Prediction of dioxin/furan incinerator emissions using low-molecular-weight volatile products of incomplete combustion.

PubMed

Lemieux, P M; Lee, C W; Ryan, J V

2000-12-01

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C2 chlorinated alkene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alkenes and PCDDs/Fs. Each data set contained one or more C2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.

Prediction of Dioxin/Furan Incinerator Emissions Using Low-Molecular-Weight Volatile Products of Incomplete Combustion.

PubMed

Lemieux, P M; Lee, C W; Ryan, J V

2000-12-01

Emissions of polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C 2 chlorinated alk-ene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C 2 chlorinated alk-enes and PCDDs/Fs. Each data set contained one or more C 2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.

78 FR 9955 - Self-Regulatory Organizations; BATS Exchange, Inc.; Notice of Filing and Immediate Effectiveness...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-12

... Change To Extend the Pilot Program Related to Trading Pauses Due to Extraordinary Market Volatility... Rule 11.18, entitled ``Trading Halts Due to Extraordinary Market Volatility.'' The text of the proposed... stocks become, on a rolling basis, subject to the Plan to Address Extraordinary Market Volatility...

Comparison of volatile organic compounds from lung cancer patients and healthy controls-challenges and limitations of an observational study.

PubMed

Schallschmidt, Kristin; Becker, Roland; Jung, Christian; Bremser, Wolfram; Walles, Thorsten; Neudecker, Jens; Leschber, Gunda; Frese, Steffen; Nehls, Irene

2016-10-12

This paper outlines the design and performance of an observational study on the profiles of volatile organic compounds (VOCs) in the breath of 37 lung cancer patients and 23 healthy controls of similar age. The need to quantify each VOC considered as a potential disease marker on the basis of individual calibration is elaborated, and the quality control measures required to maintain reproducibility in breath sampling and subsequent instrumental trace VOC analysis using solid phase microextraction-gas chromatography-mass spectrometry over a study period of 14 months are described. Twenty-four VOCs were quantified on the basis of their previously suggested potential as cancer markers. The concentration of aromatic compounds in the breath was increased, as expected, in smokers, while lung cancer patients displayed significantly increased levels of oxygenated VOCs such as aldehydes, 2-butanone and 1-butanol. Although sets of selected oxygenated VOCs displayed sensitivities and specificities between 80% and 90% using linear discriminant analysis (LDA) with leave-one-out cross validation, the effective selectivity of the breath VOC approach with regard to cancer detection is clearly limited. Results are discussed against the background of the literature on volatile cancer marker investigations and the prospects of linking increased VOC levels in patients' breath with approaches that employ sniffer dogs. Experience from this study and the literature suggests that the currently available methodology is not able to use breath VOCs to reliably discriminate between cancer patients and healthy controls. Observational studies often tend to note significant differences in levels of certain oxygenated VOCs, but without the resolution required for practical application. Any step towards the exploitation of differences in VOC profiles for illness detection would have to solve current restrictions set by the low and variable VOC concentrations. Further challenges are the technical complexity of studies involving breath sampling and possibly the limited capability of current analytical procedures to detect unstable marker candidates.

Evaluation of the Volatility Basis-Set Approach for Modeling Primary and Secondary Organic Aerosol in the Mexico City Metropolitan Area

NASA Astrophysics Data System (ADS)

Tsimpidi, A. P.; Karydis, V. A.; Pandis, S. N.; Zavala, M.; Lei, W.; Molina, L. T.

2007-12-01

Anthropogenic air pollution is an increasingly serious problem for public health, agriculture, and global climate. Organic material (OM) contributes ~ 20-50% to the total fine aerosol mass at continental mid-latitudes. Although OM accounts for a large fraction of PM2.5 concentration worldwide, the contributions of primary and secondary organic aerosol have been difficult to quantify. In this study, new primary and secondary organic aerosol modules were added to PMCAMx, a three dimensional chemical transport model (Gaydos et al., 2007), for use with the SAPRC99 chemistry mechanism (Carter, 2000; ENVIRON, 2006) based on recent smog chamber studies (Robinson et al., 2007). The new modeling framework is based on the volatility basis-set approach (Lane et al., 2007): both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The emission inventory, which uses as starting point the MCMA 2004 official inventory (CAM, 2006), is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments (Robinson et al., 2007). Sensitivity tests where POA is considered as nonvolatile and POA and SOA as chemically reactive are also described. In all cases PMCAMx is applied in the Mexico City Metropolitan Area during March 2006. The modeling domain covers a 180x180x6 km region in the MCMA with 3x3 km grid resolution. The model predictions are compared with Aerodyne's Aerosol Mass Spectrometry (AMS) observations from the MILAGRO Campaign. References Robinson, A. L.; Donahue, N. M.; Shrivastava, M. K.; Weitkamp, E. A.; Sage, A. M.; Grieshop, A. P.; Lane, T. E.; Pandis, S. N.; Pierce, J. R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262. Gaydos, T. M.; Pinder, R. W.; Koo, B.; Fahey, K. M.; Pandis, S. N., 2007. Development and application of a three- dimensional aerosol chemical transport model, PMCAMx. Atmospheric Environment 41, 2594-2611. Carter, W.P.L., 2000. Programs and Files Implementing the SAPRC-99 Mechanism and its Associates Emissions Processing Procedures for Models-3 and Other Regional Models. January 31, 2000. http://pah.cert.ucr.edu/~carter/SAPRC99.htm. Environ, 2006. User's guide to the comprehensive air quality model with extensions (CAMx). Version 4.30. Report prepared by ENVIRON International Corporation, Novato, CA. Lane, T.E.; Donahue, N. M.; Pandis, S. N. 2007. Simulating Secondary Organic Aerosol Formation using the Votality Basis-Set Approach in a Chemical Transport Model, in preperation. CAM (Comision Ambiental Metropolitana) 2006: Inventario de Emisiones 2004 de la Zona Metropolitana del Valle de Mexico, Mexico. Robinson, A. L.; Donahue, N. M.; Shrivastava, M. K.; Weitkamp, E. A.; Sage, A. M.; Grieshop, A. P.; Lane, T. E.; Pandis, S. N.; Pierce, J. R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262.

A Monte-Carlo Analysis of Organic Volatility with Aerosol Microphysics

NASA Astrophysics Data System (ADS)

Gao, Chloe; Tsigaridis, Kostas; Bauer, Susanne E.

2017-04-01

A newly developed box model, MATRIX-VBS, includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves aerosol mass and number concentrations and aerosol mixing state. The new scheme advanced the representation of organic aerosols in models by improving the traditional and simplistic treatment of organic aerosols as non-volatile and with a fixed size distribution. Further development includes adding the condensation of organics on coarse mode aerosols - dust and sea salt, thus making all organics in the system semi-volatile. To test and simplify the model, a Monte-Carlo analysis is performed to pin point which processes affect organics the most under varied chemical and meteorological conditions. Since the model's parameterizations have the ability to capture a very wide range of conditions, all possible scenarios on Earth across the whole parameter space, including temperature, humidity, location, emissions and oxidant levels, are examined. The Monte-Carlo simulations provide quantitative information on the sensitivity of the newly developed model and help us understand how organics are affecting the size distribution, mixing state and volatility distribution at varying levels of meteorological conditions and pollution levels. In addition, these simulations give information on which parameters play a critical role in the aerosol distribution and evolution in the atmosphere and which do not, that will facilitate the simplification of the box model, an important step in its implementation in the global model GISS ModelE as a module.

Financial and risk considerations for successful disease management programs.

PubMed

Baldwin, A L

1999-11-01

Results for disease management [DM] programs have not been as positive as hoped because of clinical issues, lack of access to capital, and administrative issues. The financial experience of DM programs can be quite volatile. Financial projections that are protocol-based, rather than experience-based, may understate the revenue required and the range of possible costs for a DM program by understating the impact of complicating conditions and comorbidities. Actuarial tools (risk analysis and risk projection models) support better understanding of DM contracts. In particular, these models can provide the ability to quantify the impact of the factors that drive costs of a contract and the volatility of those costs. This analysis can assist DM companies in setting appropriate revenue and capital targets. Similar analysis by health plans can identify diseases that are good candidates for DM programs and can provide the basis for performance targets.

Molecular and genomic basis of volatile-mediated indirect defense against insects in rice.

PubMed

Yuan, Joshua S; Köllner, Tobias G; Wiggins, Greg; Grant, Jerome; Degenhardt, Jörg; Chen, Feng

2008-08-01

Rice plants fed on by fall armyworm (Spodoptera frugiperda, FAW) caterpillars emit a blend of volatiles dominated by terpenoids. These volatiles were highly attractive to females of the parasitoid Cotesia marginiventris. Microarray analysis identified 196 rice genes whose expression was significantly upregulated by FAW feeding, 18 of which encode metabolic enzymes potentially involved in volatile biosynthesis. Significant induction of expression of seven of the 11 terpene synthase (TPS) genes identified through the microarray experiments was confirmd using real-time RT-PCR. Enzymes encoded by three TPS genes, Os02g02930, Os08g07100 and Os08g04500, were biochemically characterized. Os02g02930 was found to encode a monoterpene synthase producing the single product S-linalool, which is the most abundant volatile emitted from FAW-damaged rice plants. Both Os08g07100 and Os08g04500 were found to encode sesquiterpene synthases, each producing multiple products. These three enzymes are responsible for production of the majority of the terpenes released from FAW-damaged rice plants. In addition to TPS genes, several key genes in the upstream terpenoid pathways were also found to be upregulated by FAW feeding. This paper provides a comprehensive analysis of FAW-induced volatiles and the corresponding volatile biosynthetic genes potentially involved in indirect defense in rice. Evolution of the genetic basis governing volatile terpenoid biosynthesis for indirect defense is discussed.

75 FR 17987 - Self-Regulatory Organizations; Notice of Filing and Immediate Effectiveness of Proposed Rule...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-08

... time on an intraday basis at its discretion if it determined that volatility warranted deactivation. Members would be notified of intraday OPP deactivation due to volatility and any subsequent intraday...

Volatile-Compound Fingerprinting by Headspace-Gas-Chromatography Ion-Mobility Spectrometry (HS-GC-IMS) as a Benchtop Alternative to 1H NMR Profiling for Assessment of the Authenticity of Honey.

PubMed

Gerhardt, Natalie; Birkenmeier, Markus; Schwolow, Sebastian; Rohn, Sascha; Weller, Philipp

2018-02-06

This work describes a simple approach for the untargeted profiling of volatile compounds for the authentication of the botanical origins of honey based on resolution-optimized HS-GC-IMS combined with optimized chemometric techniques, namely PCA, LDA, and kNN. A direct comparison of the PCA-LDA models between the HS-GC-IMS and 1 H NMR data demonstrated that HS-GC-IMS profiling could be used as a complementary tool to NMR-based profiling of honey samples. Whereas NMR profiling still requires comparatively precise sample preparation, pH adjustment in particular, HS-GC-IMS fingerprinting may be considered an alternative approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. It was demonstrated that all tested honey samples could be distinguished on the basis of their botanical origins. Loading plots revealed the volatile compounds responsible for the differences among the monofloral honeys. The HS-GC-IMS-based PCA-LDA model was composed of two linear functions of discrimination and 10 selected PCs that discriminated canola, acacia, and honeydew honeys with a predictive accuracy of 98.6%. Application of the LDA model to an external test set of 10 authentic honeys clearly proved the high predictive ability of the model by correctly classifying them into three variety groups with 100% correct classifications. The constructed model presents a simple and efficient method of analysis and may serve as a basis for the authentication of other food types.

[Study on volatile components from flowers of Gymnema sylvestre].

PubMed

Qiu, Qin; Zhen, Han-Shen; Huang, Pei-Qian

2013-04-01

To analyze the volatile components from flowers of Gymnema sylvestre. Volatile components of flowers of Gymnema sylvestre were extracted by water vapor distilling, and the components were separated and identified by GC-MS. 55 components were separated and 33 components were identified, accounting for 88.73% of all quantity. The principal volatile components are Phytol, Pentacosane, 10-Heneicosene (c, t), 3-Eicosene, (E) -and 2-Methyl-Z-2-docosane. The research can pro-vide scientific basis for chemical component research of flowers of Gymnema sylvestre.

A Monte-Carlo Analysis of Organic Aerosol Volatility with Aerosol Microphysics

NASA Astrophysics Data System (ADS)

Gao, C. Y.; Tsigaridis, K.; Bauer, S. E.

2016-12-01

A newly developed box model scheme, MATRIX-VBS, includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves aerosol mass and number concentrations and aerosol mixing state. The new scheme advanced the representation of organic aerosols in Earth system models by improving the traditional and simplistic treatment of organic aerosols as non-volatile and with a fixed size distribution. Further development includes adding the condensation of organics on coarse mode aerosols - dust and sea salt, thus making all organics in the system semi-volatile. To test and simplify the model, a Monte-Carlo analysis is performed to pin point which processes affect organics the most under which chemical and meteorological conditions. Since the model's parameterizations have the ability to capture a very wide range of conditions, from very clean to very polluted and for a wide range of meteorological conditions, all possible scenarios on Earth across the whole parameter space, including temperature, location, emissions and oxidant levels, are examined. The Monte-Carlo simulations provide quantitative information on the sensitivity of the newly developed model and help us understand how organics are affecting the size distribution, mixing state and volatility distribution at varying levels of meteorological conditions and pollution levels. In addition, these simulations give information on which parameters play a critical role in the aerosol distribution and evolution in the atmosphere and which do not, that will facilitate the simplification of the box model, an important step in its implementation in the global model.

