lorenzo; Oliviero, Giorgia; Borbone, Nicola; Piccialli, Gennaro

2016-10-01

The ability of the water-soluble protein extracts from Zea mais L. cv. PR32-B10 to degrade some representative polycyclic aromatic hydrocarbons (PAHs), has been evaluated. Surface sterilized seeds of corn (Zea mais L. Pioneer cv. PR32-B10) were hydroponically cultivated in a growth chamber under no-stressful conditions. The water-soluble protein extracts isolated from maize tissues showed peroxidase, polyphenol oxidase and catalase activities. Incubation of the extracts with naphthalene, fluorene, phenanthrene and pyrene, led to formation of oxidized and/or degradation products. GC-MS and TLC monitoring of the processes showed that naphthalene, phenanthrene, fluorene and pyrene underwent 100%, 78%, 92% and 65% oxidative degradation, respectively, after 120 min. The chemical structure of the degradation products were determined by (1)H NMR and ESI-MS spectrometry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sphingolipid metabolism diseases.

PubMed

Kolter, Thomas; Sandhoff, Konrad

2006-12-01

Human diseases caused by alterations in the metabolism of sphingolipids or glycosphingolipids are mainly disorders of the degradation of these compounds. The sphingolipidoses are a group of monogenic inherited diseases caused by defects in the system of lysosomal sphingolipid degradation, with subsequent accumulation of non-degradable storage material in one or more organs. Most sphingolipidoses are associated with high mortality. Both, the ratio of substrate influx into the lysosomes and the reduced degradative capacity can be addressed by therapeutic approaches. In addition to symptomatic treatments, the current strategies for restoration of the reduced substrate degradation within the lysosome are enzyme replacement therapy (ERT), cell-mediated therapy (CMT) including bone marrow transplantation (BMT) and cell-mediated "cross correction", gene therapy, and enzyme-enhancement therapy with chemical chaperones. The reduction of substrate influx into the lysosomes can be achieved by substrate reduction therapy. Patients suffering from the attenuated form (type 1) of Gaucher disease and from Fabry disease have been successfully treated with ERT.

Bacterial degradation of chlorophenols and their derivatives

PubMed Central

2014-01-01

Chlorophenols (CPs) and their derivatives are persistent environmental pollutants which are used in the manufacture of dyes, drugs, pesticides and other industrial products. CPs, which include monochlorophenols, polychlorophenols, chloronitrophenols, chloroaminophenols and chloromethylphenols, are highly toxic to living beings due to their carcinogenic, mutagenic and cytotoxic properties. Several physico-chemical and biological methods have been used for removal of CPs from the environment. Bacterial degradation has been considered a cost-effective and eco-friendly method of removing CPs from the environment. Several bacteria that use CPs as their sole carbon and energy sources have been isolated and characterized. Additionally, the metabolic pathways for degradation of CPs have been studied in bacteria and the genes and enzymes involved in the degradation of various CPs have been identified and characterized. This review describes the biochemical and genetic basis of the degradation of CPs and their derivatives. PMID:24589366

Total organic carbon in a soil recovered with sewage sludge and native species of the Atlantic Forest

NASA Astrophysics Data System (ADS)

Mara Lima Goulart, Lívia; Amaral Guerrini, Iraê; Fidalgo de Faria, Marianne; Spada, Grasiela; Proença Nalesso, Pedro Henrique; Willian Carlos, Guilherme

2017-04-01

The use of organic waste such as sewage sludge, in the recovery of degraded áreas have shown very satisfactory results, because they are constituted by high contentes of organic matter and nutrients, essential to improve the physical and chemical properties of the soil. Thus, the objective of this study was to verify the total organic carbon (TOC) of a degraded soil, up to a metre deep, after 10 years of application of sewage sludge and planting native species of the Atlantic forest. The experiment was conducted at Fazenda Entre-Rios, owned by Suzano Papel e Celulose, in Itatinga, São Paulo, Brazil. The experiment was designed as randomized block with four replications, six doses of sewage sludge (0, 2.5, 5, 10, 15 and 20 t ha-1), conventional chemical fertilizer and only with potassium application, totaling eight treatments. Samples were collected every 20 cm (0-20, 20-40, 40-60, 60-80 and 80-100 cm) until reaching a metre deep. Ten years after trial deployment, the sewage sludge application in degraded soil was significantly influenced the TOC at all depths sampled. The highest values of the COT were observed in plots that received 15 and 20 t ha-1 of sewage sludge, in all depths sampled, except for the layer of 80-100 cm, which presented the highest average COT in the treatment with 10 t ha-1 of residue. As observed for all treatments, the highest TOC averages were observed in the superficial layers of the soil (0-20 and 20-40 cm). The sewage sludge application is useful to recover degraded soils, as it improving their chemical characteristics and showing to be a good alternative to the final destination of this residue.

Effect of in vitro enzymatic degradation on 3D printed poly(ε-caprolactone) scaffolds: morphological, chemical and mechanical properties.

PubMed

Ferreira, Joana; Gloria, Antonio; Cometa, Stefania; Coelho, Jorge F J; Domingos, Marco

2017-07-27

In recent years, the tissue engineering (TE) field has significantly benefited from advanced techniques such as additive manufacturing (AM), for the design of customized 3D scaffolds with the aim of guided tissue repair. Among the wide range of materials available to biomanufacture 3D scaffolds, poly(ε-caprolactone) (PCL) clearly arises as the synthetic polymer with the greatest potential, due to its unique properties - namely, biocompatibility, biodegradability, thermal and chemical stability and processability. This study aimed for the first time to investigate the effect of pore geometry on the in vitro enzymatic chain cleavage mechanism of PCL scaffolds manufactured by the AM extrusion process. Methods: Morphological properties of 3D printed PCL scaffolds before and after degradation were evaluated using Scanning Electron Microscopy (SEM) and micro-computed tomography (μ-CT). Differential Scanning Calorimetry (DSC) was employed to determine possible variations in the crystallinity of the scaffolds during the degradation period. The molecular weight was assessed using Size Exclusion Chromatography (SEC) while the mechanical properties were investigated under static compression conditions. Morphological results suggested a uniform reduction of filament diameter, while increasing the scaffolds' porosity. DSC analysis revealed and increment in the crystallinity degree while the molecular weight, evaluated through SEC, remained almost constant during the incubation period (25 days). Mechanical analysis highlighted a decrease in the compressive modulus and maximum stress over time, probably related to the significant weight loss of the scaffolds. All of these results suggest that PCL scaffolds undergo enzymatic degradation through a surface erosion mechanism, which leads to significant variations in mechanical, physical and chemical properties, but which has little influence on pore geometry.

Influence of strontium on structure, sintering and biodegradation behaviour of CaO-MgO-SrO-SiO2-P2O5-CaF2 glasses

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

Goel, Ashutosh; Rajagopal, Raghu R.; Ferreira, Jose M.

The present study investigates the influence of SrO on structure, apatite forming ability, physico-chemical degradation and sintering behaviour of melt-quenched bioactive glasses with composition: mol.% (36.07 – x) CaO – x SrO - 19.24 MgO – 5.61 P2O5 – 38.49 SiO2 – 0.59 CaF2, where x varies between 0 – 10. The detailed structural analysis of glasses has been made by infra red spectroscopy (FTIR) and magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR). Silicon was predominantly present as Q2 (Si) species while phosphorus was found in orthophosphate type environment in all the investigated glasses. The apatite forming ability of glassesmore » was investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h – 7 days. While increasing Sr2+/Ca2+ ratio in glasses did not affect the structure of glasses significantly, their apatite forming ability was decreased considerably. Further, physico-chemical degradation of glasses has been studied in accordance with ISO 10993-14 “Biological evaluation of medical devices – Part 14: Identification and quantification of degradation products from ceramics” in Tris HCl and citric acid buffer and the possible implications of ion release profile from glasses in different solutions has been discussed. The addition of strontium in glasses led to a 7-fold decrease in chemical degradation of glasses in Tris-HCl. The sintering of glass powders rendered glass-ceramics (GCs) with varying degree of crystallinity and good flexural strength (98-131 MPa) where the mechanical properties depend on the nature and amount of crystalline phases present in GCs.« less

Effect of Bacillus subtilis and NTA-APG on pyrene dissipation in phytoremediation of nickel co-contaminated wetlands by Scirpus triqueter.

PubMed

Liu, Xiaoyan; Hu, Xiaoxin; Zhang, Xinying; Chen, Xueping; Chen, Jing; Yuan, Xiaoyu

2018-06-15

A complex mix of organic pollutants and heavy metal made the remediation of contaminated wetlands more difficult. Few research focus on the remediation for pyrene enhanced by chemical reagents and pyrene degrading bacteria in the nickel co-contaminated soil. In this paper, the effect of chemical reagents (nitrilotriacetic acid and alkyl polyglucoside) and Bacillus subtilis on pyrene dissipation in phytoremediation of nickel co-contaminated soil by Scirpus triqueter was investigated. Similar seedlings of Scirpus triqueter were moved to uncontaminated soil and pyrene-nickel co-contaminated soil. The pots (14.8 cm diameter and 8.8 cm height) were set up in greenhouse and treated in different ways. After 60 days, plant biomass, radial oxygen loss (ROL), soil dehydrogenase activity (DHA) and pyrene concentration in soil were determined. Results showed that ROL rate and DHA in different groups was positively correlated with pyrene dissipation from soil. In the process of remediation, chemical reagents might have an indirect slight effect on pyrene dissipation (pyrene dissipation increased 21%) by affecting DHA firstly and redistributing pyrene fractions in the presence of pyrene degrading bacteria. Pyrene degrading bacteria were likely to affect pyrene dissipation by impacting ROL rate and DHA and played a more vital role in contributing to pyrene dissipation (pyrene dissipation increased 45%) from wetland. This study demonstrated that phytoremediation for pyrene in nickel co-contaminated soil by Scirpus triqueter can be enhanced by the application of NTA-APG and pyrene degrading bacteria and they could be reasonably restore the ecological environment of PAH-contaminated wetlands. Copyright © 2018 Elsevier Inc. All rights reserved.

Soft chemical synthesis of Ag{sub 3}SbS{sub 3} with efficient and recyclable visible light photocatalytic properties

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

Gusain, Meenakshi; Rawat, Pooja; Nagarajan, Rajamani, E-mail: rnagarajan@chemistry.du.ac.in

2014-12-15

Highlights: • Highly crystalline Ag{sub 3}SbS{sub 3} synthesized using soft chemical approach. • First time report of photocatalytic activity of Ag{sub 3}SbS{sub 3}. • Ag{sub 3}SbS{sub 3} degraded the harmful organic dyes rapidly under visible radiation. • Pseudo first order kinetics have been followed in these sets of reactions. • Up to 90% of Methylene Blue degraded even after 4th cycle of catalyst reuse. • Structure of catalyst is intact after reuse. • As the catalyst is heavy, its separation after use is quite simple. - Abstract: Application of Ag{sub 3}SbS{sub 3}, obtained by soft chemical approach involving rapid reactionmore » of air stable metal–thiourea complexes in ethylene glycol medium, as visible light photocatalyst for the degradation of dye solutions was investigated. Ag{sub 3}SbS{sub 3} was confirmed by high resolution powder X-ray diffraction pattern and its no defined morphology was present in SEM images. From UV–vis spectroscopy measurements, optical band gap of 1.77 eV was deduced for Ag{sub 3}SbS{sub 3}. Rapid degradation kinetics and recyclability was exhibited by Ag{sub 3}SbS{sub 3} towards Methylene Blue, Methyl Orange, Malachite Green, and Rhodamine 6G dye solutions under visible radiation. All these processes followed pseudo first order kinetics. High surface area (6.39 m{sup 2}/g), with mesopores (3.81 nm), arising from solvent mediated synthesis of Ag{sub 3}SbS{sub 3} has been correlated to its catalytic activity.« less

Removal of endocrine disruptors and non-steroidal anti-inflammatory drugs through wastewater chlorination: the effect of pH, total suspended solids and humic acids and identification of degradation by-products.