Volatile communication in plant-aphid interactions.

PubMed

de Vos, Martin; Jander, Georg

2010-08-01

Volatile communication plays an important role in mediating the interactions between plants, aphids, and other organisms in the environment. In response to aphid infestation, many plants initiate indirect defenses through the release of volatiles that attract ladybugs, parasitoid wasps, and other aphid-consuming predators. Aphid-induced volatile release in the model plant Arabidopsis thaliana requires the jasmonate signaling pathway. Volatile release is also induced by infection with aphid-transmitted viruses. Consistent with mathematical models of optimal transmission, viruses that are acquired rapidly by aphids induce volatile release to attract migratory aphids, but discourage long-term aphid feeding. Although the ecology of these interactions is well-studied, further research is needed to identify the molecular basis of aphid-induced and virus-induced changes in plant volatile release. Copyright 2010 Elsevier Ltd. All rights reserved.

[Study on chemical constituents of volatile oil from rhizomes and leaves of Pileostegia viburnoides var. glabrescens by GC-MS].

PubMed

Zou, Ju-Ying; Chen, Sheng-Huang; Li, Qin-Wen; Chen, Han-Jun; Liu, Bei-Bei; Du, Fan

2012-04-01

To analyze the chemical constituents of volatile oil from the rhizomes and leaves of Pileostegia viburnoides var. glabrescens by GC-MS. The volatile oil was extracted from the rhizomes and leaves of Pileostegia viburnoides var. glabrescens by steam distillation. The constituents of volatile oil were identified by GC-MS technology. 37 compounds were identified from the oil of rhizomes. 36 compounds were identified from the oil of leaves. The rhizomes and leaves volatile oil had 18 compounds in common. This study is the first one to report the volatile components of Pileostegia viburnoides var. glabrescens. It can provide a scientific basis for rational use of the rhizomes and leaves of Pileostegia viburnoides var. glabrescens.

VOLATILE ORGANIC COMPOUND DETERMINATIONS USING SURROGATE-BASED CORRECTION FOR METHOD AND MATRIX EFFECTS

EPA Science Inventory

The principal properties related to analyte recovery in a vacuum distillate are boiling point and relative volatility. The basis for selecting compounds to measure the relationship between these properties and recovery for a vacuum distillation is presented. Surrogates are incorp...

Can Condensing Organic Aerosols Lead to Less Cloud Particles?

NASA Astrophysics Data System (ADS)

Gao, C. Y.; Tsigaridis, K.; Bauer, S.

2017-12-01

We examined the impact of condensing organic aerosols on activated cloud number concentration in a new aerosol microphysics box model, MATRIX-VBS. The model includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) that resolves aerosol mass and number concentrations and aerosol mixing state. Preliminary results show that by including the condensation of organic aerosols, the new model (MATRIX-VBS) has less activated particles compared to the original model (MATRIX), which treats organic aerosols as non-volatile. Parameters such as aerosol chemical composition, mass and number concentrations, and particle sizes which affect activated cloud number concentration are thoroughly evaluated via a suite of Monte-Carlo simulations. The Monte-Carlo simulations also provide information on which climate-relevant parameters play a critical role in the aerosol evolution in the atmosphere. This study also helps simplifying the newly developed box model which will soon be implemented in the global model GISS ModelE as a module.

On multilevel RBF collocation to solve nonlinear PDEs arising from endogenous stochastic volatility models

NASA Astrophysics Data System (ADS)

Bastani, Ali Foroush; Dastgerdi, Maryam Vahid; Mighani, Abolfazl

2018-06-01

The main aim of this paper is the analytical and numerical study of a time-dependent second-order nonlinear partial differential equation (PDE) arising from the endogenous stochastic volatility model, introduced in [Bensoussan, A., Crouhy, M. and Galai, D., Stochastic equity volatility related to the leverage effect (I): equity volatility behavior. Applied Mathematical Finance, 1, 63-85, 1994]. As the first step, we derive a consistent set of initial and boundary conditions to complement the PDE, when the firm is financed by equity and debt. In the sequel, we propose a Newton-based iteration scheme for nonlinear parabolic PDEs which is an extension of a method for solving elliptic partial differential equations introduced in [Fasshauer, G. E., Newton iteration with multiquadrics for the solution of nonlinear PDEs. Computers and Mathematics with Applications, 43, 423-438, 2002]. The scheme is based on multilevel collocation using radial basis functions (RBFs) to solve the resulting locally linearized elliptic PDEs obtained at each level of the Newton iteration. We show the effectiveness of the resulting framework by solving a prototypical example from the field and compare the results with those obtained from three different techniques: (1) a finite difference discretization; (2) a naive RBF collocation and (3) a benchmark approximation, introduced for the first time in this paper. The numerical results confirm the robustness, higher convergence rate and good stability properties of the proposed scheme compared to other alternatives. We also comment on some possible research directions in this field.

Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

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

Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan

2013-04-27

Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwindmore » of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.« less

77 FR 52606 - Approval and Promulgation of Air Quality Implementation Plans; Indiana; Volatile Organic...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-30

... Promulgation of Air Quality Implementation Plans; Indiana; Volatile Organic Compounds; Architectural and... sets limits on the amount of volatile organic compounds (VOC) in architectural and industrial... Indiana SIP a new rule within Title 326, Article 8 ``Volatile Organic Compound Rules'' that limits the VOC...

Effects of chlorine on the volatilization of heavy metals during the co-combustion of sewage sludge.

PubMed

Yu, Shengrong; Zhang, Bin; Wei, Jiangxiong; Zhang, Tongsheng; Yu, Qijun; Zhang, Wensheng

2017-04-01

To clarify the volatilization of heavy metals (Cu, Ni, Pb, and Zn) in sewage sludge during co-combustion in cement kiln, effects of addition and types of four chlorides and temperature on the volatilization of heavy metals in raw meal with 25wt.% sewage sludge were investigated. The results showed that the volatilization of Cu, Ni, and Pb increased significantly with increase of chlorides addition, while no obvious change in the volatilization of Zn was observed. The effectiveness of chlorides on the volatilization of heavy metals depended on their release capacity of chlorine radicals and the chlorine combined capacity of heavy metals. Higher calcination temperature resulted in dramatically increase in the volatilization of heavy metals due to easier formation of volatile heavy metal chlorides. The results will provide a guideline for co-combusting heavy metals contained solid wastes in cement kiln on the basis of security. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of sublethal preculturing on the survival of probiotics and metabolite formation in set-yoghurt.

PubMed

Settachaimongkon, Sarn; van Valenberg, Hein J F; Winata, Vera; Wang, Xiaoxi; Nout, M J Robert; van Hooijdonk, Toon C M; Zwietering, Marcel H; Smid, Eddy J

2015-08-01

The objective of this study was to investigate the effect of preculturing of Lactobacillus rhamnosus GG and Bifidobacterium animalis subsp. lactis BB12 under sublethal stress conditions on their survival and metabolite formation in set-yoghurt. Prior to co-cultivation with yoghurt starters in milk, the two probiotic strains were precultured under sublethal stress conditions (combinations of elevated NaCl and low pH) in a batch fermentor. The activity of sublethally precultured probiotics was evaluated during fermentation and refrigerated storage by monitoring bacterial population dynamics, milk acidification and changes in volatile and non-volatile metabolite profiles of set-yoghurt. The results demonstrated adaptive stress responses of the two probiotic strains resulting in their viability improvement without adverse influence on milk acidification. A complementary metabolomic approach using SPME-GC/MS and (1)H-NMR resulted in the identification of 35 volatiles and 43 non-volatile polar metabolites, respectively. Principal component analysis revealed substantial impact of the activity of sublethally precultured probiotics on metabolite formation demonstrated by distinctive volatile and non-volatile metabolite profiles of set-yoghurt. Changes in relative abundance of various aroma compounds suggest that incorporation of stress-adapted probiotics considerably influences the organoleptic quality of product. This study provides new information on the application of stress-adapted probiotics in an actual food-carrier environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Substitution of carcinogenic solvent dichloromethane for the extraction of volatile compounds in a fat-free model food system.

PubMed

Cayot, Nathalie; Lafarge, Céline; Bou-Maroun, Elias; Cayot, Philippe

2016-07-22

Dichloromethane is known as a very efficient solvent, but, as other halogenated solvents, is recognized as a hazardous product (CMR substance). The objective of the present work is to propose substitution solvent for the extraction of volatile compounds. The most important physico-chemical parameters in the choice of an appropriate extraction solvent of volatile compounds are reviewed. Various solvents are selected on this basis and on their hazard characteristics. The selected solvents, safer than dichloromethane, are compared using the extraction efficiency of volatile compounds from a model food product able to interact with volatile compounds. Volatile compounds with different hydrophobicity are used. High extraction yields were positively correlated with high boiling points and high Log Kow values of volatile compounds. Mixtures of solvents such as azeotrope propan-2-one/cyclopentane, azeotrope ethyl acetate/ethanol, and mixture ethyl acetate/ethanol (3:1, v/v) gave higher extraction yields than those obtained with dichloromethane. Copyright © 2016 Elsevier B.V. All rights reserved.

A semiempirical correlation between enthalpy of vaporization and saturation concentration for organic aerosol.

PubMed

Epstein, Scott A; Riipinen, Ilona; Donahue, Neil M

2010-01-15

To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic compounds, we have developed a semiempirical correlation between the saturation concentration (C*, microg m(-3)) and the heat of vaporization (deltaH(VAP), kJ mol(-1)) for organics in the volatility basis set. Near room temperature, deltaH(VAP) = -11 log(10)C(300)(*) + 129. Knowledge of the relationship between C* and deltaH(VAP) constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our deltaH(VAP) values agrees well with thermal behavior observed in laboratory experiments.

78 FR 9823 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of a Group of Four...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-12

... Air Quality: Revision to Definition of Volatile Organic Compounds--Exclusion of a Group of Four... amending its definition of VOC at 40 CFR 51.100(s) to exclude a group of four HFPE's identified as HCF 2... adds four chemical compounds to the list of compounds excluded from the definition of VOC on the basis...

Fig volatile compounds--a first comparative study.

PubMed

Grison-Pigé, Laure; Hossaert-McKey, Martine; Greeff, Jaco M; Bessière, Jean-Marie

2002-09-01

We analysed the compounds of volatile blends released by receptive figs of twenty Ficus species to attract their specific pollinating wasps. In all, 99 different compounds were identified. The compounds are mainly terpenoids, aliphatic compounds and products from the shikimic acid pathway. In each species blend, there are few major compounds, which are generally common among floral fragrances. Most species blends also include rare compounds, but generally their proportion in the blend is low. A possible basis for species-specificity of Ficus-wasp interactions is discussed in relation to the patterns of volatiles found in this interspecies comparison. Copyright 2002 Elsevier Science Ltd.

Effect of different drying techniques on bioactive components, fatty acid composition, and volatile profile of robusta coffee beans.

PubMed

Dong, Wenjiang; Hu, Rongsuo; Chu, Zhong; Zhao, Jianping; Tan, Lehe

2017-11-01

This study investigated the effect of different drying techniques, namely, room-temperature drying (RTD), solar drying (SD), heat-pump drying (HPD), hot-air drying (HAD), and freeze drying (FD), on bioactive components, fatty acid composition, and the volatile compound profile of robusta coffee beans. The data showed that FD was an effective method to preserve fat, organic acids, and monounsaturated fatty acids. In contrast, HAD was ideal for retaining polyunsaturated fatty acids and amino acids. Sixty-two volatile compounds were identified in the differently dried coffee beans, representing 90% of the volatile compounds. HPD of the coffee beans produced the largest number of volatiles, whereas FD resulted in the highest volatile content. A principal component analysis demonstrated a close relationship between the HPD, SD, and RTD methods whereas the FD and HAD methods were significantly different. Overall, the results provide a basis for potential application to other similar thermal sensitive materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

77 FR 52630 - Approval and Promulgation of Air Quality Implementation Plans; Indiana; Volatile Organic...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-30

... Promulgation of Air Quality Implementation Plans; Indiana; Volatile Organic Compounds; Architectural and... rule that sets emissions limits on the amount of volatile organic compounds in architectural and... period. Any parties interested in commenting on this action should do so at this time. Please note that...

Introductory lecture: atmospheric organic aerosols: insights from the combination of measurements and chemical transport models.

PubMed

Pandis, Spyros N; Donahue, Neil M; Murphy, Benjamin N; Riipinen, Ilona; Fountoukis, Christos; Karnezi, Eleni; Patoulias, David; Skyllakou, Ksakousti

2013-01-01

The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile compounds to extremely low volatility compounds can explain the observed growth rates of new particles in rural environments.

Brain Injury Alters Volatile Metabolome

PubMed Central

Cohen, Akiva S.; Gordon, Amy R.; Opiekun, Maryanne; Martin, Talia; Elkind, Jaclynn; Lundström, Johan N.; Beauchamp, Gary K.

2016-01-01

Chemical signals arising from body secretions and excretions communicate information about health status as have been reported in a range of animal models of disease. A potential common pathway for diseases to alter chemical signals is via activation of immune function—which is known to be intimately involved in modulation of chemical signals in several species. Based on our prior findings that both immunization and inflammation alter volatile body odors, we hypothesized that injury accompanied by inflammation might correspondingly modify the volatile metabolome to create a signature endophenotype. In particular, we investigated alteration of the volatile metabolome as a result of traumatic brain injury. Here, we demonstrate that mice could be trained in a behavioral assay to discriminate mouse models subjected to lateral fluid percussion injury from appropriate surgical sham controls on the basis of volatile urinary metabolites. Chemical analyses of the urine samples similarly demonstrated that brain injury altered urine volatile profiles. Behavioral and chemical analyses further indicated that alteration of the volatile metabolome induced by brain injury and alteration resulting from lipopolysaccharide-associated inflammation were not synonymous. Monitoring of alterations in the volatile metabolome may be a useful tool for rapid brain trauma diagnosis and for monitoring recovery. PMID:26926034

Feature extraction and selection from volatile compounds for analytical classification of Chinese red wines from different varieties.