PubMed

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

2015-01-01

Endocrine disrupting chemicals (EDCs) and non-steroidal anti-inflammatory drugs (NSAIDs) are two groups of emerging pollutants the significance of which rests on their persistent detection in the aquatic environment and their possible adverse effects. Wastewater treatment plants are one of the major ways for transporting such chemicals in the aquatic environment. Chlorination is usually the last stage of treatment before wastewater being disposed to the aquatic environment. This work focuses on the evaluation of the effect of chlorine dose and specific wastewater characteristics (pH, total suspended solids and humic acids) on the removal of target EDCs and NSAIDs through chlorination. Another objective of this study is the identification of chlorination by-products of specific EDCs and NSAIDs and their dependence on contact time. Based on the results it is concluded that the effect of chlorine dose and humic acids concentration on the degradation of target compounds during chlorination is minimal. On the contrary, pH is a critical parameter which highly affects process performance. Moreover, it is concluded that not only the free available chlorine species, but also the properties of EDCs and NSAIDs under different pH conditions can affect chlorination process performance. The effect of TSS on the degradation of the target compounds during chlorination is more profound for chemicals with high Kow values and therefore higher affinity to partition to the particulate phase (i.e. nonylphenols, triclosan). Several degradation by-products were identified through chlorination of nonylphenol, bisphenol A and diclofenac. The dependence of these by-products on chlorination contact time is also demonstrated. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ereptiospiration.

PubMed

Woolley, Christine; Garcia, Antonio A; Santello, Marco

2017-04-12

Pure coconut oil, lanolin, and acetaminophen were vaporized at rates of 1-50 mg/min, using a porous network exhibiting a temperature gradient from 5000 to 5500 K/mm, without incurring noticeable chemical changes due to combustion, oxidation, or other thermally-induced chemical structural changes. The newly coined term "ereptiospiration" is used here to describe this combination of thermal transpiration at high temperature gradients since the process can force the creation of thermal aerosols by rapid heating in a localized zone. Experimental data were generated for these materials using two different supports for metering the materials to the battery powered coil: namely, a stainless steel fiber bundle and a 3-D printed steel cartridge. Heating coconut oil, lanolin, or acetaminophen in a beaker to lower temperatures than those achieved at the surface of the coil showed noticeable and rapid degradation in the samples, while visual and olfactory observations for ereptiospiration showed no noticeable degradation in lanolin and coconut oil while HPLC chromatograms along with visual observation confirm that within the limit of detection, acetaminophen remains chemically unaltered by ereptiospiration.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry

NASA Astrophysics Data System (ADS)

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-01

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry.

PubMed

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-15

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose. Copyright © 2016 Elsevier B.V. All rights reserved.

Cytotoxic macrolides from a new species of the deep-water marine sponge Leiodermatium.

PubMed

Sandler, Joel S; Colin, Patrick L; Kelly, Michelle; Fenical, William

2006-09-15

Chemical investigation of a new species of the deep-water marine sponge Leiodermatium, collected by manned submersible at a depth of 740 feet in Palau, resulted in the isolation of two cytotoxic macrolides, leiodolides A (1) and B (2). The leiodolides represent the first members of a new class of 19-membered ring macrolides, incorporating several unique functional groups including a conjugated oxazole ring, a bromine substituent, and an alpha-hydroxy-alpha-methyl carboxylic acid side-chain terminus. The structures of these new metabolites were established by spectroscopic analysis, chemical modification, and degradation. The relative and absolute stereochemistries at most chiral centers were assigned on detailed interpretation of spectroscopic data, coupled with chemical degradation and application of the modified Mosher ester method. Leiodolide A showed significant cytotoxicity (average GI(50) = 2.0 microM) in the National Cancer Institute's 60 cell line panel with enhanced activity against HL-60 leukemia and OVCAR-3 ovarian cancer cell lines.

Green synthesis of Pd NPs from Pimpinella tirupatiensis plant extract and their application in photocatalytic activity dye degradation

NASA Astrophysics Data System (ADS)

Narasaiah, Palajonna; Mandal, Badal Kumar; Sarada, N. C.

2017-11-01

The present report the synthesis of palladium nanoparticles through the green method route offers few advantages over the common chemical and physical procedures, as it is an easy and fast, eco-friendly and does not involve any costly chemicals as well as hazardous chemicals. In this study, we reported synthesis of Pd NPs by using the Pimpinella tirupatiensis plant Extract (PTPE). The synthesized Pd NPs was characterization using different technique such as UV-Visible for the formation of Pd NPs. FT-IR spectroscopy was performed to detect the bio-active molecules liable for reduction and capping of biogenic Pd NPs. Crystallinity of Pd NPs conformed by powder - XRD. In the present study performed photo catalytic activity of synthesized Pd NPs using organic dye such as Congo red (CR). Hence, this study concludes the PTPE aqueous extract produced Pd NPs can be act as promising material for the degradation of organic pollutants.

Changes of wood cell walls in response to hygro-mechanical steam treatment.

PubMed

Guo, Juan; Song, Kunlin; Salmén, Lennart; Yin, Yafang

2015-01-22

The effects of compression combined with steam treatment (CS-treatment), i.e. a hygro-mechanical steam treatment on Spruce wood were studied on a cell-structure level to understand the chemical and physical changes of the secondary cell wall occurring under such conditions. Specially, imaging FT-IR microscopy, nanoindentation and dynamic vapour absorption were used to track changes in the chemical structure, in micromechanical and hygroscopic properties. It was shown that CS-treatment resulted in different changes in morphological, chemical and physical properties of the cell wall, in comparison with those under pure steam treatment. After CS-treatment, the cellular structure displayed significant deformations, and the biopolymer components, e.g. hemicellulose and lignin, were degraded, resulting in decreased hygroscopicity and increased mechanical properties of the wood compared to both untreated and steam treated wood. Moreover, CS-treatment resulted in a higher degree of degradation especially in earlywood compared to a more uniform behaviour of wood treated only by steam. Copyright © 2014 Elsevier Ltd. All rights reserved.

Optical properties of anodically degraded ZnO

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

Messerschmidt, Daniel, E-mail: daniel.messerschmidt@bosch.com; Gnehr, Wolf-Michael; Eberhardt, Jens

2014-03-07

We discuss the optical properties of non-degraded and anodically degraded boron-doped zinc oxide (ZnO:B) deposited by low-pressure chemical vapour deposition on soda-lime glass. The optical model used to simulate the infrared reflectance in the wavelength range between 1.2 and 25 μm is based on the Maxwell-Garnett effective-medium theory. The model is sensitive to the conditions at the grain boundaries of the investigated polycrystalline ZnO:B films. We confirm that the presence of defect-rich grain boundaries, especially after degradation, causes a highly resistive ZnO:B film. Furthermore, indications of a degraded zinc oxide layer next to the ZnO:B/glass interface with different refractive index aremore » found. We present evidence for the creation of oxygen vacancies, based on Raman investigations, which correlate with a shift of the optical absorption edge of the ZnO:B. Investigations with scanning and transmission electron microscopy show microvoids at the grain boundaries after anodic degradation. This indicates that the grain/grain interfaces are the principle location of defects after degradation.« less

Quantifying pretreatment degradation compounds in solution and accumulated by cells during solids and yeast recycling in the Rapid Bioconversion with Integrated recycling Technology process using AFEX™ corn stover.

PubMed

Sarks, Cory; Higbee, Alan; Piotrowski, Jeff; Xue, Saisi; Coon, Joshua J; Sato, Trey K; Jin, Mingjie; Balan, Venkatesh; Dale, Bruce E

2016-04-01

Effects of degradation products (low molecular weight compounds produced during pretreatment) on the microbes used in the RaBIT (Rapid Bioconversion with Integrated recycling Technology) process that reduces enzyme usage up to 40% by efficient enzyme recycling were studied. Chemical genomic profiling was performed, showing no yeast response differences in hydrolysates produced during RaBIT enzymatic hydrolysis. Concentrations of degradation products in solution were quantified after different enzymatic hydrolysis cycles and fermentation cycles. Intracellular degradation product concentrations were also measured following fermentation. Degradation product concentrations in hydrolysate did not change between RaBIT enzymatic hydrolysis cycles; the cell population retained its ability to oxidize/reduce (detoxify) aldehydes over five RaBIT fermentation cycles; and degradation products accumulated within or on the cells as RaBIT fermentation cycles increased. Synthetic hydrolysate was used to confirm that pretreatment degradation products are the sole cause of decreased xylose consumption during RaBIT fermentations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by In-Situ TEM

DOE PAGES

Yang, Bin; Dyck, Ondrej K.; Univ. of Tennessee, Knoxville, TN; ...

2016-11-04

The chemical stability of organometallic halide perovskites is a major barrier facing their application in the fast rising field of next generation photovoltaics. These materials were shown to undergo degradation due to the influence of heat or moisture, significantly limiting the lifetime of associated devices. To overcome this stability issue, a fundamental understanding of degradation mechanisms is of foremost importance. Here, high resolution in situ transmission electron microscopy and electron energy loss spectroscopy elemental mapping were applied to probe morphological and structural changes in perovskite films during controlled environmental exposure treatments. Both moisture and oxygen in ambient air are revealedmore » to facilitate degradation in CH 3NH 3PbI 3 perovskites through decomposition and oxidation pathways, respectively. In addition, even in moisture- and oxygen-free environment evident degradation could be induced by heating at the solar cell s real-field operating temperature and the degradation was found to originate from defect sites. These findings provide fundamental insight to prevent degradation of perovskite materials and associated devices for realistic applications.« less

Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by In-Situ TEM

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

Yang, Bin; Dyck, Ondrej K.; Univ. of Tennessee, Knoxville, TN

The chemical stability of organometallic halide perovskites is a major barrier facing their application in the fast rising field of next generation photovoltaics. These materials were shown to undergo degradation due to the influence of heat or moisture, significantly limiting the lifetime of associated devices. To overcome this stability issue, a fundamental understanding of degradation mechanisms is of foremost importance. Here, high resolution in situ transmission electron microscopy and electron energy loss spectroscopy elemental mapping were applied to probe morphological and structural changes in perovskite films during controlled environmental exposure treatments. Both moisture and oxygen in ambient air are revealedmore » to facilitate degradation in CH 3NH 3PbI 3 perovskites through decomposition and oxidation pathways, respectively. In addition, even in moisture- and oxygen-free environment evident degradation could be induced by heating at the solar cell s real-field operating temperature and the degradation was found to originate from defect sites. These findings provide fundamental insight to prevent degradation of perovskite materials and associated devices for realistic applications.« less

Responses of soil physical and chemical properties to karst rocky desertification evolution in typical karst valley area

NASA Astrophysics Data System (ADS)

Chen, Fei; Zhou, Dequan; Bai, Xiaoyong; zeng, Cheng; Xiao, Jianyong; Qian, Qinghuan; Luo, Guangjie

2018-01-01

In order to reveal the differences of soil physical and chemical properties and their response mechanism to the evolution of KRD. The characteristics of soil physical and chemical properties of different grades of KRD were studied by field sampling method to research different types of KRD in the typical karst valley of southern China. Instead of using space of time, to explore the response and the mechanisms of the soil physical and chemical properties at the different evolution process. The results showed that: (1) There were significant differences in organic matter, pH, total nitrogen, total phosphorus, total potassium, sediment concentration, clay content and AWHC in different levels of KRD environment. However, these indicators are not with increasing desertification degree has been degraded, but improved after a first degradation trends; (2) The correlation analysis showed that soil organic matter, acid, alkali, total nitrogen, total phosphorus, total potassium and clay contents were significantly correlated with other physical and chemical factors. They are the key factors of soil physical and chemical properties, play a key role in improving soil physical and chemical properties and promoting nutrient cycling; (3) The principal component analysis showed that the cumulative contribution rate of organic matter, pH, total nitrogen, total phosphorus, total potassium and sediment concentration was 80.26%, which was the key index to evaluate rocky desertification degree based on soil physical and chemical properties. The results have important theoretical and practical significance for the protection and restoration of rocky desertification ecosystem in southwest China.

Degradation of phenolic compounds with hydrogen peroxide catalyzed by enzyme from Serratia marcescens AB 90027.

PubMed

Yao, Ri-Sheng; Sun, Min; Wang, Chun-Ling; Deng, Sheng-Song

2006-09-01

In this paper, the degradation of phenolic compounds using hydrogen peroxide as oxidizer and the enzyme extract from Serratia marcescens AB 90027 as catalyst was reported. With such an enzyme/H2O2 combination treatment, a high chemical oxygen demand (COD) removal efficiency was achieved, e.g., degradation of hydroquinone exceeded 96%. From UV-visible and IR spectra, the degradation mechanisms were judged as a process of phenyl ring cleavage. HPLC analysis shows that in the degradation p-benzoquinone, maleic acid and oxalic acid were formed as intermediates and that they were ultimately converted to CO2 and H2O. With the enzyme/H2O2 treatment, vanillin, hydroquinone, catechol, o-aminophenol, p-aminophenol, phloroglucinol and p-hydroxybenzaldehyde were readily degraded, whereas the degradation of phenol, salicylic acid, resorcinol, p-cholorophenol and p-nitrophenol were limited. Their degradability was closely related to the properties and positions of their side chain groups. Electron-donating groups, such as -OH, -NH2 and -OCH3 enhanced the degradation, whereas electron-withdrawing groups, such as -NO2, -Cl and -COOH, had a negative effect on the degradation of these compounds in the presence of enzyme/H2O2. Compounds with -OH at ortho and para positions were more readily degraded than those with -OH at meta positions.

Biodegradation pathway of an anionic surfactant (Igepon TC-42) during recycling waste water through plant hydroponics for advanced life support during long-duration space missions.

PubMed

Levine, L H; Kagie, H R; Garland, J L

2003-01-01

The degradation of an anionic surfactant (Igepon TC-42) was investigated as part of an integrated study of direct recycling of human hygiene water through hydroponic plant growth systems. Several chemical approaches were developed to characterize the degradation of Igepon and to measure the accumulation of intermediates such as fatty acids and methyl taurine. Igepon was rapidly degraded as indicated by the reduction of methylene blue active substances (MBAS) and component fatty acids. The Igepon degradation rate continued to increase over a period of several weeks following repeated daily exposure to 18 micrograms/l Igepon. The accumulation of free fatty acids and methyl taurine was also observed during decomposition of Igepon. The concentration of methyl taurine was below detection limit (0.2 nmol/ml) during the slow phase of Igepon degradation, and increased to 1-2 nmol/ml during the phase of rapid degradation. These findings support a degradation pathway involving initial hydrolysis of amide to release fatty acids and methyl taurine, and subsequent degradation of these intermediates. Published by Elsevier Science Ltd on behalf of COSPAR.

Biodegradation pathway of an anionic surfactant (Igepon TC-42) during recycling waste water through plant hydroponics for advanced life support during long-duration space missions

NASA Technical Reports Server (NTRS)

Levine, L. H.; Kagie, H. R.; Garland, J. L.

2003-01-01

The degradation of an anionic surfactant (Igepon TC-42) was investigated as part of an integrated study of direct recycling of human hygiene water through hydroponic plant growth systems. Several chemical approaches were developed to characterize the degradation of Igepon and to measure the accumulation of intermediates such as fatty acids and methyl taurine. Igepon was rapidly degraded as indicated by the reduction of methylene blue active substances (MBAS) and component fatty acids. The Igepon degradation rate continued to increase over a period of several weeks following repeated daily exposure to 18 micrograms/l Igepon. The accumulation of free fatty acids and methyl taurine was also observed during decomposition of Igepon. The concentration of methyl taurine was below detection limit (0.2 nmol/ml) during the slow phase of Igepon degradation, and increased to 1-2 nmol/ml during the phase of rapid degradation. These findings support a degradation pathway involving initial hydrolysis of amide to release fatty acids and methyl taurine, and subsequent degradation of these intermediates. Published by Elsevier Science Ltd on behalf of COSPAR.

Mechanisms of charcoal degradation during its initial stages of decomposition

NASA Astrophysics Data System (ADS)

Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W. I.

2010-05-01

Future climatic changes might result in an increased potential for wildfires, whereby incorporation of charred biomass into soil would increase. The incomplete combustion of biomass results in the production of a chemically heterogeneous class of highly condensed compounds known as pyrogenic C (PyC), which is generally considered resistant to microbial degradation. Recently, studies based on short-term laboratory incubations with soil have indicated that PyC can also eventually degrade (Baldock and Smernik, 2002; Hamer et al., 2004) and it is now widely accepted that a significant quantity of these resistant fraction of soil must have undergone degradation in terrestrial environments. Charcoal has been shown to decompose faster in the initial stages (first 2-3 months) and stabilize later (Kuzyakov et al., 2009). However, studies describing charcoal transformation processes remain scarce. The different potential degradation mechanisms have not yet been studied in combination, and therefore the relative importance for PyC degradation has not been evaluated. We are conducting an incubation experiment to study the biological, chemical and physical degradation/stabilization processes of PyC in soil under controlled conditions. We use Pinus ponderosa 13C/15N labeled (13C: 800 per mil, 15N: 4.2 atom %) wood and charcoal (pyrolysed at 450 °C under N2 atmosphere). We incubate soil from Lägeren forest (Wettingen, Switzerland) with three kind of organic inputs, labeled wood, char and no littler control. The decomposition rates would be estimated based on 13C of CO2 entrapped in NaOH. Time course destructive sampling would be done during the study. Lyophilized soil subsamples will be used for analysis of the amount of 13C incorporation in the microbial biomass using fumigation extraction method and phospholipids fatty acid analysis (PLFA). The remaining PyC in the soil would be characterized for the changes in its chemistry at the molecular level using Benzenepolycarboxlic acid (BPCA) molecular marker method and 13C 15N NMR. This communication aims to report the first four months results of this study at a higher time resolution. The outcome of this study would facilitate in elucidating the potential decomposition rate of charcoal and consequent changes in its physical, chemical and biological properties in the soil during the initial stages of decomposition. In addition, application of highly labeled 13C PyC would enable us in this study to trace the transformation products. References Baldock, J.A., and Smernik, R.J. (2002). Chemical composition and bioavailability of thermally, altered Pinus resinosa (Red Pine) wood. Organic Geochemistry 33, 1093-1109. Hamer, U., Marschner, B., Brodowski, S., and Amelung, W. (2004). Interactive priming of black carbon and glucose mineralisation. Organic Geochemistry 35, 823-830. Kuzyakov, Y., Subbotina, I., Chen, H.Q., Bogomolova, I., and Xu, X.L. (2009). Black carbon decomposition and incorporation into soil microbial biomass estimated by C-14 labeling. Soil Biology and Biochemistry 41, 210-219.

Investigating Marine Dissolved Organic Matter Fluorescence Transformations with Organic Geochemical Proxies in a Growth and Degradation Experiment using Amino Acids, Amino Sugars, and Phenols

NASA Astrophysics Data System (ADS)

Shields, M. R.; Bianchi, T. S.; Osburn, C. L.; Kinsey, J. D.; Ziervogel, K.; Schnetzer, A.

2017-12-01

The origin and mechanisms driving the formation of fluorescent dissolved organic matter (FDOM) in the open ocean remain unclear. Although recent studies have attempted to deconvolve the chemical composition and source of marine FDOM, these studies have been qualitative in nature. Here, we investigate these transformations using a more quantitative biomarker approach in a controlled growth and degradation experiment. In this experiment, a natural assemblage of phytoplankton was collected off the coast of North Carolina and incubated within roller bottles containing 0.2 µm-filtered North Atlantic surface water amended with f/2 nutrients. Samples were collected at the beginning (day 0), during exponential growth (day 13), stationary (day 20), and degradation (day 62) phases of the phytoplankton incubation. Amino acids, amino sugars, and phenolic compounds of the dissolved (DOM) were measured in conjunction with enzyme assays and bacterial counts to track shifts in OM quality as FDOM formed and was then transformed throughout the experiment. The results from the chemical analyses showed that the OM composition changed significantly from the initial and exponential phases to the stationary and degradation phases of the experiment. The percentage of aromatic amino acids to the total amino acid pool increased significantly during the exponential phase of phytoplankton growth, but then decreased significantly during the stationary and degradation phases. This increase was positively correlated to the fractional contribution of the protein-like peak in fluorescence to the total FDOM fluorescence. An increase in the concentration of amino acid degradation products during the stationary and degradation phases suggests that compositional changes in OM were driven by microbial transformation. This was further supported by a concurrent increase in total enzyme activity and increase in "humic-like" components of the FDOM. These findings link the properties and formation of FDOM to the overall quality and diagenetic state of marine OM and to the marine carbon and nitrogen cycles.

Microbial degradation of the lamprey larvicide 3-trifluoromethyl-4-nitrophenol in sediment-water systems

USGS Publications Warehouse

Kempe, Lloyd L.

1973-01-01

The selective lampricide 3-trifluoromethyl-4-nitrophenol (TFM), maintained in the water at concentrations of 1 to 6 I?g/ml for several hours, kills larval sea lampreys (Petromyzon marinus) in tributaries of the Great Lakes. Because the fate of TFM in the environment is a matter of concern, the interactions of this chemical with river and lake sediments were studied in laboratory experiments. In mixtures of TFM, water, and sediment held in aquariums, the TFM decreased progressively and nearly or completely disappeared in 1 to 4 weeks; concentrations of the fluoride ion increased; and the systems became nontoxic for sea lamprey larvae and goldfish (Carassius auratus). If the reduction in TFM ceased before all of the chemical had disappeared, the process resumed when nutrient broth was added. Loss of TFM from the systems was prevented by the addition of an antiseptic (phenol) and by heat sterilization. Enrichment cultures of microorganisms isolated from stream and lake sediments degraded TFM in nutrient broths. I conclude that TFM is degraded by microorganisms that live in sediment-water systems.

Anomalous aging of EPDM and FEPM under combined thermo-oxidative and hydrolytic conditions

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

Redline, Erica M.; Celina, Mathias C.; Harris, Charles E.

Previous observation of EPDM and FEPM materials aged in thermo-oxidative and thermo-oxidative plus hydrolytic environments revealed an unusual trend: the degradation and disintegration of these polymers in the former case but the ability to maintain mechanical performance and shape in the latter. No abnormalities were observed in the chemical (oxidation rates, FTIR spectra, solvent uptake, gel content, and weight loss vs. temperature) or physical (modulus profile) measurements that could explain these empirically observed aging differences. A second controlled aging test was conducted to verify this trend using only EPDM. Once again it was shown that thermo-oxidative conditions appear to causemore » more degradative damage (enhanced embrittlement) than observed for the combined thermo-oxidative plus hydrolytic environments. From these data we conclude that water may favorably interfere with normal thermo-oxidative degradation processes. This interference may occur via some combination of chemical and physical property changes in the presence of steam such as: oxidation rate and O 2 permeability changes, additional sensitivity to hydrolytic damage, and/or mechanistic changes in relation to pH and hydroperoxide formation.« less

Change of the structure and the digestibility of myofibrillar proteins in Nanjing dry-cured duck during processing.

PubMed

Du, Xiaojing; Sun, Yangying; Pan, Daodong; Wang, Ying; Ou, Changrong; Cao, Jinxuan

2018-06-01

To investigate the change of bioavailability and structure of myofibrillar proteins during Nanjing dry-cured duck processing, carbonyl content, sulfhydryl (SH) group, disulfide (SS) group, sodium dodecyl sulfate polyacrylamide gel electrophoresis, surface hydrophobicity, secondary structures and in vitro digestibility were determined. During processing, carbonyl content and surface hydrophobicity increased; SH turned into SS group; α-helix turned into β-sheet and random coil fractions. Protein degradation occurred during dry-curing and drying-ripening stages. The in vitro digestibility of pepsin and pancreatic proteases increased during the salt curing stage and decreased during the drying-ripening stage. The increase of digestibility could be attributed to the mild oxidation, degradation and unfolding of proteins while the decrease of digestibility was related to the intensive oxidation and aggregation of proteins. Protein degradation was not a main factor of digestibility during the drying-ripening stage. Results demonstrated that the bioavailability loss of myofibrillar proteins in Nanjing dry-cured duck occurred during the stage of drying-ripening instead of curing. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Anomalous aging of EPDM and FEPM under combined thermo-oxidative and hydrolytic conditions

DOE PAGES

Redline, Erica M.; Celina, Mathias C.; Harris, Charles E.; ...