PubMed

Zhang, Jian; Li, Li; Gao, Nianfa; Wang, Depei; Gao, Qiang; Jiang, Shengping

2010-03-10

This work was undertaken to evaluate whether it is possible to determine the variety of a Chinese wine on the basis of its volatile compounds, and to investigate if discrimination models could be developed with the experimental wines that could be used for the commercial ones. A headspace solid-phase microextraction gas chromatographic (HS-SPME-GC) procedure was used to determine the volatile compounds and a blind analysis based on Ac/Ais (peak area of volatile compound/peak area of internal standard) was carried out for statistical purposes. One way analysis of variance (ANOVA), principal component analysis (PCA) and stepwise linear discriminant analysis (SLDA) were used to process data and to develop discriminant models. Only 11 peaks enabled to differentiate and classify the experimental wines. SLDA allowed 100% recognition ability for three grape varieties, 100% prediction ability for Cabernet Sauvignon and Cabernet Gernischt wines, but only 92.31% for Merlot wines. A more valid and robust way was to use the PCA scores to do the discriminant analysis. When we performed SLDA this way, 100% recognition ability and 100% prediction ability were obtained. At last, 11 peaks which selected by SLDA from raw analysis set had been identified. When we demonstrated the models using commercial wines, the models showed 100% recognition ability for the wines collected directly from winery and without ageing, but only 65% for the others. Therefore, the varietal factor was currently discredited as a differentiating parameter for commercial wines in China. Nevertheless, this method could be applied as a screening tool and as a complement to other methods for grape base liquors which do not need ageing and blending procedures. 2010 Elsevier B.V. All rights reserved.

Influence of different proteolytic strains of Streptococcus thermophilus in co-culture with Lactobacillus delbrueckii subsp. bulgaricus on the metabolite profile of set-yoghurt.

PubMed

Settachaimongkon, Sarn; Nout, M J Robert; Antunes Fernandes, Elsa C; Hettinga, Kasper A; Vervoort, Jacques M; van Hooijdonk, Toon C M; Zwietering, Marcel H; Smid, Eddy J; van Valenberg, Hein J F

2014-05-02

Proto-cooperation between Streptococcus thermophilus and Lactobacillus delbrueckii subsp. bulgaricus is one of the key factors that determine the fermentation process and final quality of yoghurt. In this study, the interaction between different proteolytic strains of S. thermophilus and L. delbrueckii subsp. bulgaricus was investigated in terms of microbial growth, acidification and changes in the biochemical composition of milk during set-yoghurt fermentation. A complementary metabolomics approach was applied for global characterization of volatile and non-volatile polar metabolite profiles of yoghurt associated with proteolytic activity of the individual strains in the starter cultures. The results demonstrated that only non-proteolytic S. thermophilus (Prt-) strain performed proto-cooperation with L. delbrueckii subsp. bulgaricus. The proto-cooperation resulted in significant higher populations of the two species, faster milk acidification, significant abundance of aroma volatiles and non-volatile metabolites desirable for a good organoleptic quality of yoghurt. Headspace SPME-GC/MS and (1)H NMR resulted in the identification of 35 volatiles and 43 non-volatile polar metabolites, respectively. Furthermore, multivariate statistical analysis allows discriminating set-yoghurts fermented by different types of starter cultures according to their metabolite profiles. Our finding underlines that selection of suitable strain combinations in yoghurt starters is important for achieving the best technological performance regarding the quality of product. Copyright © 2014 Elsevier B.V. All rights reserved.

Sources and atmospheric transformations of semivolatile organic aerosols

NASA Astrophysics Data System (ADS)

Grieshop, Andrew P.

Fine atmospheric particulate matter (PM2.5) is associated with increased mortality, a fact which led the EPA to promulgate a National Ambient Air Quality Standard (NAAQS) for PM2.5 in 1997. Organic material contributes a substantial portion of the PM2.5 mass; organic aerosols (OA) are either directly emitted (primary OA or POA) or formed via the atmospheric oxidation of volatile precursor compounds as secondary OA (SOA). The relative contributions of POA and SOA to atmospheric OA are uncertain, as are the contributions from various source classes (e.g. motor vehicles, biomass burning). This dissertation first assesses the importance of organic PM within the context of current US air pollution regulations. Most control efforts to date have focused on the inorganic component of PM. Although growing evidence strongly implicates OA, especially which from motor vehicles, in the health effects of PM, uncertain and complex source-receptor relationships for OA discourage its direct control for NAAQS compliance. Analysis of both ambient data and chemical transport modeling results indicate that OA does not play a dominant role in NAAQS violations in most areas of the country under current and likely future regulations. Therefore, new regulatory approaches will likely be required to directly address potential health impacts associated with OA. To help develop the scientific understanding needed to better regulate OA, this dissertation examined the evolution of organic aerosol emitted by combustion systems. The current conceptual model of POA is that it is non-volatile and non-reactive. Both of these assumptions were experimental investigated in this dissertation. Novel dilution measurements were carried out to investigate the gas-particle partitioning of OA at atmospherically-relevant conditions. The results demonstrate that POA from combustion sources is semivolatile. Therefore its gas-particle partitioning depends on temperature and atmospheric concentrations; heating and dilution both cause it to evaporate. Gas-particle partitioning was parameterized using absorptive partitioning theory and the volatility basis-set framework. The dynamics of particle evaporation proved to be much slower than expected and measurements of aerosol composition indicate that particle composition varies with partitioning. These findings have major implications for the measurement and modeling of POA from combustion sources. Source tests need to be conducted at atmospheric concentrations and temperatures. Upon entering the atmosphere, organic aerosol emissions are aged via photochemical reactions. Experiments with dilute wood-smoke demonstrate the dramatic evolution these emissions undergo within hours of emission. Aging produced substantial new OA (doubling or tripling OA levels within hours) and changed particle composition and volatility. These changes are consistent with model predictions based on the partitioning and aging (via gas-phase photochemistry) of semi-volatile species represented with the basis-set framework. Aging of wood-smoke OA made created a much more oxygenated aerosol and formed material spectrally similar to oxygenated OA found widely in the atmosphere. The oxygenated aerosol is also similar that formed with similar experiments conducted with diesel engine emissions. Therefore, aging of emissions from diverse sources may produce chemically similar OA, complicating the establishment of robust source-receptor relationships.

Sources of atmospheric ammonia

NASA Technical Reports Server (NTRS)

Harriss, R. C.; Michaels, J. T.

1982-01-01

The information available on factors that influence emissions from the principal societal sources of ammonia to the atmosphere, namely combustion processes, volatilization of farm animal wastes, and volatilization of fertilizers, is reviewed. Emission factors are established for each major source of atmospheric ammonia. The factors are then multiplied by appropriate source characterization descriptors to obtain calculated fluxes of ammonia to the atmosphere on a state-by-state basis for the United States.

Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

NASA Astrophysics Data System (ADS)

Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

2015-08-01

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

Scientific results of the NASA-sponsored study project on Mars: Evolution of volcanism, tectonics, and volatiles

NASA Technical Reports Server (NTRS)

Solomon, Sean C. (Editor); Sharpton, Virgil L. (Editor); Zimbelman, James R. (Editor)

1990-01-01

The objectives of the Mars: Evolution of Volcanism, Tectonics, and Volatiles (MEVTV) project are to outline the volcanic and tectonic history of Mars; to determine the influence of volatiles on Martian volcanic and tectonic processes; and to attempt to determine the compositional, thermal, and volatile history of Mars from its volcanic and tectonic evolution. Available data sets were used to test general models of the volcanic and tectonic history of Mars.

Volatile constituents of Trifolium pratense and T. repens from N.E. Italian alpine pastures.

PubMed

Tava, Aldo; Ramella, Daniele; Grecchi, Maris; Aceto, Paolo; Paoletti, Renato; Piano, Efisio

2009-06-01

The composition of the volatile fraction of two important forage legumes from Italian sub-alpine N.E. pastureland, namely Trifolium pratense L. subsp. pratense (red clover) and T. repens subsp. repens (white clover) were investigated. The volatile oil was obtained from the fresh aerial parts by steam distillation and analyzed by GC/FID and GC/MS. The oil yield was 0.018 and 0.021% (weight/fresh weight basis) for T. pratense and T. repens, respectively. Several classes of compounds were found in both the oils, including alcohols, aldehydes, ketones, terpenes, esters, hydrocarbons, phenolics and acids. Qualitative and quantitative differences were found.

Volatility, house edge and prize structure of gambling games.

PubMed

Turner, Nigel E

2011-12-01

This study used simulations to examine the effect of prize structure on the outcome volatility and the number of winners of various game configurations. The two most common prize structures found in gambling games are even money payoff games (bet $1; win $2) found on most table games and multilevel prizes structures found in gambling machine games. Simulations were set up to examine the effect of prize structure on the long-term outcomes of these games. Eight different prize structures were compared in terms of the number of winners and volatility. It was found that the standard table game and commercial gambling machines produced fairly high numbers of short term winners (1 h), but few long term winners (50 h). It was found that the typical even money game set up produced the lowest level of volatility. Of the multilevel prize structures examined, the three simulations based on commercial gambling machines were the least volatile. The results are examined in terms of the pragmatics of game design.

[Application characteristics and situation analysis of volatile oils in database of Chinese patent medicine].

PubMed

Wang, Sai-Jun; Wu, Zhen-Feng; Yang, Ming; Wang, Ya-Qi; Hu, Peng-Yi; Jie, Xiao-Lu; Han, Fei; Wang, Fang

2014-09-01

Aromatic traditional Chinese medicines have a long history in China, with wide varieties. Volatile oils are active ingredients extracted from aromatic herbal medicines, which usually contain tens or hundreds of ingredients, with many biological activities. Therefore, volatile oils are often used in combined prescriptions and made into various efficient preparations for oral administration or external use. Based on the sources from the database of Newly Edited National Chinese Traditional Patent Medicines (the second edition), the author selected 266 Chinese patent medicines containing volatile oils in this paper, and then established an information sheet covering such items as name, dosage, dosage form, specification and usage, and main functions. Subsequently, on the basis of the multidisciplinary knowledge of pharmaceutics, traditional Chinese pharmacology and basic theory of traditional Chinese medicine, efforts were also made in the statistics of the dosage form and usage, variety of volatile oils and main functions, as well as the status analysis on volatile oils in terms of the dosage form development, prescription development, drug instruction and quality control, in order to lay a foundation for the further exploration of the market development situations of volatile oils and the future development orientation.

Scaling properties of foreign exchange volatility

NASA Astrophysics Data System (ADS)

Gençay, Ramazan; Selçuk, Faruk; Whitcher, Brandon

2001-01-01

In this paper, we investigate the scaling properties of foreign exchange volatility. Our methodology is based on a wavelet multi-scaling approach which decomposes the variance of a time series and the covariance between two time series on a scale by scale basis through the application of a discrete wavelet transformation. It is shown that foreign exchange rate volatilities follow different scaling laws at different horizons. Particularly, there is a smaller degree of persistence in intra-day volatility as compared to volatility at one day and higher scales. Therefore, a common practice in the risk management industry to convert risk measures calculated at shorter horizons into longer horizons through a global scaling parameter may not be appropriate. This paper also demonstrates that correlation between the foreign exchange volatilities is the lowest at the intra-day scales but exhibits a gradual increase up to a daily scale. The correlation coefficient stabilizes at scales one day and higher. Therefore, the benefit of currency diversification is the greatest at the intra-day scales and diminishes gradually at higher scales (lower frequencies). The wavelet cross-correlation analysis also indicates that the association between two volatilities is stronger at lower frequencies.

Effect of hot air drying on volatile compounds of Flammulina velutipes detected by HS-SPME-GC-MS and electronic nose.

PubMed

Yang, Wenjian; Yu, Jie; Pei, Fei; Mariga, Alfred Mugambi; Ma, Ning; Fang, Yong; Hu, Qiuhui

2016-04-01

Volatile compounds are important factors that affect the flavor quality of Flammulina velutipes, but the changes occurring during hot air drying is still unclear. To clarify the dynamic changes of flavor components during hot air drying, comprehensive flavor characterization and volatile compounds of F. velutipes were evaluated using electronic nose technology and headspace solid phase micro-extraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS), respectively. Results showed that volatile components in F. velutipes significantly changed during hot air drying according to the principal component analysis and radar fingerprint chart of electronic nose. Volatile compounds of fresh F. velutipes consisted mainly of ketones, aldehydes and alcohols, and 3-octanone was the dominant compound. Drying process could significantly decrease the relative content of ketones and promoted the generation of alcohols, acids, and esters, which became the main volatile compounds of dried F. velutipes. These may provide a theoretical basis for the formation mechanism of flavor substances in dried F. velutipes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of Morphology, Volatile Profiles, and Molecular Markers in Edible Desert Truffles from the Negev Desert.

PubMed

Kamle, Madhu; Bar, Einat; Lewinsohn, Dalia; Shavit, Elinoar; Roth-Bejerano, Nurit; Kagan-Zur, Varda; Barak, Ze'ev; Guy, Ofer; Zaady, Eli; Lewinsohn, Efraim; Sitrit, Yaron

2017-03-28

Desert truffles are mycorrhizal, hypogeous fungi considered a delicacy. On the basis of morphological characters, we identified three desert truffle species that grow in the same habitat in the Negev desert. These include Picoa lefebvrei (Pat.), Tirmania nivea (Desf.) Trappe, and Terfezia boudieri (Chatain), all associated with Helianthemum sessiliflorum. Their taxonomy was confirmed by PCR-RFLP. The main volatiles of fruit bodies of T. boudieri and T. nivea were 1-octen-3-ol and hexanal; however, volatiles of the latter species further included branched-chain amino acid derivatives such as 2-methylbutanal and 3-methylbutanal, phenylalanine derivatives such as benzaldehyde and benzenacetaldehyde, and methionine derivatives such as methional and dimethyl disulfide. The least aromatic truffle, P. lefebvrei, contained low levels of 1-octen-3-ol as the main volatile. Axenic mycelia cultures of T. boudieri displayed a simpler volatile profile compared to its fruit bodies. This work highlights differences in the volatile profiles of desert truffles and could hence be of interest for selecting and cultivating genotypes with the most likable aroma.

Concentrations of Volatiles in the Lunar Regolith

NASA Technical Reports Server (NTRS)

Taylor, Jeff; Taylor, Larry; Duke, Mike

2007-01-01

To set lower and upper limits on the overall amounts and types of volatiles released during heating of polar regolith, we examined the data for equatorial lunar regolith and for the compositions of comets. The purpose, specifically, was to answer these questions: 1. Upper/Lower limits and 'best guess' for total amount of volatiles (by weight %) released from lunar regolith up to 150C 2. Upper/Lower limit and 'best guess' for composition of the volatiles released from the lunar regolith by weight %

Childhood Income Volatility and Adult Outcomes. University of Kentucky Center for Poverty Research Discussion Paper Series, DP2012-03

ERIC Educational Resources Information Center

Hardy, Bradley

2012-01-01

Using data linked across generations in the Panel Study of Income Dynamics, I estimate the relationship between exposure to volatile income during childhood and a set of socioeconomic outcomes in adulthood. The empirical framework is an augmented intergenerational income mobility model that includes controls for income volatility. I measure income…

The Distribution of Ice in Lunar Permanently Shadowed Regions: Science Enabling Exploration (Invited)

NASA Astrophysics Data System (ADS)

Hurley, D.; Elphic, R. C.; Bussey, B.; Hibbitts, C.; Lawrence, D. J.

2013-12-01

Recent prospecting indicates that water ice occurs in enhanced abundances in some lunar PSRs. That water constitutes a resource that enables lunar exploration if it can be harvested for fuel and life support. Future lunar exploration missions will need detailed information about the distribution of volatiles in lunar permanently shadowed regions (PSRs). In addition, the volatiles also offer key insights into the recent and distant past, as they have trapped volatiles delivered to the moon over ~2 Gyr. This comprises an unparalleled reservoir of past inner solar system volatiles, and future scientific missions are needed to make the measurements that will reveal the composition of those volatiles. These scientific missions will necessarily have to acquire and analyze samples of volatiles from the PSRs. For both exploration and scientific purposes, the precise location of volatiles will need to be known. However, data indicate that ice is distributed heterogeneously on the Moon. It is unlikely that the distribution will be known a priori with enough spatial resolution to guarantee access to volatiles using a single point sample. Some mechanism for laterally or vertically distributed access will increase the likelihood of acquiring a rich sample of volatiles. Trade studies will need to be conducted to anticipate the necessary range and duration of missions to lunar PSRs that will be needed to accomplish the mission objectives. We examine the spatial distribution of volatiles in lunar PSRs reported from data analyses and couple those with models of smaller scale processes. FUV and laser data from PSRs that indicate the average surface distribution is consistent with low abundances on the extreme surface in most PSRs. Neutron and radar data that probe the distribution at depth show heterogeneity at broad spatial resolution. We consider those data in conjunction with the model to understand the full, 3-D nature of the heterogeneity. A Monte Carlo technique simulates the stochastic process of impact gardening on a putative ice deposit. The model uses the crater production function as a basis for generating a random selection of impact craters over time. Impacts are implemented by modifying the topography, volatile content, and depth distribution in the simulation volume on a case by case basis. This technique will never be able to reproduce the exact impact history of a particular area. But by conducting multiple runs with the same initial conditions and a different seed to the random number generator, we are able to calculate the probability of situations occurring. Further, by repeating the simulations with varied initial conditions, we calculate the dependence of the expectation values on the inputs. We present findings regarding the heterogeneity of volatiles in PSRs as a function of age, initial ice thickness, and contributions from steady sources.

Comparison of two headspace sampling techniques for the analysis of off-flavour volatiles from oat based products.

PubMed

Cognat, Claudine; Shepherd, Tom; Verrall, Susan R; Stewart, Derek

2012-10-01

Two different headspace sampling techniques were compared for analysis of aroma volatiles from freshly produced and aged plain oatcakes. Solid phase microextraction (SPME) using a Carboxen-Polydimethylsiloxane (PDMS) fibre and entrainment on Tenax TA within an adsorbent tube were used for collection of volatiles. The effects of variation in the sampling method were also considered using SPME. The data obtained using both techniques were processed by multivariate statistical analysis (PCA). Both techniques showed similar capacities to discriminate between the samples at different ages. Discrimination between fresh and rancid samples could be made on the basis of changes in the relative abundances of 14-15 of the constituents in the volatile profiles. A significant effect on the detection level of volatile compounds was observed when samples were crushed and analysed by SPME-GC-MS, in comparison to undisturbed product. The applicability and cost effectiveness of both methods were considered. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photoacid generator study for chemically amplified negative resists for high-resolution lithography

NASA Astrophysics Data System (ADS)

Dentinger, Paul M.; Knapp, Kurtis G.; Reynolds, Geoffrey W.; Taylor, James W.; Fedynyshyn, Theodore H.; Richardson, Todd A.

1998-06-01

The effect of photoacid generator and photogenerated acid molecular structures on a negative-tone chemically-amplified resist was tested using two different sets of acid generators, each set with one formulation creating a 'volatile' acid, and the other formulation creating a 'non- volatile' acid when exposed to x-rays. The acids from one set were generated from a derivative of iodonium salt and the acids from the other set were generated from a covalently bound photoacid generator. Both sets were compared to Shipley SAL 605 resist. In this study of five formulations, normalized remaining thickness (NRT) curves, SEM images of printed lines, spectrophotometric titration of the photogenerated acid, real-time curves, SEM images of printed lines, spectrophotometric titration of the photogenerated acid, real-time FTIR for kinetics of the PEB reaction, dissolution rate measurements, and atomic force microscopy for surface roughness were employed. RT-FTIR suggested that both the proposed 'volatile' and 'non- volatile' acids were retained to approximately the same extent within the films cast from these formulations. A mechanism is suggested where the type of photogenerated acid has an effect on the kinetics of the reaction and the photogenerated acid or photoacid effect on the kinetics of the reaction and the photogenerated acid or photoacid generator has a large effect on the ability of the aqueous developer to penetrate or dissolve the film.

Volatile Metabolites

PubMed Central

Rowan, Daryl D.

2011-01-01

Volatile organic compounds (volatiles) comprise a chemically diverse class of low molecular weight organic compounds having an appreciable vapor pressure under ambient conditions. Volatiles produced by plants attract pollinators and seed dispersers, and provide defense against pests and pathogens. For insects, volatiles may act as pheromones directing social behavior or as cues for finding hosts or prey. For humans, volatiles are important as flavorants and as possible disease biomarkers. The marine environment is also a major source of halogenated and sulfur-containing volatiles which participate in the global cycling of these elements. While volatile analysis commonly measures a rather restricted set of analytes, the diverse and extreme physical properties of volatiles provide unique analytical challenges. Volatiles constitute only a small proportion of the total number of metabolites produced by living organisms, however, because of their roles as signaling molecules (semiochemicals) both within and between organisms, accurately measuring and determining the roles of these compounds is crucial to an integrated understanding of living systems. This review summarizes recent developments in volatile research from a metabolomics perspective with a focus on the role of recent technical innovation in developing new areas of volatile research and expanding the range of ecological interactions which may be mediated by volatile organic metabolites. PMID:24957243

Evaluation of Organic Aerosol Formation and Apportionment in a polluted Megacity

NASA Astrophysics Data System (ADS)

Tsimpidi, A. P.; Karydis, V. A.; Zavala, M.; Lei, W.; Decarlo, P. F.; Ulbrich, I.; Jimenez, J. L.; Molina, L. T.; Pandis, S. N.

2009-04-01

Pollution from megacities and large urban areas is important not only for local effects on health, visibility, and ecosystems but also because of their collective influence on atmospheric chemistry and radiative forcing in regional and global scale. Organic species account for a large fraction of the submicron aerosol mass at most megacities. Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) have been difficult to quantify. In this study, new primary and secondary organic aerosol modules were added to PMCAMx, a three dimensional chemical transport model (Gaydos et al., 2007). The new modeling framework is based on the volatility basis-set approach (Lane et al., 2007): both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments (Robinson et al., 2007). PMCAMx is applied in the Mexico City Metropolitan Area during April 2003 and March 2006. The model predictions are compared with Aerodyne's Aerosol Mass Spectrometer (AMS) observations from the MCMA and MILAGRO campaigns respectively. Furthermore, the predicted concentrations over Mexico City are compared against measurements from a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) which was onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign (DeCarlo et al., 2008). The organic aerosol (OA) to CO ratio is used as an indicator in order to evaluate the photo-oxidation of the predicted OA after its horizontal and vertical advection. References Gaydos, T.M.; Pinder, R.W.; Koo, B.; Fahey, K.M.; Pandis, S.N., 2007. Development and application of a three-dimensional aerosol chemical transport model, PMCAMx. Atmospheric Environment 41, 2594-2611. Lane, T.E.; Donahue, N.M.; Pandis, S.N. 2008. Simulating Secondary Organic Aerosol Formation using the Votality Basis-Set Approach in a Chemical Transport Model, Atmospheric Environment 42, 7439-7451 Robinson, A.L.; Donahue, N.M.; Shrivastava, M.K.; Weitkamp, E.A.; Sage, A.M.; Grieshop, A.P.; Lane, T.E.; Pandis, S.N.; Pierce, J.R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262. DeCarlo, P.F.; Dunlea, E.J., Kimmel,et al., 2008. Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign, Atmos. Chem. Phys., 8, 4027-4048.

Identification Of Geographical Origin Of Coffee Before And After Roasting By Electronic Noses

NASA Astrophysics Data System (ADS)

Sberveglieri, V.; Concina, I.; Falasconi, M.; Ongo, E.; Pulvirenti, A.; Fava, P.

2011-09-01

Geographical origin traceability of food is a relevant issue for both producers' business protection and customers' rights safeguard. Differentiation of coffees on the basis of geographical origin is still a challenging issue, though possible by means of chemical techniques [1]. Between the most widely consumed beverage, coffee is a valuable one, with an aroma constituted by hundreds of volatiles [2]. Since the final global volatile composition is also determined by the cultivation climatic conditions, Electronic Noses (ENs) could be interesting candidates for distinguishing the geographical provenience by exploiting differences in chemical volatile profile. The present investigation is directed toward the characterization of green and roasted coffees samples according to their geographical origin.

Time-varying volatility in Malaysian stock exchange: An empirical study using multiple-volatility-shift fractionally integrated model

NASA Astrophysics Data System (ADS)

Cheong, Chin Wen

2008-02-01

This article investigated the influences of structural breaks on the fractionally integrated time-varying volatility model in the Malaysian stock markets which included the Kuala Lumpur composite index and four major sectoral indices. A fractionally integrated time-varying volatility model combined with sudden changes is developed to study the possibility of structural change in the empirical data sets. Our empirical results showed substantial reduction in fractional differencing parameters after the inclusion of structural change during the Asian financial and currency crises. Moreover, the fractionally integrated model with sudden change in volatility performed better in the estimation and specification evaluations.

Efficient Arsenic Methylation and Volatilization Mediated by a Novel Bacterium from an Arsenic-Contaminated Paddy Soil.

PubMed

Huang, Ke; Chen, Chuan; Zhang, Jun; Tang, Zhu; Shen, Qirong; Rosen, Barry P; Zhao, Fang-Jie

2016-06-21

Microbial arsenic (As) methylation and volatilization are important processes controlling the As biogeochemical cycle in paddy soils. To further understand these processes, we isolated a novel bacterial strain, SM-1, from an As-contaminated paddy soil. SM-1 showed strong As methylation and volatilization abilities, converting almost all arsenite (10 μM) to dimethylarsenate and trimethylarsenic oxide in the medium and trimethylarsine gas into the headspace within 24 h, with trimethylarsine accounting for nearly half of the total As. On the basis of the 16S rRNA sequence, strain SM-1 represents a new species in a new genus within the family Cytophagaceae. Strain SM-1 is abundant in the paddy soil and inoculation of SM-1 greatly enhanced As methylation and volatilization in the soil. An arsenite methyltransferase gene (ArarsM) was cloned from SM-1. When expressed in Escherichia coli, ArArsM conferred the As methylation and volatilization abilities to E. coli and increased its resistance to arsenite. The high As methylation and volatilization abilities of SM-1 are likely attributed to an efficient ArArsM enzyme coupled with low arsenite efflux. These results suggest that strain SM-1 plays an important role in As methylation and volatilization in the paddy soil and has a great potential for As bioremediation.

Study on the composition of the volatile fraction of Hamamelis virginiana.