2017-09-15

Previous observation of EPDM and FEPM materials aged in thermo-oxidative and thermo-oxidative plus hydrolytic environments revealed an unusual trend: the degradation and disintegration of these polymers in the former case but the ability to maintain mechanical performance and shape in the latter. No abnormalities were observed in the chemical (oxidation rates, FTIR spectra, solvent uptake, gel content, and weight loss vs. temperature) or physical (modulus profile) measurements that could explain these empirically observed aging differences. A second controlled aging test was conducted to verify this trend using only EPDM. Once again it was shown that thermo-oxidative conditions appear to causemore » more degradative damage (enhanced embrittlement) than observed for the combined thermo-oxidative plus hydrolytic environments. From these data we conclude that water may favorably interfere with normal thermo-oxidative degradation processes. This interference may occur via some combination of chemical and physical property changes in the presence of steam such as: oxidation rate and O 2 permeability changes, additional sensitivity to hydrolytic damage, and/or mechanistic changes in relation to pH and hydroperoxide formation.« less

Effect of pre-heating on the chemical oxidation efficiency: implications for the PAH availability measurement in contaminated soils.

PubMed

Biache, Coralie; Lorgeoux, Catherine; Andriatsihoarana, Sitraka; Colombano, Stéfan; Faure, Pierre

2015-04-09

Three chemical oxidation treatments (KMnO4, H2O2 and Fenton-like) were applied on three PAH-contaminated soils presenting different properties to determine the potential use of these treatments to evaluate the available PAH fraction. In order to increase the available fraction, a pre-heating (100 °C under N2 for one week) was also applied on the samples prior oxidant addition. PAH and extractable organic matter contents were determined before and after treatment applications. KMnO4 was efficient to degrade PAHs in all the soil samples and the pre-heating slightly improved its efficiency. H2O2 and Fenton-like treatments presented low efficiency to degrade PAH in the soil presenting poor PAH availability, however, the PAH degradation rates were improved with the pre-heating. Consequently H2O2-based treatments (including Fenton-like) are highly sensitive to contaminant availability and seem to be valid methods to estimate the available PAH fraction in contaminated soils. Copyright © 2014 Elsevier B.V. All rights reserved.

In situ analysis of capacity fade in thin-film anodes for high performance Li-ion all-solid-state batteries

NASA Astrophysics Data System (ADS)

Leite, Marina S.; Gong, Chen; Ruzmetov, Dmitry; Talin, A. Alec

There is still a pressing need to understand how the solid-interfaces in Li-ion all-solid-batteries form, including their chemical composition and electrical characteristics. In order to resolve the origin of the degradation mechanism in Al anodes, we combine in situ scanning electron microscopy in ultra-high vacuum with electrochemical cycling, in addition to ex situ characterization of the morphological, chemical, and electrical changes of the Al anodes upon lithiation. An AlLi alloy capped by a stable Al-Li-O is formed on the top surface of the anode, trapping Li, which results in the capacity fade, from 48.0 to 41.5 μ.Ah/cm2 in two cycles. The addition of a Cu capping layer is insufficient to prevent the device degradation because of the fast Li diffusion within Al. Yet, Si present extremely stable cycling: >92% of capacity retention after 100 cycles, with average Coulombic efficiency of 98%. Our in situ measurements represent a new platform for probing the real-time degradation of electrodes in all-solid-state batteries for energy storage devices.

Degradation of Toxic Chemicals by Zero-Valent Metal Nanoparticles - A Literature Review

DTIC Science & Technology

2005-11-01

oxidative reactions. Oxidative reactions are of primary interest to us as they have the potential to degrade organophosphorous nerve agents as well...a) mustard and b) nerve agent (general structure). To decontaminate mustard there are two approaches, dechlorination or oxidation of the sulfur, the...later of which is preferable due to the reversibility of the former. To decontaminate the nerve agents oxidation is required to replace X2, X3 and

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

Coleman, R.

Plastics can be made from starchy food waste. This article describes a method by which these plastics break down into harmless chemicals when exposed to sunlight, water or bacteria. Degradable trash bags and agricultural mulch films can replace some of the millions of pounds of nondegradable plastics used each year. Researchers at Argonne National Laboratory developed that involves enzymatically converting potato waste into glucose, fermenting the glucose to lactic acid using bacteria, and then using the lactic acid to construct fully degradable plastics.

The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

USGS Publications Warehouse

Spiker, E. C.; Hatcher, P.G.

1987-01-01

Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the ??13C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on ??13C values should consider the possibility of a 1 to 2 per mil decrease in the ??13C value of degraded wood. ?? 1987.

Class and Home Problems: Modeling of an Industrial Anaerobic Digester: A Case Study for Undergraduate Students

ERIC Educational Resources Information Center

Durruty, Ignacio; Ayude, María A.

2014-01-01

The case study discussed in this work is used at the chemical reaction engineering course, offered in fifth-year of the chemical engineering undergraduate program at National University of Mar del Plata (UNMdP). A serial-parallel reaction system based on the anaerobic degradation of particulate-containing potato processing wastewater is presented.…

A Rapid and Inexpensive Bioassay to Evaluate the Decontamination of Organophosphates

DTIC Science & Technology

2012-01-01

weather natu- rally over time. Actual chemical degradation of the tox- in often relied on harsh chemicals such as calcium oxide and chlorine dioxide...New decontaminating compounds have been developed that are more effective or more en- vironmentally friendly, including organophosphorous acid ...quires sophisticated instrumental analytical techniques such as liquid or gas chromatography, which involves expensive equipment and trained personnel

Stormwater filtration of toxic heavy metal ions using lignocellulosic materials selection process, fiberization, chemical modification, and mat formation

Treesearch

James S. Han

1999-01-01

Lignocellulosic materials were evaluated for their effectiveness in filtering toxic heavy metals from stormwater. Kenaf, alfalfa, juniper, and aspen fibers were used as models to evaluate the effectiveness and limitations of chemical modification and the extent of fiber degradation. Individual and mixed aqueous solutions of nickel, copper, zinc, and cadmium in various...

Effects of hydrologic conditions on biogeochemical processes and organic pollutant degradation in salt marsh sediments

Treesearch

W. James Catallo

2000-01-01

This work addressed the influence of tidal vs. static hydrologic conditions on biogeochemical processes and the transformation of pollutant organic chemicals (eight representative N-, O-, and S-heterocycles (NOSHs) from coal chemicals, crude oils, and pyrogenic mixtures) in salt marsh sediments. The goals were to: (1) determine the effects of static (flooded, drained)...

Chemical smoke marker emissions during flaming and smoldering phases of laboratory open burning of wildland fuels

Treesearch

Taehyoung Lee; Amy P. Sullivan; Laura Mack; Jose L. Jimenez; Sonia M. Kreidenweis; Timothy B. Onasch; Douglas R. Worsnop; William Malm; Cyle E. Wold; Wei Min Hao; Jeffrey L. Collett

2010-01-01

Smoke emitted by prescribed and wild fires can make a substantial contribution to ambient aerosol (McMeeking et al. 2006; Park et al. 2007; Spracklen et al. 2007). Approaches to investigate these contributions have used a variety of different chemical smoke markers, including levoglucosan, produced by thermal degradation of cellulose, and water-soluble potassium (...

Protein and Lipid Binding Parameters in Rainbow Trout (Oncorhynchus mykiss) Blood and Liver Fractions to Extrapolate from an in Vitro metabolic Degradation Assay to in Vivo Bioaccumulation Potential of Hydrophobic Organic Chemicals

EPA Science Inventory

Biotransformation reduces the extent to which environmental contaminants accumulate in fish and other aquatic biota. Unfortunately, the tendency for compounds to be metabolized is not easily predicted from physico-chemical properties (e.g., octanol:water partitioning) or an exam...

Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents.

PubMed

Bobbitt, N Scott; Mendonca, Matthew L; Howarth, Ashlee J; Islamoglu, Timur; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

2017-06-06

Owing to the vast diversity of linkers, nodes, and topologies, metal-organic frameworks can be tailored for specific tasks, such as chemical separations or catalysis. Accordingly, these materials have attracted significant interest for capture and/or detoxification of toxic industrial chemicals and chemical warfare agents. In this paper, we review recent experimental and computational work pertaining to the capture of several industrially-relevant toxic chemicals, including NH 3 , SO 2 , NO 2 , H 2 S, and some volatile organic compounds, with particular emphasis on the challenging issue of designing materials that selectively adsorb these chemicals in the presence of water. We also examine recent research on the capture and catalytic degradation of chemical warfare agents such as sarin and sulfur mustard using metal-organic frameworks.

Computational Chemistry and Lubrication

NASA Technical Reports Server (NTRS)

Zehe, Michael J.

1998-01-01

Members of NASA Lewis Research Center's Tribology and Surface Science Branch are applying high-level computational chemistry techniques to the development of new lubrication systems for space applications and for future advanced aircraft engines. The next generation of gas turbine engines will require a liquid lubricant to function at temperatures in excess of 350 C in oxidizing environments. Conventional hydrocarbon-based lubricants are incapable of operating in these extreme environments, but a class of compounds known as the perfluoropolyether (PFAE) liquids (see the preceding illustration) shows promise for such applications. These commercially available products are already being used as lubricants in conditions where low vapor pressure and chemical stability are crucial, such as in satellite bearings and composite disk platters. At higher temperatures, however, these compounds undergo a decomposition process that is assisted (catalyzed) by metal and metal oxide bearing surfaces. This decomposition process severely limits the applicability of PFAE's at higher temperatures. A great deal of laboratory experimentation has revealed that the extent of fluid degradation depends on the chemical properties of the bearing surface materials. Lubrication engineers would like to understand the chemical breakdown mechanism to design a less vulnerable PFAE or to develop a chemical additive to block this degradation.

Operational and biological analyses of branched water-adjustment and combined treatment of wastewater from a chemical industrial park.

PubMed

Xu, Ming; Cao, Jiashun; Li, Chao; Tu, Yong; Wu, Haisuo; Liu, Weijing

2018-01-01

The combined biological processes of branched water-adjustment, chemical precipitation, hydrolysis acidification, secondary sedimentation, Anoxic/Oxic and activated carbon treatment were used for chemical industrial wastewater treatment in the Taihu Lake Basin. Full-scale treatment resulted in effluent chemical oxygen demand, total nitrogen, NH 3 -N and total phosphorus of 35.1, 5.20, 3.10 and 0.15 mg/L, respectively, with a total removal efficiency of 91.1%, 67.1%, 70.5% and 89.3%, respectively. In this process, short-circuited organic carbon from brewery wastewater was beneficial for denitrification and second-sulfate reduction. The concentration of effluent fluoride was 6.22 mg/L, which also met the primary standard. Gas Chromatography-Mass Spectrometry analysis revealed that many types of refractory compounds were present in the inflow. Microbial community analysis performed in the summer by PCR-denaturing gradient gel electrophoresis and MiSeq demonstrated that certain special functional bacteria, such as denitrificans, phosphorus-accumulating bacteria, sulfate- and perhafnate-reducing bacteria, aromatic compound-degrading bacteria and organic fluoride-degrading bacteria, present in the bio-tanks were responsible for the acceptable specific biological pollutant reduction achieved.

Organic Dye Degradation Under Solar Irradiation by Hydrothermally Synthesized ZnS Nanospheres

NASA Astrophysics Data System (ADS)

Samanta, Dhrubajyoti; Chanu, T. Inakhunbi; Basnet, Parita; Chatterjee, Somenath

2018-02-01

The green synthesis of ZnS nanospheres using Citrus limetta (sweet lime) juice as a capping agent through a conventional hydrothermal method was studied. The particle size, morphology, chemical composition, band gap, and optical properties of the synthesized ZnS nanospheres were characterized using x-ray diffraction spectroscopy, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and ultraviolet-visible spectroscopy. The photocatalytic activity of the ZnS nanospheres was evaluated by degradation of rhodamine B (RhB) and methyl orange (MO) under solar irradiation. Upon 150 min of solar irradiation, the extent of degradation was 94% and 77% for RhB and MO, respectively.

When synthetic chemicals degrade in the environment: What are the absolute fate, effects, and potential risks to humans and the ecosystem?

USGS Publications Warehouse

Boxall, Alistair; Sinclair, C.; Fenner, Kathrin; Kolpin, Dana W.; Maund, S.

2004-01-01

Although some regulatory schemes require information about the impacts of degradates on human and environmental health, that information does not exist for many compounds (25, 26). Pesticides are the exception. In this article, we bring together the available data to address the environmental behavior of degradates and their effects on organisms and discuss how to identify substances of potential concern. In addition, we cite gaps in the current knowledge and make recommendations for future research requirements. While the article focuses on pesticides, we believe these observations can be extended to biologically active compounds and some industrial substances.

Degradation of toxaphene in water during anaerobic and aerobic conditions.

PubMed

LacayoR, M; van Bavel, B; Mattiasson, B

2004-08-01

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.

Microstructural and strength stability of CVD SiC fibers in argon environment

NASA Technical Reports Server (NTRS)

Bhatt, Ramakrishna T.; Hull, David R.

1991-01-01

The room temperature tensile strength and microstructure of three types of commercially available chemically vapor deposited silicon carbide fibers were measured after 1, 10, and 100 hour heat treatments under argon pressures of 0.1 to 310 MPa at temperatures to 2100 C. Two types of fiber had carbon-rich surface coatings and the other contained no coating. All three fiber types showed strength degradation beyond 1400 C. Time and temperature of exposure had greater influence on strength degradation than argon pressure. Recrystallization and growth of near stoichiometric SiC grains appears to be the dominant mechanism for the strength degradation.

Microstructural and strength stability of CVD SiC fibers in argon environments

NASA Technical Reports Server (NTRS)

Bhatt, Ramakrishna T.; Hull, David R.

1991-01-01

The room temperature tensile strength and microstructure of three types of commercially available chemically vapor deposited silicon carbide fibers were measured after 1, 10, and 100 hour heat treatments under argon pressures of 0.1 to 310 MPa at temperatures to 2100 C. Two types of fiber had carbon-rich surface coatings and the other contained no coating. All three fiber types showed strength degradation beyond 1400 C. Time and temperature of exposure had greater influence on strength degradation than argon pressure. Recrystallization and growth of near stoichiometric SiC grains appears to be the dominant mechanism for the strength degradation.

Indicators: Fish Assemblage

EPA Pesticide Factsheets

Fish assemblage refers to the variety and abundance of fish species in a given waterbody. Fish are sensitive indicators of physical and chemical habitat degradation, environmental contamination, migration barriers, and overall ecosystem productivity.

Concordant Chemical Reaction Networks

PubMed Central

Shinar, Guy; Feinberg, Martin

2015-01-01

We describe a large class of chemical reaction networks, those endowed with a subtle structural property called concordance. We show that the class of concordant networks coincides precisely with the class of networks which, when taken with any weakly monotonic kinetics, invariably give rise to kinetic systems that are injective — a quality that, among other things, precludes the possibility of switch-like transitions between distinct positive steady states. We also provide persistence characteristics of concordant networks, instability implications of discordance, and consequences of stronger variants of concordance. Some of our results are in the spirit of recent ones by Banaji and Craciun, but here we do not require that every species suffer a degradation reaction. This is especially important in studying biochemical networks, for which it is rare to have all species degrade. PMID:22659063

Strategies to characterize fungal lipases for applications in medicine and dairy industry.

PubMed

Gopinath, Subash C B; Anbu, Periasamy; Lakshmipriya, Thangavel; Hilda, Azariah

2013-01-01

Lipases are water-soluble enzymes that act on insoluble substrates and catalyze the hydrolysis of long-chain triglycerides. Lipases play a vital role in the food, detergent, chemical, and pharmaceutical industries. In the past, fungal lipases gained significant attention in the industries due to their substrate specificity and stability under varied chemical and physical conditions. Fungal enzymes are extracellular in nature, and they can be extracted easily, which significantly reduces the cost and makes this source preferable over bacteria. Soil contaminated with spillage from the products of oil and dairy harbors fungal species, which have the potential to secrete lipases to degrade fats and oils. Herein, the strategies involved in the characterization of fungal lipases, capable of degrading fatty substances, are narrated with a focus on further applications.

Covalent attachment and growth of nanocrystalline films of photocatalytic TiOF2

NASA Astrophysics Data System (ADS)

Zhu, Jian; Lv, Fujian; Xiao, Shengxiong; Bian, Zhenfeng; Buntkowsky, Gerd; Nuckolls, Colin; Li, Hexing

2014-11-01

This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation.This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation. Electronic supplementary information (ESI) available: Methods for sample preparation, characterization and Fig. S1-S8. See DOI: 10.1039/c4nr05598e

Strategies to Characterize Fungal Lipases for Applications in Medicine and Dairy Industry

PubMed Central

Gopinath, Subash C. B.; Anbu, Periasamy; Lakshmipriya, Thangavel; Hilda, Azariah

2013-01-01

Lipases are water-soluble enzymes that act on insoluble substrates and catalyze the hydrolysis of long-chain triglycerides. Lipases play a vital role in the food, detergent, chemical, and pharmaceutical industries. In the past, fungal lipases gained significant attention in the industries due to their substrate specificity and stability under varied chemical and physical conditions. Fungal enzymes are extracellular in nature, and they can be extracted easily, which significantly reduces the cost and makes this source preferable over bacteria. Soil contaminated with spillage from the products of oil and dairy harbors fungal species, which have the potential to secrete lipases to degrade fats and oils. Herein, the strategies involved in the characterization of fungal lipases, capable of degrading fatty substances, are narrated with a focus on further applications. PMID:23865040

Hydroxycinnamic acid degradation, a broadly conserved trait, protects Ralstonia solanacearum from chemical plant defenses and contributes to root colonization and virulence

PubMed Central

Lowe, Tiffany M.; Ailloud, Florent; Allen, Caitilyn

2014-01-01

Plants produce hydroxycinnamic acid defense compounds (HCAs) to combat pathogens, such as the bacterium Ralstonia solanacearum. We showed that an HCA degradation pathway is genetically and functionally conserved across diverse R. solanacearum strains. Further, a Δfcs (feruloyl-CoA synthetase) mutant that cannot degrade HCAs was less virulent on tomato plants. To understand the role of HCA degradation in bacterial wilt disease, we tested the following hypotheses: HCA degradation helps the pathogen (1) grow, as a carbon source; (2) spread, by reducing physical barriers HCA-derived; and (3) survive plant antimicrobial compounds. Although HCA degradation enabled R. solanacearum growth on HCAs in vitro, HCA degradation was dispensable for growth in xylem sap and root exudate, suggesting that HCAs are not significant carbon sources in planta. Acetyl-bromide quantification of lignin demonstrated that R. solanacearum infections did not affect the gross quantity or distribution of stem lignin. However, the Δfcs mutant was significantly more susceptible to inhibition by two HCAs: caffeate and p-coumarate. Finally, plant colonization assays suggested that HCA degradation facilitates early stages of infection and root colonization. Together, these results indicated that ability to degrade HCAs contributes to bacterial wilt virulence by facilitating root entry and by protecting the pathogen from HCA toxicity. PMID:25423265

Radiation-induced degradation of cyclohexanebutyric acid in aqueous solutions by gamma ray irradiation

NASA Astrophysics Data System (ADS)

Jia, Wenbao; He, Yanquan; Ling, Yongsheng; Hei, Daqian; Shan, Qing; Zhang, Yan; Li, Jiatong

2015-04-01

The radiation-induced degradation of cyclohexanebutyric acid under gamma ray irradiation was investigated. Degradation experiments were performed with 100 mL sealed Pyrex glass vessels loaded with 80 mL of cyclohexanebutyric acid solutions at various initial concentrations of 10, 20, and 40 mg L-1. The absorbed doses were controlled at 0, 0.65, 1.95, 3.25, 6.5, 9.75, and 13 kGy. The results showed that gamma ray irradiation could effectively degrade cyclohexanebutyric acid in aqueous solutions. The removal rate of cyclohexanebutyric acid increased significantly with the increase of absorbed dose and the decrease of its initial concentration. At the same time, the removal of chemical oxygen demand (COD) was as effective as that of cyclohexanebutyric acid. The kinetic studies showed that the degradation of cyclohexanebutyric acid followed pseudo first-order reaction. Above all, the proposed mechanism obtained when NaNO2, NaNO3 and tert-butanol were added showed that the •OH radical played a major role in the gamma degradation process of cyclohexanebutyric acid, while •H and eaq- played a minor role in the gamma degradation process. The degradation products were identified by Fourier transform infrared spectroscopy (FTIR) and gas chromatography/mass spectrometry (GC/MS) during cyclohexanebutyric acid degradation.

High Temperature Degradation Mechanisms in Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Cunningham, Ronan A.

1996-01-01

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Diffusion Dominant Solute Transport Modelling in Fractured Media Under Deep Geological Environment - 12211

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

Kwong, S.; Jivkov, A.P.

2012-07-01

Deep geologic disposal of high activity and long-lived radioactive waste is gaining increasing support in many countries, where suitable low permeability geological formation in combination with engineered barriers are used to provide long term waste contaminant and minimise the impacts to the environment and risk to the biosphere. This modelling study examines the solute transport in fractured media under low flow velocities that are relevant to a deep geological environment. In particular, reactive solute transport through fractured media is studied using a 2-D model, that considers advection and diffusion, to explore the coupled effects of kinetic and equilibrium chemical processes.more » The effects of water velocity in the fracture, matrix porosity and diffusion on solute transport are investigated and discussed. Some illustrative modelled results are presented to demonstrate the use of the model to examine the effects of media degradation on solute transport, under the influences of hydrogeological (diffusion dominant) and microbially mediated chemical processes. The challenges facing the prediction of long term degradation such as cracks evolution, interaction and coalescence are highlighted. The potential of a novel microstructure informed modelling approach to account for these effects is discussed, particularly with respect to investigating multiple phenomena impact on material performance. The GRM code is used to examine the effects of media degradation for a geological waste disposal package, under the combined hydrogeological (diffusion dominant) and chemical effects in low groundwater flow conditions that are typical of deep geological disposal systems. An illustrative reactive transport modelling application demonstrates the use of the code to examine the interplay of kinetic controlled biogeochemical reactive processes with advective and diffusive transport, under the influence of media degradation. The initial model results are encouraging which show the disposal system to evolve in a physically realistic manner. In the example presented the reactive-transport coupling develops chemically reducing zones, which limit the transport of uranium. This illustrates the potential significance of media degradation and chemical effect on the transport of radionuclides which would need to be taken into account when examining the long-term behaviour and containment properties of the geological disposal system. Microstructure-informed modelling and its potential linkage with continuum flow modelling is a subject of ongoing studies. The approach of microstructure-informed modelling is discussed to provide insight and a mechanistic understanding of macroscopic parameters and their evolution. The proposed theoretical and methodological basis for microstructure-informed modelling of porous quasi-brittle media has the potential to develop into an explanatory and predictive tool for deriving mechanism-based, as opposed to phenomenological, evolution laws for macroscopic properties. These concepts in micro-scale modelling are likely to be applicable to the diffusion process, in addition to advective transport illustrated here for porous media. (authors)« less

Wood preservation

Treesearch

Kevin Archer; Stan Lebow

2006-01-01

Wood preservation can be interpreted to mean protection from fire, chemical degradation, mechanical wear, weathering, as well as biological attack. In this chapter, the term preservation is applied more restrictively to protection from biological hazards.

40 CFR 725.1075 - Burkholderia cepacia complex.

Code of Federal Regulations, 2010 CFR

2010-07-01

... CONTROL ACT REPORTING REQUIREMENTS AND REVIEW PROCESSES FOR MICROORGANISMS Significant New Uses for... significant new use is any use other than research and development in the degradation of chemicals via...

40 CFR 725.1075 - Burkholderia cepacia complex.

Code of Federal Regulations, 2013 CFR

2013-07-01

... CONTROL ACT REPORTING REQUIREMENTS AND REVIEW PROCESSES FOR MICROORGANISMS Significant New Uses for... significant new use is any use other than research and development in the degradation of chemicals via...

40 CFR 725.1075 - Burkholderia cepacia complex.

Code of Federal Regulations, 2012 CFR

2012-07-01

... CONTROL ACT REPORTING REQUIREMENTS AND REVIEW PROCESSES FOR MICROORGANISMS Significant New Uses for... significant new use is any use other than research and development in the degradation of chemicals via...

40 CFR 725.1075 - Burkholderia cepacia complex.

Code of Federal Regulations, 2011 CFR

2011-07-01

... CONTROL ACT REPORTING REQUIREMENTS AND REVIEW PROCESSES FOR MICROORGANISMS Significant New Uses for... significant new use is any use other than research and development in the degradation of chemicals via...