PubMed

Engel, R; Gutmann, M; Hartisch, C; Kolodziej, H; Nahrstedt, A

1998-04-01

The volatile fractions, obtained by water distillation from the leaves and bark of Hamamelis virginiana L. were analysed in detail by GC-MS. About 175 (leaves) and 168 (bark) compounds have been identified or at least partly characterized on the basis of a computerized database (SeKoMS). The dominating substances were represented by a homologous series of alkanes, alkenes, aliphatic alcohols, related aldehydes, ketones, and fatty acid esters. Importantly, significant differences in the terpenoid and phenylpropanoid patterns of the products obtained from the bark and leaves are apparent: whereas the product of bark distillation was found to typically contain phenylpropanoids and mainly sesquiterpenoids, that obtained from the leaves included some distinct monoterpenoids detected in comparably higher amounts. The chemical composition of the volatiles, when taken together with the absence of specific accumulation sites of lipophilics, emphasizes the definition "volatile fraction" rather than "essential oil".

[Study on dynamic accumulation of index components from Bupleurum chinense in various collecting periods].

PubMed

Wang, Qi-shuai; Li, Xiao-kun; Yang, Yun; Xiao, Gong-sheng; Feng, Wei-sheng

2010-08-01

To study the dynamic change law of volatile oil, saikosaponin a, d and alcohol-extract from Bupleurum chinense at Songxian region in Henan province, and to explore the optimal harvest period of Bupleurum chinense. With the contents of saikosaponin a and d, absorbance of volatile oil and percentage of alcohol-extract as indexes, HPLC-ELSD and ultraviolet spectrophotometry were successively used to analyze them. There are obvious differences among the contents of volatile oil, saikosaponin a, d and alcohol-extract in various collecting periods sample, the absorption of volatile oil in distillation was the highest in October, the content of saikosaponin a was the highest in September, the saikosaponin d in December and the percentage of alcohol-extract in October. The optimal harvest period of Bupleurum chinense at Songxian region in Henan is identified, which can provide scientific basis for crude drug production and processing.

Evaluation of volatile metabolites as markers in Lycopersicon esculentum L. cultivars discrimination by multivariate analysis of headspace solid phase microextraction and mass spectrometry data.

PubMed

Figueira, José; Câmara, Hugo; Pereira, Jorge; Câmara, José S

2014-02-15

To gain insights on the effects of cultivar on the volatile metabolomic expression of different tomato (Lycopersicon esculentum L.) cultivars--Plum, Campari, Grape, Cherry and Regional, cultivated under similar edafoclimatic conditions, and to identify the most discriminate volatile marker metabolites related to the cultivar, the chromatographic profiles resulting from headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-qMS) analysis, combined with multivariate analysis were investigated. The data set composed by the 77 volatile metabolites identified in the target tomato cultivars, 5 of which (2,2,6-trimethylcyclohexanone, 2-methyl-6-methyleneoctan-2-ol, 4-octadecyl-morpholine, (Z)-methyl-3-hexenoate and 3-octanone) are reported for the first time in tomato volatile metabolomic composition, was evaluated by chemometrics. Firstly, principal component analysis was carried out in order to visualise data trends and clusters, and then, linear discriminant analysis in order to detect the set of volatile metabolites able to differentiate groups according to tomato cultivars. The results obtained revealed a perfect discrimination between the different Lycopersicon esculentum L. cultivars considered. The assignment success rate was 100% in classification and 80% in prediction ability by using "leave-one-out" cross-validation procedure. The volatile profile was able to differentiate all five cultivars and revealed complex interactions between them including the participation in the same biosynthetic pathway. The volatile metabolomic platform for tomato samples obtained by HS-SPME/GC-qMS here described, and the interrelationship detected among the volatile metabolites can be used as a roadmap for biotechnological applications, namely to improve tomato aroma and their acceptance in the final consumer, and for traceability studies. Copyright © 2013 Elsevier Ltd. All rights reserved.

Trace Element Study of H Chondrites: Evidence for Meteoroid Streams.

NASA Astrophysics Data System (ADS)

Wolf, Stephen Frederic

1993-01-01

Multivariate statistical analyses, both linear discriminant analysis and logistic regression, of the volatile trace elemental concentrations in H4-6 chondrites reveal compositionally distinguishable subpopulations. Observed difference in volatile trace element composition between Antarctic and non-Antarctic H4-6 chondrites (Lipschutz and Samuels, 1991) can be explained by a compositionaily distinct subpopulation found in Victoria Land, Antarctica. This population of H4-6 chondrites is compositionally distinct from non-Antarctic H4-6 chondrites and from Antarctic H4 -6 chondrites from Queen Maud Land. Comparisons of Queen Maud Land H4-6 chondrites with non-Antarctic H4-6 chondrites do not give reason to believe that these two populations are distinguishable from each other on the basis of the ten volatile trace element concentrations measured. ANOVA indicates that these differences are not the result of trivial causes such as weathering and analytical bias. Thermoluminescence properties of these populations parallels the results of volatile trace element comparisons. Given the differences in terrestrial age between Victoria Land, Queen Maud Land, and modern H4-6 chondrite falls, these results are consistent with a variation in H4-6 chondrite flux on a 300 ky timescale. This conclusion requires the existence of co-orbital meteoroid streams. Statistical analyses of the volatile trace elemental concentrations in non-Antarctic modern falls of H4-6 chondrites also demonstrate that a group of 13 H4-6 chondrites, Cluster 1, selected exclusively for their distinct fall parameters (Dodd, 1992) is compositionally distinguishable from a control group of 45 non-Antarctic modern H4-6 chondrites on the basis of the ten volatile trace element concentrations measured. Model-independent randomization-simulations based on both linear discriminant analysis and logistic regression verify these results. While ANOVA identifies two possible causes for this difference, analytical bias and group classification, a test validation experiment verifies that group classification is the more significant cause of compositional difference between Cluster 1 and non-Cluster 1 modern H4-6 chondrite falls. Thermoluminescence properties of these populations parallels the results of volatile trace element comparisons. This suggests that these meteorites are fragments of a co-orbital meteorite stream derived from a single parent body.

Volatility Properties of Internally- and Externally-Mixed Ambient Aerosols at an Anthropogenically-influenced Forest Site in Southeastern USA

NASA Astrophysics Data System (ADS)

Khlystov, A.; Subramanian, R.

2015-12-01

Secondary organic aerosol (SOA) from biogenic sources has a significant contribution to ambient aerosol loadings in Southeastern USA and thus contributes to adverse health effects of air pollution and influences regional and global climate. Volatility properties of biogenic SOA determine its concentration, reactivity, and lifetime, but are still largely unknown. As part of a larger study to assess the effect of biogenic SOA on aerosol optical properties, a set of instruments, including scanning mobility sizers (SMPS), single particle soot photometer (SP2), and a thermodenuder, was deployed during June 2015 at a Duke Forest site near Chapel Hill, NC. The site is characterized by a significant contribution of both biogenic and urban (mostly traffic) sources. Measurements of changes in aerosol volume and optical size upon heating in the thermodenuder at different temperatures are used to derive volatility properties of the ambient aerosol. A limited set of experiments was carried out using the tandem differential mobility analysis (TDMA) approach to investigate whether the ambient aerosol at the Duke Forest site is internally mixed with respect to its volatility properties. In this presentation we will discuss equilibrium and kinetic aspects of aerosol volatility observed during this study and implications of external vs. internal mixing for derivation of bulk volatility properties of ambient aerosol.

Panel proposes solar system missions

NASA Astrophysics Data System (ADS)

Showstack, Randy

A proposed probe to the Kuiper Belt and Pluto and another to Europa are among the priority Solar System exploration missions that should be pursued by NASA over the next decade, according to an 11 July report by a steering group of the Space Studies Board of the U.S. National Research Council (NRC).The report, "New Frontiers in the Solar System: An Integrated Exploration Strategy," was requested by NASA, and proposes a set of new missions and facilities to respond to key questions in four cross-cutting themes. The themes, which the report indicates form the basis for an integrated space exploration strategy are: the first billion years of Solar System history; volatiles and organics: the stuff of life; the origin and evolution of habitable worlds; and processes: how planets work.

Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

DOE PAGES

Zheng, Y.; Unger, N.; Hodzic, A.; ...

2015-08-28

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO x = NO + NO 2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NO x-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitudemore » and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NO x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO x can be largely attributed to buffering in chemical pathways (low- and high-NO x pathways, O 3 versus NO 3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

Host Plant Species Differentiation in a Polyphagous Moth: Olfaction is Enough.

PubMed

Conchou, Lucie; Anderson, Peter; Birgersson, Göran

2017-08-01

Polyphagous herbivorous insects need to discriminate suitable from unsuitable host plants in complex plant communities. While studies on the olfactory system of monophagous herbivores have revealed close adaptations to their host plant's characteristic volatiles, such adaptive fine-tuning is not possible when a large diversity of plants is suitable. Instead, the available literature on polyphagous herbivore preferences suggests a higher level of plasticity, and a bias towards previously experienced plant species. It is therefore necessary to take into account the diversity of plant odors that polyphagous herbivores encounter in the wild in order to unravel the olfactory basis of their host plant choice behaviour. In this study we show that a polyphagous moth, Spodoptera littoralis, has the sensory ability to distinguish five host plant species using olfaction alone, this being a prerequisite to the ability to make a choice. We have used gas chromatography mass spectrometry (GC-MS) and gas chromatography electroantennographic detection (GC-EAD) in order to describe host plant odor profiles as perceived by S. littoralis. We find that each plant emits specific combinations and proportions of GC-EAD active volatiles, leading to statistically distinct profiles. In addition, at least four of these plants show GC-EAD active compound proportions that are conserved across individual plants, a characteristic that enables insects to act upon previous olfactory experiences during host plant choice. By identifying the volatiles involved in olfactory differentiation of alternative host plants by Spodoptera littoralis, we set the groundwork for deeper investigations of how olfactory perceptions translate into behaviour in polyphagous herbivores.

COMPACT, CONTINUOUS MONITORING FOR VOLATILE ORGANIC COMPOUNDS - PHASE I

EPA Science Inventory

Improved methods for onsite measurement of multiple volatile organic compounds are needed for process control, monitoring, and remediation. This Phase I SBIR project sets forth an optical measurement method that meets these needs. The proposed approach provides an instantaneous m...

Analysis of flame spread over multicomponent combustibles

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

Ohtani, H.; Sato, J.

1985-01-01

A theoretical model of volatile component diffusion in the condensed phase is carried out in order to form a basis for predicting the flame spread rate in thermally thick multicomponent combustibles in a non-fluid condensed phase. The fuels could be, e.g., crude oil, heavy oil, or light oil. Mass transfer occurs only by diffusion so the gas phase volatile concentration at the surface is estimated from the condensed phase volatile concentration and the surface temperature, which increases close to the leading flame edge. The flame spread rate is assumed steady. The velocity of the flame spread is shown to bemore » a function of the initial condensed phase temperature and the temperature at the leading flame edge.« less

The Conformational Landscape of L-Threonine Matrix Isolation Infrared and {AB-INITIO Studies

NASA Astrophysics Data System (ADS)

Dubey, Pankaj; Mukhopadhyay, Anamika; Viswanathan, K. S.

2017-06-01

Amino acids, containing hydroxy side chains such as L-threonine and tyrosine play an important role in molecular recognition, such as in the docking of propofol, which is a commonly used anaesthetic. A rich conformational landscape of these amino acids makes them interesting candidates in the study of intra and intermolecular interactions. In this work, the conformational landscape of L-threonine was studied, as it can be expected to serve as a basis for understanding structure and functions of polypeptides and other biomolecules. The matrix isolation technique (MI) coupled with a high temperature effusive molecular beam (EMB) nozzle was used to trap conformers of amino acid, which were then characterized using FTIR spectroscopy. The usefulness of MI-EMB-FTIR spectroscopy is that it can trap structures corresponding to the local minima along with the global minimum and hence allows for a better exploration of the potential energy surface. A major challenge in conformational analysis of amino acids using matrix isolation FTIR arises from its non-volatile nature. A home built heating system which was mounted close to the cryotip, was used to evaporate the non-volatile amino acids. Our infrared spectra show that three conformations were trapped in the matrix. Experimental results were supported by {ab-initio calculations performed using the CCSD(T), MP2 and M06-2X methods together with 6-311++G(d,p) and aug/cc-pVDZ basis sets. The side chains of the amino acids appeared to have an influence on the preferential stabilisation of a particular backbone structure of amino acids. Factors such as entropy, anomeric effect and intramolecular H-bonding were also found to play an important role in determining conformal preferences, which will be discussed.

Harnessing Insect-Microbe Chemical Communications To Control Insect Pests of Agricultural Systems.

PubMed

Beck, John J; Vannette, Rachel L

2017-01-11

Insect pests cause serious economic, yield, and food safety problems to managed crops worldwide. Compounding these problems, insect pests often vector pathogenic or toxigenic microbes to plants. Previous work has considered plant-insect and plant-microbe interactions separately. Although insects are well-understood to use plant volatiles to locate hosts, microorganisms can produce distinct and abundant volatile compounds that in some cases strongly attract insects. In this paper, we focus on the microbial contribution to plant volatile blends, highlighting the compounds emitted and the potential for variation in microbial emission. We suggest that these aspects of microbial volatile emission may make these compounds ideal for use in agricultural applications, as they may be more specific or enhance methods currently used in insect control or monitoring. Our survey of microbial volatiles in insect-plant interactions suggests that these emissions not only signal host suitability but may indicate a distinctive time frame for optimal conditions for both insect and microbe. Exploitation of these host-specific microbe semiochemicals may provide important microbe- and host-based attractants and a basis for future plant-insect-microbe chemical ecology investigations.