40 CFR 725.1075 - Burkholderia cepacia complex.

Code of Federal Regulations, 2014 CFR

2014-07-01

... CONTROL ACT REPORTING REQUIREMENTS AND REVIEW PROCESSES FOR MICROORGANISMS Significant New Uses for... significant new use is any use other than research and development in the degradation of chemicals via...

Review: Impacts of permafrost degradation on inorganic chemistry of surface fresh water

NASA Astrophysics Data System (ADS)

Colombo, Nicola; Salerno, Franco; Gruber, Stephan; Freppaz, Michele; Williams, Mark; Fratianni, Simona; Giardino, Marco

2018-03-01

Recent studies have shown that climate change is impacting the inorganic chemical characteristics of surface fresh water in permafrost areas and affecting aquatic ecosystems. Concentrations of major ions (e.g., Ca2 +, Mg2 +, SO42 -, NO3-) can increase following permafrost degradation with associated deepening of flow pathways and increased contributions of deep groundwater. In addition, thickening of the active layer and melting of near-surface ground ice can influence inorganic chemical fluxes from permafrost into surface water. Permafrost degradation has also the capability to modify trace element (e.g., Ni, Mn, Al, Hg, Pb) contents in surface water. Although several local and regional modifications of inorganic chemistry of surface fresh water have been attributed to permafrost degradation, a comprehensive review of the observed changes is lacking. The goal of this paper is to distil insight gained across differing permafrost settings through the identification of common patterns in previous studies, at global scale. In this review we focus on three typical permafrost configurations (pervasive permafrost degradation, thermokarst, and thawing rock glaciers) as examples and distinguish impacts on (i) major ions and (ii) trace elements. Consequences of warming climate have caused spatially-distributed progressive increases of major ion and trace element delivery to surface fresh water in both polar and mountain areas following pervasive permafrost degradation. Moreover, localised releases of major ions and trace elements to surface water due to the liberation of soluble materials sequestered in permafrost and ground ice have been found in ice-rich terrains both at high latitude (thermokarst features) and high elevation (rock glaciers). Further release of solutes and related transport to surface fresh water can be expected under warming climatic conditions. However, complex interactions among several factors able to influence the timing and magnitude of the impacts of permafrost degradation on inorganic chemistry of surface fresh water (e.g., permafrost sensitivity to thawing, modes of permafrost degradation, characteristics of watersheds) require further conceptual and mechanistic understanding together with quantitative diagnosis of the involved mechanisms in order to predict future changes with confidence.

The effect of soil texture on the degradation of textiles associated with buried bodies.

PubMed

Lowe, A C; Beresford, D V; Carter, D O; Gaspari, F; O'Brien, R C; Stuart, B H; Forbes, S L

2013-09-10

There are many factors which affect the rate of decomposition in a grave site including; the depth of burial, climatic conditions, physical conditions of the soil (e.g. texture, pH, moisture), and method of burial (e.g. clothing, wrappings). Clothing is often studied as a factor that can slow the rate of soft tissue decomposition. In contrast, the effect of soft tissue decomposition on the rate of textile degradation is usually reported as anecdotal evidence rather than being studied under controlled conditions. The majority of studies in this area have focused on the degradation of textiles buried directly in soil. The purpose of this study was to investigate the effect of soil texture on the degradation and/or preservation of textile materials associated with buried bodies. The study involved the burial of clothed domestic pig carcasses and control clothing in contrasting soil textures (silty clay loam, fine sand and fine sandy loam) at three field sites in southern Ontario, Canada. Graves were exhumed after 2, 12 and 14 months burial to observe the degree of degradation for both natural and synthetic textiles. Recovered textile samples were chemically analyzed using infrared (IR) spectroscopy and gas chromatography-mass spectrometry (GC-MS) to investigate the lipid decomposition by-products retained in the textiles. The findings of this study demonstrate that natural textile in contact with a buried decomposing body will be preserved for longer periods of time when compared to the same textile buried directly in soil and not in contact with a body. The soil texture did not visually impact the degree of degradation or preservation. Furthermore, the natural-synthetic textile blend was resistant to degradation, regardless of soil texture, contact with the body or time since deposition. Chemical analysis of the textiles using GC-MS correctly identified a lipid degradation profile consistent with the degree of soft tissue decomposition. Such information may be important for estimating time since deposition in instances where only grave goods and associated materials are recovered from a burial site. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) biodegradation potential and diversity of microbial consortia enriched from tsunami sediments in Miyagi, Japan.

PubMed

Bacosa, Hernando Pactao; Inoue, Chihiro

2015-01-01

The Great East Japan Earthquake caused tsunamis and resulted in widespread damage to human life and infrastructure. The disaster also resulted in contamination of the environment by chemicals such as polycyclic aromatic hydrocarbons (PAHs). This study was conducted to investigate the degradation potential and describe the PAH-degrading microbial communities from tsunami sediments in Miyagi, Japan. PAH-degrading bacteria were cultured by enrichment using PAH mixture or pyrene alone as carbon and energy sources. Among the ten consortia tested for PAH mixture, seven completely degraded fluorene and more than 95% of phenanthrene in 10 days, while only four consortia partially degraded pyrene. Six consortia partially degraded pyrene as a single substrate. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) revealed that each sample was dominated by unique microbial populations, regardless of sampling location. The consortia were dominated by known PAHs degraders including Sphingomonas, Pseudomonas, and Sphingobium; and previously unknown degraders such as Dokdonella and Luteimonas. A potentially novel and PAH-degrading Dokdonella was detected for the first time. PAH-ring hydroxylating dioxygenase (PAH-RHDα) gene was shown to be more effective than nidA in estimating pyrene-degrading bacteria in the enriched consortia. The consortia obtained in this study are potential candidates for remediation of PAHs contaminated soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Evaluation of the potential of soil remediation by direct multi-channel pulsed corona discharge in soil.

PubMed

Wang, Tie Cheng; Qu, Guangzhou; Li, Jie; Liang, Dongli

2014-01-15

A novel approach, named multi-channel pulsed corona discharge in soil, was developed for remediating organic pollutants contaminated soil, with p-nitrophenol (PNP) as the model pollutant. The feasibility of PNP degradation in soil was explored by evaluating effects of pulse discharge voltage, air flow rate and soil moisture on PNP degradation. Based on roles of chemically active species and evolution of degradation intermediates, PNP degradation processes were discussed. Experimental results showed that about 89.4% of PNP was smoothly degraded within 60min of discharge treatment at pulse discharge voltage 27kV, soil moisture 5% and air flow rate 0.8Lmin(-1), and the degradation process fitted the first-order kinetic model. Increasing pulse discharge voltage was found to be favorable for PNP degradation, but not for energy yield. There existed appropriate air flow rate and soil moisture for obtaining gratifying PNP degradation efficacy. Roles of radical scavenger and measurement of active species suggested that ozone, H2O2, and OH radicals played very important roles in PNP degradation. CN bond in PNP molecule was cleaved, and the main intermediate products such as hydroquinone, benzoquinone, catechol, phenol, acetic acid, formic acid, oxalic acid, NO2(-) and NO3(-) were identified. Possible pathway of PNP degradation in soil in such a system was proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

The influence of effective microorganisms (EM) and yeast on the degradation of strobilurins and carboxamides in leafy vegetables monitored by LC-MS/MS and health risk assessment.

PubMed

Wołejko, Elżbieta; Łozowicka, Bożena; Kaczyński, Piotr; Jankowska, Magdalena; Piekut, Jolanta

2016-01-01

The aim of this study was to determine the behaviour of strobilurin and carbocyamides commonly used in chemical protection of lettuce depending on carefully selected effective microorganisms (EM) and yeast (Y). Additionally, the assessment of the chronic health risk during a 2-week experiment was performed. The statistical method for correlation of physico-chemical parameters and time of degradation for pesticides was applied. In this study, the concentration of azoxystrobin, boscalid, pyraclostrobin and iprodione using liquid chromatography-mass spectrometry (LC-MS/MS) in the matrix of lettuce plants was performed, and there was no case of concentration above maximum residues levels. Before harvest, four fungicides and their mixture with EM (1 % and 10 %) and/or yeast 5 % were applied. In our work, the mixtures of 1%EM + Y and 10%EM + Y both stimulated and inhibited the degradation of the tested active substances. Adding 10%EM to the test substances strongly inhibited the degradation of iprodione, and its concentration decreased by 30 %, and in the case of other test substances, the degradation was approximately 60 %. Moreover, the addition of yeast stimulated the distribution of pyraclostrobin and boscalid in lettuce leaves. The risk assessment for the pesticides ranged from 0.4 to 64.8 % on day 1, but after 14 days, it ranged from 0.0 to 20.9 % for children and adults, respectively. It indicated no risk of adverse effects following exposure to individual pesticides and their mixtures with EM and yeast.

Microbial Consortium with High Cellulolytic Activity (MCHCA) for Enhanced Biogas Production

PubMed Central

Poszytek, Krzysztof; Ciezkowska, Martyna; Sklodowska, Aleksandra; Drewniak, Lukasz

2016-01-01

The use of lignocellulosic biomass as a substrate in agricultural biogas plants is very popular and yields good results. However, the efficiency of anaerobic digestion, and thus biogas production, is not always satisfactory due to the slow or incomplete degradation (hydrolysis) of plant matter. To enhance the solubilization of the lignocellulosic biomass various physical, chemical and biological pretreatment methods are used. The aim of this study was to select and characterize cellulose-degrading bacteria, and to construct a microbial consortium, dedicated for degradation of maize silage and enhancing biogas production from this substrate. Over 100 strains of cellulose-degrading bacteria were isolated from: sewage sludge, hydrolyzer from an agricultural biogas plant, cattle slurry and manure. After physiological characterization of the isolates, 16 strains (representatives of Bacillus, Providencia, and Ochrobactrum genera) were chosen for the construction of a Microbial Consortium with High Cellulolytic Activity, called MCHCA. The selected strains had a high endoglucanase activity (exceeding 0.21 IU/mL CMCase activity) and a wide range of tolerance to various physical and chemical conditions. Lab-scale simulation of biogas production using the selected strains for degradation of maize silage was carried out in a two-bioreactor system, similar to those used in agricultural biogas plants. The obtained results showed that the constructed MCHCA consortium is capable of efficient hydrolysis of maize silage, and increases biogas production by even 38%, depending on the inoculum used for methane fermentation. The results in this work indicate that the mesophilic MCHCA has a great potential for application on industrial scale in agricultural biogas plants. PMID:27014244

Comparative bacterial degradation and detoxification of model and kraft lignin from pulp paper wastewater and its metabolites

NASA Astrophysics Data System (ADS)

Abhishek, Amar; Dwivedi, Ashish; Tandan, Neeraj; Kumar, Urwashi

2017-05-01

Continuous discharge of lignin containing colored wastewater from pulp paper mill into the environment has resulted in building up their high level in various aquatic systems. In this study, the chemical texture of kraft lignin in terms of pollution parameters (COD, TOC, BOD, etc.) was quite different and approximately twofold higher as compared to model lignin at same optical density (OD 3.7 at 465 nm) and lignin content (2000 mg/L). For comparative bacterial degradation and detoxification of model and kraft lignin two bacteria Citrobacter freundii and Serratia marcescens were isolated, screened and applied in axenic and mixed condition. Bacterial mixed culture was found to decolorize 87 and 70 % model and kraft lignin (2000 mg/L), respectively; whereas, axenic culture Citrobacter freundii and Serratia marcescens decolorized 64, 60 % model and 50, 55 % kraft lignin, respectively, at optimized condition (34 °C, pH 8.2, 140 rpm). In addition, the mixed bacterial culture also showed the removal of 76, 61 % TOC; 80, 67 % COD and 87, 65 % lignin from model and kraft lignin, respectively. High pollution parameters (like TOC, COD, BOD, sulphate) and toxic chemicals slow down the degradation of kraft lignin as compared to model lignin. The comparative GC-MS analysis has suggested that the interspecies collaboration, i.e., each bacterial strain in culture medium has cumulative enhancing effect on growth, and degradation of lignin rather than inhibition. Furthermore, toxicity evaluation on human keratinocyte cell line after bacterial treatment has supported the degradation and detoxification of model and kraft lignin.

Transport and fate of nitrate and pesticides: Hydrogeology and riparian zone processes

USGS Publications Warehouse

Puckett, L.J.; Hughes, W.B.