Study on the rheological properties and volatile release of cold-set emulsion-filled protein gels.

PubMed

Mao, Like; Roos, Yrjö H; Miao, Song

2014-11-26

Emulsion-filled protein gels (EFP gels) were prepared through a cold-set gelation process, and they were used to deliver volatile compounds. An increase in the whey protein isolate (WPI) content from 4 to 6% w/w did not show significant effect on the gelation time, whereas an increase in the oil content from 5 to 20% w/w resulted in an earlier onset of gelation. Gels with a higher WPI content had a higher storage modulus and water-holding capacity (WHC), and they presented a higher force and strain at breaking, indicating that a more compact gel network was formed. An increase in the oil content contributed to gels with a higher storage modulus and force at breaking; however, this increase did not affect the WHC of the gels, and gels with a higher oil content became more brittle, resulting in a decreased strain at breaking. GC headspace analysis showed that volatiles released at lower rates and had lower air-gel partition coefficients in EFP gels than those in ungelled counterparts. Gels with a higher WPI content had lower release rates and partition coefficients of the volatiles. A change in the oil content significantly modified the partition of volatiles at equilibrium, but it produced a minor effect on the release rate of the volatiles. The findings indicated that EFP gels could be potentially used to modulate volatile release by varying the rheological properties of the gel.

Estimation of stochastic volatility by using Ornstein-Uhlenbeck type models

NASA Astrophysics Data System (ADS)

Mariani, Maria C.; Bhuiyan, Md Al Masum; Tweneboah, Osei K.

2018-02-01

In this study, we develop a technique for estimating the stochastic volatility (SV) of a financial time series by using Ornstein-Uhlenbeck type models. Using the daily closing prices from developed and emergent stock markets, we conclude that the incorporation of stochastic volatility into the time varying parameter estimation significantly improves the forecasting performance via Maximum Likelihood Estimation. Furthermore, our estimation algorithm is feasible with large data sets and have good convergence properties.

Analysis of volatile organic compounds from illicit cocaine samples

NASA Astrophysics Data System (ADS)

Robins, W. H.; Wright, Bob W.

1994-10-01

Detection of illicit cocaine hydrochloride shipments can be improved if there is a greater understanding of the identity and quantity of volatile compounds present. This study provides preliminary data concerning the volatile organic compounds detected in a limited set of cocaine hydrochloride samples. In all cases, cocaine was one of the major volatile compounds detected. Other tropeines were detected in almost all samples. Low concentrations of compounds which may be residues of processing solvents were observed in some samples. The equilibrium emissivity of cocaine from cocaine hydrochloride was investigated and a value of 83 parts-per-trillion was determined.

40 CFR 98.464 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... = Degradable organic content of waste stream in Year X (weight fraction, wet basis) FDOC = Fraction of the volatile residue that is degradable organic carbon (weight fraction). Use a default value of 0.6...

[GC-MS combined with AMDIS and Kováts retention index to investigate dynamic change rules of volatile components from Atractylodis Macrocephalae Rhizoma with different stir-baking degrees].

PubMed

Chen, Hong-Ping; Pan, Huan-Huan; Zhang, Xin; Liu, Fei; Chen, Mei-Jun; Luo, Guan-Hua; Liu, You-Ping

2016-07-01

To investigate the dynamic change rules of volatile components from Atractylodis Macrocephalae Rhizoma with different stir-baking degrees (from slight stir-baking, stir-baking to yellow, stir-baking to brown, to stir-baking to scorch). In the present experiment, the Atractylodis Macrocephalae Rhizoma samples with different stir-baking degrees were collected at different processing time points. The contents of volatile oil in various samples were determined by steam distillation method, and the volatile compounds were extracted by using static headspace sampling method. Gas chromatography-mass spectrography (GC-MS) and automated mass spectral deconrolution and identification system (AMDIS) were combined with Kováts retention index to analyze the chemical constituents of the volatile compounds. The results showed that with the deepening of the stir-baking degree, the content of volatile oil was decreased step by step in 4 phases, and both the compositions and contents of volatile components from Atractylodis Macrocephalae Rhizoma showed significant changes. The results showed that the dynamic change rules of volatile components from Atractylodis Macrocephalae Rhizoma in the process of stir-baking were closely related to the processing degree; in addition, Atractylodis Macrocephalae Rhizoma and honey bran had adsorption on each other. These results can provide a scientific basis for elucidating the stir-baking (with bran) mechanism of Atractylodis Macrocephalae Rhizoma. Copyright© by the Chinese Pharmaceutical Association.

Theoretical predictions of volatile bearing phases and volatile resources in some carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra; Saxena, Surendra K.

1989-01-01

Carbonaceous chondrites are usually believed to be the primary constituents of near-Earth asteroids and Phobos and Diemos, and are potential resources of fuels which may be exploited for future planetary missions. The nature and abundances are calculated of the major volatile bearing and other phases, including the vapor phase that should form in C1 and C2 type carbonaceous chondrites as functions of pressure and temperature. The results suggest that talc, antigorite plus or minus magnesite are the major volatile bearing phases and are stable below 400 C at 1 bar in these chondritic compositions. Simulated heating of a kilogram of C2 chondrite at fixed bulk composition between 400 and 800 C at 1 bar yields about 135 gm of volatile, which is made primarily of H2O, H2, CH4, CO2 and CO. The relative abundances of these volatile species change as functions of temperature, and on a molar basis, H2 becomes the most dominant species above 500 C. In contrast, Cl chondrites yield about 306 gm of volatile under the same condition, which consist almost completely of 60 wt percent H2O and 40 wt percent CO2. Preliminary kinetic considerations suggest that equilibrium dehydration of hydrous phyllosilicates should be attainable within a few hours at 600 C. These results provide the framework for further analyses of the volatile and economic resource potentials of carbonaceous chondrites.

Field-based Evaluation of a Novel SPME-GC-MS Method for Investigation of Below-ground Interaction between Brassica Roots and Larvae of Cabbage Root Fly, Delia radicum L.

PubMed

Deasy, William; Shepherd, Tom; Alexander, Colin J; Birch, A Nicholas E; Evans, K Andrew

2016-11-01

Collection of volatiles from plant roots poses technical challenges due to difficulties accessing the soil environment without damaging the roots. To validate a new non-invasive method for passive sampling of root volatiles in situ, from plants grown under field conditions, using solid phase micro-extraction (SPME). SPME fibres were inserted into perforated polytetrafluoroethene (PTFE) tubes positioned in the soil next to broccoli plants for collection of root volatiles pre- and post-infestation with Delia radicum larvae. After sample analysis by gas chromatography-mass spectrometry (GC-MS), principal component analysis (PCA) was applied to determine differences in the profiles of volatiles between samples. GC-MS analysis revealed that this method can detect temporal changes in root volatiles emitted before and after Delia radicum damage. PCA showed that samples collected pre- and post-infestation were compositionally different due to the presence of root volatiles induced by D. radicum feeding. Sulphur containing compounds, in particular, accounted for the differences observed. Root volatiles emission patterns post-infestation are thought to follow the feeding and developmental progress of larvae. This study shows that volatiles released by broccoli roots can be collected in situ using SPME fibres within perforated PTFE tubes under field conditions. Plants damaged by Delia radicum larvae could be distinguished from plants sampled pre-infestation and soil controls on the basis of larval feeding-induced sulphur-containing volatiles. These results show that this new method is a powerful tool for non-invasive sampling of root volatiles below-ground. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Global transcriptomic responses of Escherichia coli K-12 to volatile organic compounds.

PubMed

Yung, Pui Yi; Grasso, Letizia Lo; Mohidin, Abeed Fatima; Acerbi, Enzo; Hinks, Jamie; Seviour, Thomas; Marsili, Enrico; Lauro, Federico M

2016-01-28

Volatile organic compounds (VOCs) are commonly used as solvents in various industrial settings. Many of them present a challenge to receiving environments, due to their toxicity and low bioavailability for degradation. Microorganisms are capable of sensing and responding to their surroundings and this makes them ideal detectors for toxic compounds. This study investigates the global transcriptomic responses of Escherichia coli K-12 to selected VOCs at sub-toxic levels. Cells grown in the presence of VOCs were harvested during exponential growth, followed by whole transcriptome shotgun sequencing (RNAseq). The analysis of the data revealed both shared and unique genetic responses compared to cells without exposure to VOCs. Results suggest that various functional gene categories, for example, those relating to Fe/S cluster biogenesis, oxidative stress responses and transport proteins, are responsive to selected VOCs in E. coli. The differential expression (DE) of genes was validated using GFP-promoter fusion assays. A variety of genes were differentially expressed even at non-inhibitory concentrations and when the cells are at their balanced-growth. Some of these genes belong to generic stress response and others could be specific to VOCs. Such candidate genes and their regulatory elements could be used as the basis for designing biosensors for selected VOCs.

Global transcriptomic responses of Escherichia coli K-12 to volatile organic compounds

PubMed Central

Yung, Pui Yi; Grasso, Letizia Lo; Mohidin, Abeed Fatima; Acerbi, Enzo; Hinks, Jamie; Seviour, Thomas; Marsili, Enrico; Lauro, Federico M.

2016-01-01

Volatile organic compounds (VOCs) are commonly used as solvents in various industrial settings. Many of them present a challenge to receiving environments, due to their toxicity and low bioavailability for degradation. Microorganisms are capable of sensing and responding to their surroundings and this makes them ideal detectors for toxic compounds. This study investigates the global transcriptomic responses of Escherichia coli K-12 to selected VOCs at sub-toxic levels. Cells grown in the presence of VOCs were harvested during exponential growth, followed by whole transcriptome shotgun sequencing (RNAseq). The analysis of the data revealed both shared and unique genetic responses compared to cells without exposure to VOCs. Results suggest that various functional gene categories, for example, those relating to Fe/S cluster biogenesis, oxidative stress responses and transport proteins, are responsive to selected VOCs in E. coli. The differential expression (DE) of genes was validated using GFP-promoter fusion assays. A variety of genes were differentially expressed even at non-inhibitory concentrations and when the cells are at their balanced-growth. Some of these genes belong to generic stress response and others could be specific to VOCs. Such candidate genes and their regulatory elements could be used as the basis for designing biosensors for selected VOCs. PMID:26818886

Volatility forecasting for low-volatility portfolio selection in the US and the Korean equity markets

NASA Astrophysics Data System (ADS)

Kim, Saejoon

2018-01-01

We consider the problem of low-volatility portfolio selection which has been the subject of extensive research in the field of portfolio selection. To improve the currently existing techniques that rely purely on past information to select low-volatility portfolios, this paper investigates the use of time series regression techniques that make forecasts of future volatility to select the portfolios. In particular, for the first time, the utility of support vector regression and its enhancements as portfolio selection techniques is provided. It is shown that our regression-based portfolio selection provides attractive outperformances compared to the benchmark index and the portfolio defined by a well-known strategy on the data-sets of the S&P 500 and the KOSPI 200.

Differential Profiling of Volatile Organic Compound Biomarker Signatures Utilizing a Logical Statistical Filter-Set and Novel Hybrid Evolutionary Classifiers

DTIC Science & Technology

2012-04-01

for automated SPME headspace sampling and in-line with a Thermo DSQII single quadrupole mass spectrometer. Collection of organic volatiles from the...urine was accomplished using a 2cm CAR/DVB/PDMS solid phase micro extraction fiber ( SPME ), Supelco supplier, inserted by the Triplus autosampler into...automated direct injection. Volatiles gathered by the SPME fiber were analyzed through desorption of the fiber by heating to elevated temperature and

An integrative “omics” approach identifies new candidate genes to impact aroma volatiles in peach fruit

PubMed Central

2013-01-01

Background Ever since the recent completion of the peach genome, the focus of genetic research in this area has turned to the identification of genes related to important traits, such as fruit aroma volatiles. Of the over 100 volatile compounds described in peach, lactones most likely have the strongest effect on fruit aroma, while esters, terpenoids, and aldehydes have minor, yet significant effects. The identification of key genes underlying the production of aroma compounds is of interest for any fruit-quality improvement strategy. Results Volatile (52 compounds) and gene expression (4348 genes) levels were profiled in peach fruit from a maturity time-course series belonging to two peach genotypes that showed considerable differences in maturation characteristics and postharvest ripening. This data set was analyzed by complementary correlation-based approaches to discover the genes related to the main aroma-contributing compounds: lactones, esters, and phenolic volatiles, among others. As a case study, one of the candidate genes was cloned and expressed in yeast to show specificity as an ω-6 Oleate desaturase, which may be involved in the production of a precursor of lactones/esters. Conclusions Our approach revealed a set of genes (an alcohol acyl transferase, fatty acid desaturases, transcription factors, protein kinases, cytochromes, etc.) that are highly associated with peach fruit volatiles, and which could prove useful in breeding or for biotechnological purposes. PMID:23701715

Fungistatic activity of some perfumes against otomycotic pathogens.

PubMed

Jain, S K; Agrawal, S C

2002-04-01

The sporostatic effect of five otomycotic pathogens, i.e. Aspergillus niger, A. flavus, Absidia corymbifera, Penicillium nigricans and Candida albicans to nine different perfumes was determined on the basis of their spore germination. These organisms were isolated from patients suffering from fungal infection of the external auditory canal. Volatile vapours emanating from musk, phulwari, jasmine, nagchampa and bela caused approximately 100% inhibition in spore germination of all the test fungi. Volatiles emanating from chandan, khas and hina showed no inhibition for the test pathogens, displaying their resistant character to these perfumes.

Pricing European option with transaction costs under the fractional long memory stochastic volatility model

NASA Astrophysics Data System (ADS)

Wang, Xiao-Tian; Wu, Min; Zhou, Ze-Min; Jing, Wei-Shu

2012-02-01

This paper deals with the problem of discrete time option pricing using the fractional long memory stochastic volatility model with transaction costs. Through the 'anchoring and adjustment' argument in a discrete time setting, a European call option pricing formula is obtained.

Typification of cider brandy on the basis of cider used in its manufacture.

PubMed

Rodríguez Madrera, Roberto; Mangas Alonso, Juan J

2005-04-20

A study of typification of cider brandies on the basis of the origin of the raw material used in their manufacture was conducted using chemometric techniques (principal component analysis, linear discriminant analysis, and Bayesian analysis) together with their composition in volatile compounds, as analyzed by gas chromatography with flame ionization to detect the major volatiles and by mass spectrometric to detect the minor ones. Significant principal components computed by a double cross-validation procedure allowed the structure of the database to be visualized as a function of the raw material, that is, cider made from fresh apple juice versus cider made from apple juice concentrate. Feasible and robust discriminant rules were computed and validated by a cross-validation procedure that allowed the authors to classify fresh and concentrate cider brandies, obtaining classification hits of >92%. The most discriminating variables for typifying cider brandies according to their raw material were 1-butanol and ethyl hexanoate.

Volatile-bearing phases in carbonaceous chondrites: Compositions, modal abundance, and reaction kinetics

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra

1990-01-01

The spectral and density characteristics of Phobos and Deimos (the two small natural satellites of Mars) strongly suggest that a significant fraction of the near-earth asteroids are made of carbonaceous chondrites, which are rich in volatile components and, thus, could serve as potential resources for propellants and life supporting systems in future planetary missions. However, in order to develop energy efficient engineering designs for the extraction of volatiles, knowledge of the nature and modal abundance of the minerals in which the volatiles are structurally bound and appropriate kinetic data on the rates of the devolatilization reactions is required. Theoretical calculations to predict the modal abundances and compositions of the major volatile-bearing and other mineral phases that could develop in the bulk compositions of C1 and C2 classes (the most volatile rich classes among the carbonaceous chondrites) were performed as functions of pressure and temperature. The rates of dehydration of talc at 585, 600, 637, and 670 C at P(total) = 1 bar were determine for the reaction: Talc = 3 enstatite + quartz + water. A scanning electron microscopic study was conducted to see if the relative abundance of phases can be determined on the basis of the spectral identification and x ray mapping. The results of this study and the other studies within the project are discussed.

Stable Local Volatility Calibration Using Kernel Splines

NASA Astrophysics Data System (ADS)

Coleman, Thomas F.; Li, Yuying; Wang, Cheng

2010-09-01

We propose an optimization formulation using L1 norm to ensure accuracy and stability in calibrating a local volatility function for option pricing. Using a regularization parameter, the proposed objective function balances the calibration accuracy with the model complexity. Motivated by the support vector machine learning, the unknown local volatility function is represented by a kernel function generating splines and the model complexity is controlled by minimizing the 1-norm of the kernel coefficient vector. In the context of the support vector regression for function estimation based on a finite set of observations, this corresponds to minimizing the number of support vectors for predictability. We illustrate the ability of the proposed approach to reconstruct the local volatility function in a synthetic market. In addition, based on S&P 500 market index option data, we demonstrate that the calibrated local volatility surface is simple and resembles the observed implied volatility surface in shape. Stability is illustrated by calibrating local volatility functions using market option data from different dates.

Abundances of volatile-bearing phases in carbonaceous chondrites and cooling rates of meteorites based on cation ordering of orthopyroxenes

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra

1989-01-01

Results of preliminary calculations of volatile abundances in carbonaceous chondrites are discussed. The method (Ganguly 1982) was refined for the calculation of cooling rate on the basis of cation ordering in orthopyroxenes, and it was applied to the derivation of cooling rates of some stony meteorites. Evaluation of cooling rate is important to the analysis of condensation, accretion, and post-accretionary metamorphic histories of meteorites. The method of orthopyroxene speedometry is widely applicable to meteorites and would be very useful in the understanding of the evolutionary histories of carbonaceous chondrites, especially since the conventional metallographic and fission track methods yield widely different results in many cases. Abstracts are given which summarize the major conclusions of the volatile abundance and cooling rate calculations.

In-situ remediation system and method for contaminated groundwater

DOEpatents

Corey, John C.; Looney, Brian B.; Kaback, Dawn S.

1989-01-01

A system for removing volatile contaminants from a subsurface plume of contamination comprising two sets of wells, a well for injecting a fluid into a saturated zone on one side of the plume and an extracting well for collecting the fluid together with volatilized contaminants from the plume on the other side of the plume. The fluid enables the volatile contaminants to be volatilized and carried therewith through the ground to the extracting well. Injecting and extracting wells are preferably horizontal wells positioned below the plume in the saturated zone and above the plume in the vadose zone, respectively. The fluid may be air or other gas or a gas and liquid mixture depending on the type of contaminant to be removed and may be preheated to facilitate volatilization. Treatment of the volatilized contamination may be by filtration, incineration, atmospheric dispersion or the like.

In-situ remediation system and method for contaminated groundwater

DOEpatents

Corey, J.C.; Looney, B.B.; Kaback, D.S.

1989-05-23

A system for removing volatile contaminants from a subsurface plume of contamination comprising two sets of wells, a well for injecting a fluid into a saturated zone on one side of the plume and an extracting well for collecting the fluid together with volatilized contaminants from the plume on the other side of the plume. The fluid enables the volatile contaminants to be volatilized and carried therewith through the ground to the extracting well. Injecting and extracting wells are preferably horizontal wells positioned below the plume in the saturated zone and above the plume in the vadose zone, respectively. The fluid may be air or other gas or a gas and liquid mixture depending on the type of contaminant to be removed and may be preheated to facilitate volatilization. Treatment of the volatilized contamination may be by filtration, incineration, atmospheric dispersion or the like. 3 figs.

Exploring the modulation of hypoxia-inducible factor (HIF)-1α by volatile anesthetics as a possible mechanism underlying volatile anesthetic-induced CNS injury.

PubMed

Giles, Emma K; Lawrence, Andrew J; Duncan, Jhodie R

2014-09-01

This review summarizes recent research on the potential cognitive and behavioural abnormalities induced by exposure to volatile anesthetics and suggests a role of hypoxia-inducible factor (HIF)-1α in mediating these events. Volatile anesthetics are widely utilized in clinical and research settings, yet the long-term safety of exposure to these agents is under debate. Findings from various animal models suggest volatile anesthetics induce widespread apoptosis in the central nervous system (CNS) that correlates with lasting deficits in learning and memory. Longitudinal analysis of clinical data highlight an increased risk of developmental disorders later in life when children are exposed to volatile anesthetics, particularly when exposures occur over multiple sessions. However, the mechanisms underlying these events have yet to be established. Considering the extensive use of volatile anesthetics, it is crucial that these events are better understood. The possible role of HIF-1α in volatile anesthetic-induced CNS abnormalities will be suggested and areas requiring urgent attention will be outlined.

Scaling and efficiency determine the irreversible evolution of a market

PubMed Central

Baldovin, F.; Stella, A. L.

2007-01-01

In setting up a stochastic description of the time evolution of a financial index, the challenge consists in devising a model compatible with all stylized facts emerging from the analysis of financial time series and providing a reliable basis for simulating such series. Based on constraints imposed by market efficiency and on an inhomogeneous-time generalization of standard simple scaling, we propose an analytical model which accounts simultaneously for empirical results like the linear decorrelation of successive returns, the power law dependence on time of the volatility autocorrelation function, and the multiscaling associated to this dependence. In addition, our approach gives a justification and a quantitative assessment of the irreversible character of the index dynamics. This irreversibility enters as a key ingredient in a novel simulation strategy of index evolution which demonstrates the predictive potential of the model.

Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Danielson, L.; Nickodem, K.

2014-01-01

Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.

Use of Molecular Modeling to Determine the Interaction and Competition of Gases within Coal for Carbon Dioxide Sequestration

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

Jeffrey D. Evanseck; Jeffry D. Madura

A 3-dimensional coal structural model for the Argonne Premium Coal Pocahontas No. 3 has been generated. The model was constructed based on the wealth of structural information available in the literature with the enhancement that the structural diversity within the structure was represented implicitly (for the first time) based on image analysis of HRTEM in combination with LDMS data. The complex and large structural model (>10,000 carbon atoms) will serve as a basis for examining the interaction of gases within this low volatile bituminous coal. Simulations are of interest to permit reasonable simulations of the host-guest interactions with regard tomore » carbon dioxide sequestration within coal and methane displacement from coal. The molecular structure will also prove useful in examining other coal related behavior such as solvent swelling, liquefaction and other properties. Molecular models of CO{sub 2} have been evaluated with water to analyze which classical molecular force-field parameters are the most reasonable to predict the interactions of CO{sub 2} with water. The comparison of the molecular force field models was for a single CO{sub 2}-H{sub 2}O complex and was compared against first principles quantum mechanical calculations. The interaction energies and the electrostatic interaction distances were used as criteria in the comparison. The ab initio calculations included Hartree-Fock, B3LYP, and Moeller-Plesset 2nd, 3rd, and 4th order perturbation theories with basis sets up to the aug-cc-pvtz basis set. The Steele model was the best literature model, when compared to the ab initio data, however, our new CO{sub 2} model reproduces the QM data significantly better than the Steele force-field model.« less

Endogenous Lunar Volatiles: Insights into the Abundances of Volatiles in the Moon from Lunar Apatite

NASA Technical Reports Server (NTRS)

McCubbin, Francis

2016-01-01

At the time of publication of New Views of the Moon, it was thought that the Moon was bone dry with less than about 1 ppb H2O. However in 2007, initial reports at the 38th Lunar and Planetary Science Conference speculated that H-species were present in both apatites and pyroclastic volcanic lunar glasses. These early reports were later confirmed through peer-review, which motivated many subsequent studies on magmatic volatiles in and on the Moon within the last decade. Some of these studies have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. The mineral apatite has been one of the pillars of this new field of study, and it will be the primary focus of this abstract. Although apatite has been used both to understand the abundances of volatiles in lunar systems as well as the isotopic compositions of those volatiles, the focus here will be on the abundances of F, Cl, and H2O. This work demonstrates the utility of apatite in advancing our understanding of lunar volatiles, hence apatite should be among the topics covered in the endogenous lunar volatile chapter in NVM II. Truncated ternary plot of apatite X-site occupancy (mol%) from highlands apatite and mare basalt apatite plotted on the relative volatile abundance diagram from. The solid black lines delineate fields of relative abundances of F, Cl, and H2O (on a weight basis) in the melt from which the apatite crystallized. The diagram was constructed using available apatite/melt partitioning data for fluorine, chlorine, and hydroxyl.

Formation of secondary organic aerosol in the Paris pollution plume and its impact on surrounding regions

NASA Astrophysics Data System (ADS)

Zhang, Q. J.; Beekmann, M.; Freney, E.; Sellegri, K.; Pichon, J. M.; Schwarzenboeck, A.; Colomb, A.; Bourrianne, T.; Michoud, V.; Borbon, A.

2015-03-01

Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plume of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI project, an intensive campaign was launched in the Greater Paris Region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind the Paris region. Slopes of the plume OA levels vs. Ox (= O3 + NO2) show secondary OA (SOA) formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. Simulated and observed slopes are in good agreement, when the most realistic "high-NOx" yields are used in the Volatility-Basis-Set scheme implemented into the model. In addition, these slopes are relatively stable from one day to another, which suggest that they are characteristic for the given megacity plume environment. Since OA within the plume is mainly formed from anthropogenic precursors (VOC and primary OA, POA), this work allows a specific evaluation of anthropogenic SOA and SOA formed from primary semi-volatile and intermediate volatile VOCs (SI-SOA) formation scheme in a model. For specific plumes, this anthropogenic OA build-up can reach about 10 μg m-3. For the average of the month of July 2009, maximum increases occur close to the agglomeration for primary OA are noticed at several tens (for POA) to hundred (for SI-SOA) kilometers of distance from the Paris agglomeration.

Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

2015-12-01

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9-5.6, 6.4-12.0 and 0.9-2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

A Comparison of Parameterizations of Secondary Organic Aerosol Production: Global Budget and Spatiotemporal Variability

NASA Astrophysics Data System (ADS)

Liu, J.; Chen, Z.; Horowitz, L. W.; Carlton, A. M. G.; Fan, S.; Cheng, Y.; Ervens, B.; Fu, T. M.; He, C.; Tao, S.

2014-12-01

Secondary organic aerosols (SOA) have a profound influence on air quality and climate, but large uncertainties exist in modeling SOA on the global scale. In this study, five SOA parameterization schemes, including a two-product model (TPM), volatility basis-set (VBS) and three cloud SOA schemes (Ervens et al. (2008, 2014), Fu et al. (2008) , and He et al. (2013)), are implemented into the global chemical transport model (MOZART-4). For each scheme, model simulations are conducted with identical boundary and initial conditions. The VBS scheme produces the highest global annual SOA production (close to 35 Tg·y-1), followed by three cloud schemes (26-30 Tg·y-1) and TPM (23 Tg·y-1). Though sharing a similar partitioning theory to the TPM scheme, the VBS approach simulates the chemical aging of multiple generations of VOCs oxidation products, resulting in a much larger SOA source, particularly from aromatic species, over Europe, the Middle East and Eastern America. The formation of SOA in VBS, which represents the net partitioning of semi-volatile organic compounds from vapor to condensed phase, is highly sensitivity to the aging and wet removal processes of vapor-phase organic compounds. The production of SOA from cloud processes (SOAcld) is constrained by the coincidence of liquid cloud water and water-soluble organic compounds. Therefore, all cloud schemes resolve a fairly similar spatial pattern over the tropical and the mid-latitude continents. The spatiotemporal diversity among SOA parameterizations is largely driven by differences in precursor inputs. Therefore, a deeper understanding of the evolution, wet removal, and phase partitioning of semi-volatile organic compounds, particularly above remote land and oceanic areas, is critical to better constrain the global-scale distribution and related climate forcing of secondary organic aerosols.