2005-01-01

There is continuing concern over potential impacts of widespread application of nutrients and pesticides on ground- and surface-water quality. Transport and fate of nitrate and pesticides were investigated in a shallow aquifer and adjacent stream, Cow Castle Creek, in Orangeburg County, South Carolina. Pesticide and pesticide degradate concentrations were detected in ground water with greatest frequency and largest concentrations directly beneath and downgradient from the corn (Zea mays L.) field where they were applied. In almost all samples in which they were detected, concentrations of pesticide degradates greatly exceeded those of parent compounds, and were still present in ground waters that were recharged during the previous 18 yr. The absence of both parent and degradate compounds in samples collected from deeper in the aquifer suggests that this persistence is limited or that the ground water had recharged before use of the pesticide. Concentrations of NO3- in ground water decreased with increasing depth and age, but denitrification was not a dominant controlling factor. Hydrologic and chemical data indicated that ground water discharges to the creek and chemical exchange takes place within the upper 0.7 m of the streambed. Ground water had its greatest influence on surface-water chemistry during low-flow periods, causing a decrease in concentrations of Cl-, NO3-, pesticides, and pesticide degradates. Conversely, shallow subsurface drainage dominates stream chemistry during high-flow periods, increasing stream concentrations of Cl-, NO3-, pesticides, and pesticide degradates. These results point out the importance of understanding the hydrogeologic setting when investigating transport and fate of contaminants in ground water and surface water. ?? ASA, CSSA, SSSA.

Microbial Enrichment from Six Hydraulic Fracturing Fluids and Biogeochemical Characteristics of Flowback Waters in Oklahoma Shale Formations

NASA Astrophysics Data System (ADS)

Krzmarzick, M. J.; McCutchan, A.; Carroll, J.; Lozano, T.

2017-12-01

Hydraulic fracturing of oil and gas formations has revolutionized the industry, but little is known regarding the interactions of the microbiology in formations and the hydraulic fracturing chemicals used. In the first part of this study, six representative hydraulic fracturing fluids were incubated in bench scale microcosms with surface soils over six months at 1× concentrations used in the field. These fluids differed greatly in terms of biocide, surfactants, corrosion inhibitors and crosslinking agents (if any). The changes in microbial communities were measured by Illumina 16S rRNA gene analysis and quantitative-PCR. As a whole, the microbial communities enriched were significantly varied between fluids, with the magnitude of the difference tightly linked to the total organic carbon of each fluid. Most enriched bacteria heavily grew within just the first couple of weeks, and belonged to genera well-linked to xenobiotic degradation, such as Azospirillum, Ralstonia, and Comamonas. This, combined with bulk parameters such as chemical oxygen demand of the water, indicates that a significant fraction of these fluids are readily degradable, though individual chemicals were not monitored for recalcitrance. In the second component of this work, the flowback waters from sixteen newly completed wells in south-central Oklahoma were monitored over two months for compositions of boron, dissolved solids, BTEX, chloride, and their microbial communities. As expected, dissolved solids increased over time as the flowback waters became more characteristic of the formation waters. In these wells, boron, a carefully measured component of the fracturing fluid for cross-linking applications, was either stable or increased over time. The microbial community characteristics are pending but will be compared between formations, to the chemical data, and to the results in the bench-top degradation study.

Environmentally induced chemical and morphological heterogeneity of zinc oxide thin films

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

Jiang, Hua; Chou, Kang Wei; Petrash, Stanislas

Zinc oxide (ZnO) thin films have been reported to suffer from degradation in electrical properties, when exposed to elevated heat and humidity, often leading to failures of electronic devices containing ZnO films. This degradation appears to be linked to water and oxygen penetration into the ZnO film. However, a direct observation in the ZnO film morphological evolution detailing structural and chemical changes has been lacking. Here, we systematically investigated the chemical and morphological heterogeneities of ZnO thin films caused by elevated heat and humidity, simulating an environmental aging. X-ray fluorescence microscopy, X-ray absorption spectroscopy, grazing incidence small angle and widemore » angle X-ray scattering, scanning electron microscopy (SEM), ultra-high-resolution SEM, and optical microscopy were carried out to examine ZnO and Al-doped ZnO thin films on two different substrates—silicon wafers and flexible polyethylene terephthalate (PET) films. In the un-doped ZnO thin film, the simulated environmental aging is resulting in pin-holes. In the Al-doped ZnO thin films, significant morphological changes occurred after the treatment, with an appearance of platelet-shaped structures that are 100–200 nm wide by 1 μm long. Synchrotron x-ray characterization further confirmed the heterogeneity in the aged Al-doped ZnO, showing the formation of anisotropic structures and disordering. X-ray diffraction and X-ray absorption spectroscopy indicated the formation of a zinc hydroxide in the aged Al-doped films. Utilizing advanced characterization methods, our studies provided information with an unprecedented level of details and revealed the chemical and morphologically heterogeneous nature of the degradation in ZnO thin films.« less

Environmentally induced chemical and morphological heterogeneity of zinc oxide thin films

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

Jiang, Hua; Chou, Kang Wei; Petrash, Stanislas

Zinc oxide (ZnO) thin films have been reported to suffer from degradation in electrical properties, when exposed to elevated heat and humidity, often leading to failures of electronic devices containing ZnO films. This degradation appears to be linked to water and oxygen penetration into the ZnO film. However, a direct observation in the ZnO film morphological evolution detailing structural and chemical changes has been lacking. Here, we systematically investigated the chemical and morphological heterogeneities of ZnO thin films caused by elevated heat and humidity, simulating an environmental aging. X-ray fluorescence microscopy, X-ray absorption spectroscopy, grazing incidence small angle and widemore » angle X-ray scattering, scanning electron microscopy (SEM), ultra-high-resolution SEM, and optical microscopy were carried out to examine ZnO and Al-doped ZnO thin films on two different substrates—silicon wafers and flexible polyethylene terephthalate (PET) films. In the un-doped ZnO thin film, the simulated environmental aging is resulting in pin-holes. In the Al-doped ZnO thin films, significant morphological changes occurred after the treatment, with an appearance of platelet-shaped structures that are 100–200 nm wide by 1μm long. Synchrotron x-ray characterization further confirmed the heterogeneity in the aged Al-doped ZnO, showing the formation of anisotropic structures and disordering. X-ray diffraction and X-ray absorption spectroscopy indicated the formation of a zinc hydroxide in the aged Al-doped films. In conclusion, utilizing advanced characterization methods, our studies provided information with an unprecedented level of details and revealed the chemical and morphologically heterogeneous nature of the degradation in ZnO thin films.« less

Environmentally induced chemical and morphological heterogeneity of zinc oxide thin films

DOE PAGES

Jiang, Hua; Chou, Kang Wei; Petrash, Stanislas; ...

2016-09-02

Zinc oxide (ZnO) thin films have been reported to suffer from degradation in electrical properties, when exposed to elevated heat and humidity, often leading to failures of electronic devices containing ZnO films. This degradation appears to be linked to water and oxygen penetration into the ZnO film. However, a direct observation in the ZnO film morphological evolution detailing structural and chemical changes has been lacking. Here, we systematically investigated the chemical and morphological heterogeneities of ZnO thin films caused by elevated heat and humidity, simulating an environmental aging. X-ray fluorescence microscopy, X-ray absorption spectroscopy, grazing incidence small angle and widemore » angle X-ray scattering, scanning electron microscopy (SEM), ultra-high-resolution SEM, and optical microscopy were carried out to examine ZnO and Al-doped ZnO thin films on two different substrates—silicon wafers and flexible polyethylene terephthalate (PET) films. In the un-doped ZnO thin film, the simulated environmental aging is resulting in pin-holes. In the Al-doped ZnO thin films, significant morphological changes occurred after the treatment, with an appearance of platelet-shaped structures that are 100–200 nm wide by 1μm long. Synchrotron x-ray characterization further confirmed the heterogeneity in the aged Al-doped ZnO, showing the formation of anisotropic structures and disordering. X-ray diffraction and X-ray absorption spectroscopy indicated the formation of a zinc hydroxide in the aged Al-doped films. In conclusion, utilizing advanced characterization methods, our studies provided information with an unprecedented level of details and revealed the chemical and morphologically heterogeneous nature of the degradation in ZnO thin films.« less

Heat-induced Protein Structure and Subfractions in Relation to Protein Degradation Kinetics and Intestinal Availability in Dairy Cattle

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

Doiron, K.; Yu, P; McKinnon, J

2009-01-01

The objectives of this study were to reveal protein structures of feed tissues affected by heat processing at a cellular level, using the synchrotron-based Fourier transform infrared microspectroscopy as a novel approach, and quantify protein structure in relation to protein digestive kinetics and nutritive value in the rumen and intestine in dairy cattle. The parameters assessed included (1) protein structure a-helix to e-sheet ratio; (2) protein subfractions profiles; (3) protein degradation kinetics and effective degradability; (4) predicted nutrient supply using the intestinally absorbed protein supply (DVE)/degraded protein balance (OEB) system for dairy cattle. In this study, Vimy flaxseed protein wasmore » used as a model feed protein and was autoclave-heated at 120C for 20, 40, and 60 min in treatments T1, T2, and T3, respectively. The results showed that using the synchrotron-based Fourier transform infrared microspectroscopy revealed and identified the heat-induced protein structure changes. Heating at 120C for 40 and 60 min increased the protein structure a-helix to e-sheet ratio. There were linear effects of heating time on the ratio. The heating also changed chemical profiles, which showed soluble CP decreased upon heating with concomitant increases in nonprotein nitrogen, neutral, and acid detergent insoluble nitrogen. The protein subfractions with the greatest changes were PB1, which showed a dramatic reduction, and PB2, which showed a dramatic increase, demonstrating a decrease in overall protein degradability. In situ results showed a reduction in rumen-degradable protein and in rumen-degradable dry matter without differences between the treatments. Intestinal digestibility, determined using a 3-step in vitro procedure, showed no changes to rumen undegradable protein. Modeling results showed that heating increased total intestinally absorbable protein (feed DVE value) and decreased degraded protein balance (feed OEB value), but there were no differences between the treatments. There was a linear effect of heating time on the DVE and a cubic effect on the OEB value. Our results showed that heating changed chemical profiles, protein structure a-helix to e-sheet ratio, and protein subfractions; decreased rumen-degradable protein and rumen-degradable dry matter; and increased potential nutrient supply to dairy cattle. The protein structure a-helix to e-sheet ratio had a significant positive correlation with total intestinally absorbed protein supply and negative correlation with degraded protein balance.« less

Optimal design of active spreading systems to remediate sorbing groundwater contaminants in situ

NASA Astrophysics Data System (ADS)

Piscopo, Amy N.; Neupauer, Roseanna M.; Kasprzyk, Joseph R.

2016-07-01

The effectiveness of in situ remediation to treat contaminated aquifers is limited by the degree of contact between the injected treatment chemical and the groundwater contaminant. In this study, candidate designs that actively spread the treatment chemical into the contaminant are generated using a multi-objective evolutionary algorithm. Design parameters pertaining to the amount of treatment chemical and the duration and rate of its injection are optimized according to objectives established for the remediation - maximizing contaminant degradation while minimizing energy and material requirements. Because groundwater contaminants have different reaction and sorption properties that influence their ability to be degraded with in situ remediation, optimization was conducted for six different combinations of reaction rate coefficients and sorption rates constants to represent remediation of the common groundwater contaminants, trichloroethene, tetrachloroethene, and toluene, using the treatment chemical, permanganate. Results indicate that active spreading for contaminants with low reaction rate coefficients should be conducted by using greater amounts of treatment chemical mass and longer injection durations relative to contaminants with high reaction rate coefficients. For contaminants with slow sorption or contaminants in heterogeneous aquifers, two different design strategies are acceptable - one that injects high concentrations of treatment chemical mass over a short duration or one that injects lower concentrations of treatment chemical mass over a long duration. Thus, decision-makers can select a strategy according to their preference for material or energy use. Finally, for scenarios with high ambient groundwater velocities, the injection rate used for active spreading should be high enough for the groundwater divide to encompass the entire contaminant plume.

In Situ Biological Treatment Test at Kelly Air Force Base. Volume 2. Field Test Results and Cost Model.

DTIC Science & Technology

1987-07-01

degradation of organic contaminants. In situ treatment affects contaminants sorbed to soil as well as dissolved in groundwater. It is potentially ...indigenous soil micro - organisms to multiply and degrade the waste material. Exxon’s Baytown refinery has been disposing of oily wastes by land farming...Group (ERG). Chemical analyses performed on soil samples included priority pollutant volatile and metal compounds, total hydrocarbons (alkanes), oil and

PLA recycling by hydrolysis at high temperature

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

Cristina, Annesini Maria; Rosaria, Augelletti; Sara, Frattari, E-mail: sara.frattari@uniroma1.it

In this work the process of PLA hydrolysis at high temperature was studied, in order to evaluate the possibility of chemical recycling of this polymer bio-based. In particular, the possibility to obtain the monomer of lactic acid from PLA degradation was investigated. The results of some preliminary tests, performed in a laboratory batch reactor at high temperature, are presented: the experimental results show that the complete degradation of PLA can be obtained in relatively low reaction times.

Bio and nanomaterials in tribocorrosion systems

NASA Astrophysics Data System (ADS)

Benea, Lidia

2017-02-01

The growing attention that the scientific community has paid in the last decades to the corrosion phenomena, including tribocorrosion is related to the huge economic, social and environmental losses (3,5 % GDP in industrialized countries as USA, UK, Japan and Germany), that result from the spread of damage of several metal constructions and devices. Tribocorrosion is defined as the chemical-electrochemical-mechanical process leading to a degradation of materials in sliding, rolling or erosion contacts immersed in a corrosive environment or even in water. That degradation results from the combined action of corrosion and wear are higher compared with addition of corrosion and wear degradation separately. This synergism between chemical, electrochemical, and mechanical processes on materials in sliding, abrasive or erosive contacts immersed in a liquid requires a multi-disciplinary approach (material science, electrochemistry, tribology, mechanics, and surface engineering). This paper presents few summary results obtained by studying the materials degradation by complex tribocorrosion processes in terms of two broad categories of applications: tribocorrosion in industrial systems with improved behaviour of nanomaterials as hybrid and nanocomposite layers and tribocorrosion in living systems with improved behaviour by surface modifications of biomaterials applying electrochemical techniques. The purpose of this paper is to provide information on the surface conditions of materials in sliding contacts and also on the kinetics of reactions that control the corrosion component in the material loss during tribocorrosion tests.

Two decades of warming increases diversity of a potentially lignolytic bacterial community

PubMed Central

Pold, Grace; Melillo, Jerry M.; DeAngelis, Kristen M.

2015-01-01

As Earth's climate warms, the massive stores of carbon found in soil are predicted to become depleted, and leave behind a smaller carbon pool that is less accessible to microbes. At a long-term forest soil-warming experiment in central Massachusetts, soil respiration and bacterial diversity have increased, while fungal biomass and microbially-accessible soil carbon have decreased. Here, we evaluate how warming has affected the microbial community's capability to degrade chemically-complex soil carbon using lignin-amended BioSep beads. We profiled the bacterial and fungal communities using PCR-based methods and completed extracellular enzyme assays as a proxy for potential community function. We found that lignin-amended beads selected for a distinct community containing bacterial taxa closely related to known lignin degraders, as well as members of many genera not previously noted as capable of degrading lignin. Warming tended to drive bacterial community structure more strongly in the lignin beads, while the effect on the fungal community was limited to unamended beads. Of those bacterial operational taxonomic units (OTUs) enriched by the warming treatment, many were enriched uniquely on lignin-amended beads. These taxa may be contributing to enhanced soil respiration under warming despite reduced readily available C availability. In aggregate, these results suggest that there is genetic potential for chemically complex soil carbon degradation that may lead to extended elevated soil respiration with long-term warming. PMID:26042112

Glutaraldehyde degradation in hospital wastewater by photoozonation.

PubMed

Kist, Lourdes Teresinha; Rosa, Ellen Caroline; Machado, Enio Leandro; Camargo, Maria Emilia; Moro, Celso Camilo

2013-01-01

In this paper, we assessed aqueous solutions of glutaraldehyde (GA), a chemical used for the disinfection of hospital materials, using advanced oxidative processes, O3, and UV, and the combination of the latter two. Assays with different ozone concentrations at distinct pH levels were conducted to determine the best treatment process. GA concentrations before and after each treatment were measured by spectrophotometry. The best treatment was that which combined O3 and UV, yielding a degradation of 72.0-75.0% in relation to the initial concentration with pH between 4 and 9. Kinetics demonstrated that GA degradation is not dependent on pH, as there was a first-order reaction with a rate constant of k = 0.0180 min(-1) for initial pH 9 and of k = 0.0179 min(-1) for initial pH 7, that is, the values are virtually the same. Secondary wastewater samples were also analysed using the septic tank/filter system of a regional hospital in Vale do Rio Pardo, state of Rio Grande do Sul, southern Brazil. In this case, the characteristics of the wastewater were described and, after treatment, a GA degradation rate of 23.3% was noted, with reductions of 75% for chemical oxygen demand, 81% for biochemical oxygen demand, 68% for turbidity, 70% for surfactants and total disinfection in terms of thermotolerant coliforms.

Pseudomonas putida F1 uses energy taxis to sense hydroxycinnamic acids

PubMed Central

Hughes, Jonathan G.; Zhang, Xiangsheng; Parales, Juanito V.; Ditty, Jayna L.; Parales, Rebecca E.

2017-01-01

Soil bacteria such as pseudomonads are widely studied due to their diverse metabolic capabilities, particularly the ability to degrade both naturally occurring and xenobiotic aromatic compounds. Chemotaxis, the directed movement of cells in response to chemical gradients, is common in motile soil bacteria and the wide range of chemicals detected often mirrors the metabolic diversity observed. Pseudomonas putida F1 is a soil isolate capable of chemotaxis toward, and degradation of, numerous aromatic compounds. We showed that P. putida F1 is capable of degrading members of a class of naturally occurring aromatic compounds known as hydroxycinnamic acids, which are components of lignin and are ubiquitous in the soil environment. We also demonstrated the ability of P. putida F1 to sense three hydroxycinnamic acids: p-coumaric, caffeic and ferulic acids. The chemotaxis response to hydroxycinnamic acids was induced during growth in the presence of hydroxycinnamic acids and was negatively regulated by HcaR, the repressor of the hydroxycinnamic acid catabolic genes. Chemotaxis to the three hydroxycinnamic acids was dependent on catabolism, as a mutant lacking the gene encoding feruloyl-CoA synthetase (Fcs), which catalyzes the first step in hydroxycinnamic acid degradation, was unable to respond chemotactically toward p-coumaric, caffeic, or ferulic acids. We tested whether an energy taxis mutant could detect hydroxycinnamic acids and determined that hydroxycinnamic acid sensing is mediated by the energy taxis receptor Aer2. PMID:28954643

Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses.

PubMed

Boyd, Thomas J; Montgomery, Michael T; Cuenca, Richard H; Hagimoto, Yutaka

2016-10-21

A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal - or rather the absence of signal - is evenly distributed throughout a contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the 14 C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually <30,000 years old). Given a known radiocarbon content for NOM (a site background), a two end-member mixing model can be used to determine the CO2 derived from a fossil source in a given soil gas or groundwater sample. Coupling the percent CO2 derived from the contaminant with the CO2 respiration rate provides an estimate for the total amount of contaminant degraded per unit time. Finally, determining a zone of influence (ZOI) representing the volume from which site CO2 is collected allows determining the contaminant degradation per unit time and volume. Along with estimates for total contaminant mass, this can ultimately be used to calculate time-to-remediate or otherwise used by site managers for decision-making.

Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses

PubMed Central

Boyd, Thomas J.; Montgomery, Michael T.; Cuenca, Richard H.; Hagimoto, Yutaka

2016-01-01

A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal — or rather the absence of signal — is evenly distributed throughout a contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the 14C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually <30,000 years old). Given a known radiocarbon content for NOM (a site background), a two end-member mixing model can be used to determine the CO2 derived from a fossil source in a given soil gas or groundwater sample. Coupling the percent CO2 derived from the contaminant with the CO2 respiration rate provides an estimate for the total amount of contaminant degraded per unit time. Finally, determining a zone of influence (ZOI) representing the volume from which site CO2 is collected allows determining the contaminant degradation per unit time and volume. Along with estimates for total contaminant mass, this can ultimately be used to calculate time-to-remediate or otherwise used by site managers for decision-making. PMID:27805601

In Vitro Corrosion and Cytocompatibility of ZK60 Magnesium Alloy Coated with Hydroxyapatite by a Simple Chemical Conversion Process for Orthopedic Applications

PubMed Central

Wang, Bing; Huang, Ping; Ou, Caiwen; Li, Kaikai; Yan, Biao; Lu, Wei

2013-01-01

Magnesium and its alloys—a new class of degradable metallic biomaterials—are being increasingly investigated as a promising alternative for medical implant and device applications due to their advantageous mechanical and biological properties. However, the high corrosion rate in physiological environments prevents the clinical application of Mg-based materials. Therefore, the objective of this study was to develop a hydroxyapatite (HA) coating on ZK60 magnesium alloy substrates to mediate the rapid degradation of Mg while improving its cytocompatibility for orthopedic applications. A simple chemical conversion process was applied to prepare HA coating on ZK60 magnesium alloy. Surface morphology, elemental compositions, and crystal structures were characterized using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction, respectively. The corrosion properties of samples were investigated by immersion test and electrochemical test. Murine fibroblast L-929 cells were harvested and cultured with coated and non-coated ZK60 samples to determine cytocompatibility. The degradation results suggested that the HA coatings decreased the degradation of ZK60 alloy. No significant deterioration in compression strength was observed for all the uncoated and coated samples after 2 and 4 weeks’ immersion in simulated body fluid (SBF). Cytotoxicity test indicated that the coatings, especially HA coating, improved cytocompatibility of ZK60 alloy for L929 cells. PMID:24300096

Montmorillonite Functionalized with Pralidoxime as a Material for Chemical Protection against Organophosphorous Compounds

DTIC Science & Technology

2011-03-25

implied is via iondipole forces.5,6 It is well-known that clays such as montmorillonite and kaolinite accelerate the degradation of insecticides such...REPORT Montmorillonite Functionalized with Pralidoxime As a Material for Chemical Protection against Organophosphorous Compounds 14. ABSTRACT 16...SECURITY CLASSIFICATION OF: Montmorillonite K-10 functionalized with ?-nucleophilic 2-pralidoxime (PAM) and its zwitterionic oximate form (PAMNa) is

Dynamics of Chemical Degradation in Water Using Photocatalytic Reactions in an Ultraviolet Light Emitting Diode Reactor

DTIC Science & Technology

2017-09-14

one such study, AOPs were investigated for the removal of organophosphorus pesticides in wastewater by selecting and optimizing oxidation processes...micropollutants (primarily pharmaceuticals, personal care products, and pesticides ) in four 64 different river water sources (Colorado River, Passaic...the National Institutes of Health PubChem data repository (National Institutes of Health 2016). Additional chemical properties were also selected for

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

PubMed Central

Febbraio, Ferdinando

2017-01-01

Addressing the problems related to the widespread presence of an increasing number of chemicals released into the environment by human activities represents one of the most important challenges of this century. In the last few years, to replace the high cost, in terms of time and money, of conventional technologies, the scientific community has directed considerable research towards the development both of new detection systems for the measurement of the contamination levels of chemicals in people’s body fluids and tissue, as well as in the environment, and of new remediation strategies for the removal of such chemicals from the environment, as a means of the prevention of human diseases. New emerging biosensors for the analysis of environmental chemicals have been proposed, including VHH antibodies, that combine the antibody performance with the affinity for small molecules, genetically engineered microorganisms, aptamers and new highly stable enzymes. However, the advances in the field of chemicals monitoring are still far from producing a continuous real-time and on-line system for their detection. Better results have been obtained in the development of strategies which use organisms (microorganisms, plants and animals) or metabolic pathway-based approaches (single enzymes or more complex enzymatic solutions) for the fixation, degradation and detoxification of chemicals in the environment. Systems for enzymatic detoxification and degradation of toxic agents in wastewater from chemical and manufacturing industries, such as ligninolytic enzymes for the treatment of wastewater from the textile industry, have been proposed. Considering the high value of these research studies, in terms of the protection of human health and of the ecosystem, science must play a major role in guiding policy changes in this field. PMID:28289515

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

PubMed

Febbraio, Ferdinando

2017-02-26

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