Olfactory basis of floral preference of the malaria vector Anopheles gambiae (Diptera: Culicidae) among common African plants.

PubMed

Nikbakhtzadeh, Mahmood R; Terbot, John W; Otienoburu, Philip E; Foster, Woodbridge A

2014-12-01

Mosquitoes of both sexes feed on plants to obtain sugar. Nocturnal species probably locate the plants primarily by their volatile semiochemicals that also form the basis for the mosquitoes' innate plant-species preferences. To evaluate these olfactory preferences quantitatively, we used a two-choice wind-tunnel olfactometer to measure the upwind orientation of Anopheles gambiae Giles, an important vector of malaria in equatorial Africa, toward odor plumes produced by nine plant species common where this mosquito occurs. These plants are reported to induce feeding behaviors in An. gambiae and to produce floral or extrafloral nectar. Results presented here demonstrated that the volatiles of S. didymobotrya, P. hysterophorus, S. occidentalis, and L. camara, in descending order of numbers of mosquitoes responding, were all attractive, compared to a control plant species, whereas D. stramonium, R. communis, S. bicapsularis, T. stans, and T. diversifolia were not. As expected, chromatographic analysis of the headspace of attractive plants whose volatiles were captured by stir-bar sorptive extraction revealed a wide range of compounds, primarily terpenoids. Once their bioactivity and attractiveness for An. gambiae, alone and in blends, has been firmly established, some of these semiochemicals may have applications in population sampling and control. © 2014 The Society for Vector Ecology.

Simulating the behavior of volatiles belonging to the C-O-H-S system in silicate melts under magmatic conditions with the software D-Compress

NASA Astrophysics Data System (ADS)

Burgisser, Alain; Alletti, Marina; Scaillet, Bruno

2015-06-01

Modeling magmatic degassing, or how the volatile distribution between gas and melt changes at pressure varies, is a complex task that involves a large number of thermodynamical relationships and that requires dedicated software. This article presents the software D-Compress, which computes the gas and melt volatile composition of five element sets in magmatic systems (O-H, S-O-H, C-S-O-H, C-S-O-H-Fe, and C-O-H). It has been calibrated so as to simulate the volatiles coexisting with three common types of silicate melts (basalt, phonolite, and rhyolite). Operational temperatures depend on melt composition and range from 790 to 1400 °C. A specificity of D-Compress is the calculation of volatile composition as pressure varies along a (de)compression path between atmospheric and 3000 bars. This software was prepared so as to maximize versatility by proposing different sets of input parameters. In particular, whenever new solubility laws on specific melt compositions are available, the model parameters can be easily tuned to run the code on that composition. Parameter gaps were minimized by including sets of chemical species for which calibration data were available over a wide range of pressure, temperature, and melt composition. A brief description of the model rationale is followed by the presentation of the software capabilities. Examples of use are then presented with outputs comparisons between D-Compress and other currently available thermodynamical models. The compiled software and the source code are available as electronic supplementary materials.

Chemical composition and antimicrobial activity of the volatile fractions from leaves and flowers of the wild Iraqi Kurdish plant Prangos peucedanifolia FENZL.

PubMed

Brusotti, Gloria; Ibrahim, Mohammed Farhad; Dentamaro, Alessandra; Gilardoni, Gianluca; Tosi, Solveig; Grisoli, Pietro; Dacarro, Cesare; Guglielminetti, Maria Lidia; Hussain, Faiq Hama Saeed; Caccialanza, Gabriele; Vidari, Giovanni

2013-02-01

The volatile fractions isolated from Prangos peucedanifolia FENZL leaves and flowers were investigated for their phytochemical composition and biological properties. Flower and leaf hydrodistillation afforded 3.14 and 0.49 g of yellowish oils in 1.25 and 0.41% yields, respectively, from dry vegetable materials. According to the GC-FID and GC/MS analyses, 36 (99.35% of the total oil composition) and 26 compounds (89.12%) were identified in the two oils, respectively. The major constituents in the flower volatile fraction were β-pinene (35.58%), α-pinene (22.13%), and β-phellandrene (12.54%), while m-cresol (50.38%) was the main constituent of the leaf volatile fraction. The antimicrobial activity was evaluated against several bacterial and fungal strains, on the basis of the minimum inhibitory concentration (MIC) by the micro- and macrodilution methods. The two volatile fractions showed moderate antifungal and antibacterial activities, especially against Trichophyton rubrum (MIC of 2×10(3) μg/ml), Streptococcus mutans, Streptococcus pyogenes, and Staphylococcus aureus (MIC≤1.9×10(3) μg/ml for all). Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

Direct screening and confirmation of priority volatile organic pollutants in drinking water.

PubMed

Caro, J; Serrano, A; Gallego, M

2007-01-05

A screening tool was proposed for the rapid detection of eight priority volatile organic pollutants according to European standards in drinking water. The method is based on the direct coupling of a headspace sampler with a mass spectrometer, using a chromatographic column heated to 175 degrees C as an interface. The water sample was subjected to the headspace extraction process and the volatile fraction was introduced directly into the mass spectrometer, without prior chromatographic separation, achieving low detection limits (0.6-1.2 ng/ml) for all compounds. The mass spectrum resulting from the simultaneous ionization and fragmentation of the mixture of molecules constitutes the volatile profile of each sample. An appropriate chemometric treatment of these signals permitted them to be classified, on the basis of their volatile composition, as contaminated or uncontaminated with respect to the legally established concentration levels for these compounds in drinking water, and providing no false negatives. A conventional confirmation method was carried out to analyze positive water samples by using the same instrumental setup as in the screening method, but using an appropriate temperature program in the chromatographic column to separate, identify and quantify each analyte.

The history of Martian volatiles

NASA Astrophysics Data System (ADS)

Jakosky, Bruce M.; Jones, John H.

The behavior of water and other volatiles on Mars is key to understanding the evolution of the climate. The early climate played a fundamental role in producing the observed surface morphology and possibly in enabling the existence of an early biosphere. Geochemical and isotopic data can be used to infer the history of volatiles. On the basis of the isotopic data from the atmosphere and from components of the surface (as measured in meteorites that come from Mars), there appear to be at least two reservoirs of volatiles, one that has undergone exchange with the atmosphere and has been isotopically fractionated, and a second that is unfractionated and may represent juvenile gases. The fractionation of the atmospheric component has occurred primarily through the escape of gas to space. In addition, the atmospheric gases have mixed substantially with crustal reservoirs of volatiles. Such exchange may have occurred in aqueous or hydrothermal environments. The history of escape to space, as driven by the properties of the Sun through time, is consistent with the surface geomorphology. Together, they suggest an early environment that was substantially different from the present one and the evolution through time to a colder, dryer climate.

The effects of diet and breed on the volatile compounds of cooked lamb.

PubMed

Elmore, J S; Mottram, D S; Enser, M; Wood, J D

2000-06-01

The effect of varying the n-3 polyunsaturated fatty acid (PUFA) composition of lamb muscle on the formation of aroma volatiles during cooking has been examined. The meat was obtained from four groups of Suffolk and Soay lambs fed different supplementary fats: a palm-oil based control; bruised whole linseed, which increased muscle levels of α-linolenic acid (C18:3 n-3); fish oil, which increased eicosapentaenoic acid (EPA, C20:5 n-3) and docosahexaenoic acid (DHA, C22:6 n-3); and equal quantities of linseed and fish oil (fat basis). Higher quantities of lipid oxidation products were found in the aroma volatiles of lamb muscle from animals fed fish oil, compared to the control. In particular, unsaturated aldehydes, unsaturated hydrocarbons and alkylfurans increased up to fourfold. These compounds derived from the autoxidation of PUFAs during cooking. Although some of these volatiles were increased in meat from animals fed the linseed supplement, the effect was not as great as with the fish oil fed lambs. Levels of volatiles derived from the Maillard reaction, such as pyrazines and sulfur compounds, were up to four times higher in Soays than Suffolks.

76 FR 23351 - Self-Regulatory Organizations; The NASDAQ Stock Market LLC; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-26

... Exchange would also be able to temporarily deactivate OPP from time to time on an intraday basis at its... intraday OPP deactivation due to volatility and any subsequent intraday reactivation by the Exchange...

Variational formulation for Black-Scholes equations in stochastic volatility models

NASA Astrophysics Data System (ADS)

Gyulov, Tihomir B.; Valkov, Radoslav L.

2012-11-01

In this note we prove existence and uniqueness of weak solutions to a boundary value problem arising from stochastic volatility models in financial mathematics. Our settings are variational in weighted Sobolev spaces. Nevertheless, as it will become apparent our variational formulation agrees well with the stochastic part of the problem.

Analysis of Floral Volatile Components and Antioxidant Activity of Different Varieties of Chrysanthemum morifolium.

PubMed

Yang, Lu; Cheng, Ping; Wang, Jin-Hui; Li, Hong

2017-10-23

This study investigated the volatile flavor compounds and antioxidant properties of the essential oil of chrysanthemums that was extracted from the fresh flowers of 10 taxa of Chrysanthemum morifolium from three species; namely Dendranthema morifolium (Ramat.) Yellow, Dendranthema morifolium (Ramat.) Red, Dendranthema morifolium (Ramat.) Pink, Dendranthema morifolium (Ramat.) White, Pericallis hybrid Blue, Pericallis hybrid Pink, Pericallis hybrid Purple, Bellis perennis Pink, Bellis perennis Yellow, and Bellis perennis White. The antioxidant capacity of the essential oil was assayed by spectrophotometric analysis. The volatile flavor compounds from the fresh flowers were collected using dynamic headspace collection, analyzed using auto thermal desorber-gas chromatography/mass spectrometry, and identified with quantification using the external standard method. The antioxidant activities of Chrysanthemum morifolium were evaluated by DPPH and FRAP assays, and the results showed that the antioxidant activity of each sample was not the same. The different varieties of fresh Chrysanthemum morifolium flowers were distinguished and classified by fingerprint similarity evaluation, principle component analysis (PCA), and cluster analysis. The results showed that the floral volatile component profiles were significantly different among the different Chrysanthemum morifolium varieties. A total of 36 volatile flavor compounds were identified with eight functional groups: hydrocarbons, terpenoids, aromatic compounds, alcohols, ketones, ethers, aldehydes, and esters. Moreover, the variability among Chrysanthemum morifolium in basis to the data, and the first three principal components (PC1, PC2, and PC3) accounted for 96.509% of the total variance (55.802%, 30.599%, and 10.108%, respectively). PCA indicated that there were marked differences among Chrysanthemum morifolium varieties. The cluster analysis confirmed the results of the PCA analysis. In conclusion, the results of this study provide a basis for breeding Chrysanthemum cultivars with desirable floral scents, and they further support the view that some plants are promising sources of natural antioxidants.

Cohesiveness in Financial News and its Relation to Market Volatility

PubMed Central

Piškorec, Matija; Antulov-Fantulin, Nino; Novak, Petra Kralj; Mozetič, Igor; Grčar, Miha; Vodenska, Irena; Šmuc, Tomislav

2014-01-01

Motivated by recent financial crises, significant research efforts have been put into studying contagion effects and herding behaviour in financial markets. Much less has been said regarding the influence of financial news on financial markets. We propose a novel measure of collective behaviour based on financial news on the Web, the News Cohesiveness Index (NCI), and we demonstrate that the index can be used as a financial market volatility indicator. We evaluate the NCI using financial documents from large Web news sources on a daily basis from October 2011 to July 2013 and analyse the interplay between financial markets and finance-related news. We hypothesise that strong cohesion in financial news reflects movements in the financial markets. Our results indicate that cohesiveness in financial news is highly correlated with and driven by volatility in financial markets. PMID:24849598

Origin and timescale of volatile element depletion in crustal and mantle reservoirs

NASA Astrophysics Data System (ADS)

Moynier, Frederic; Day, James M. D.

2014-05-01

Volatile elements play a fundamental role in the evolution of planets. Understanding of how volatile budgets were set in planets, and how and to what extent planetary bodies became volatile-depleted during the earliest stages of Earth and Solar System formation remain poorly understood, however. It has been proposed that the depletion is due to incomplete condensation (volatile elements were not there in the first place, in which case the timing would have to be fast, <1Myr), or that planetary bodies lost volatile elements through evaporation (post-accretion volatilization). Volatilization is known to fractionate isotopes, thus comparing isotope ratios of volatile element between samples is a powerful tool for understanding the origin of volatile element abundance variations. For example, recent work has shown that lunar basalts are enriched in the heavier isotopes of Zn (~1 ‰ for 66Zn/64Zn) compared to chondrites, terrestrial and martian basalts. We will discuss these Zn isotopic data of crustal and mantle rocks, as well as other stable isotopic systems (e.g., Si) in relation with the giant impact theory of lunar origin, as well as the lunar magma ocean and expand to other parent bodies (e.g., angrites). The timescale of depletion in volatile elements of Solar System material is estimated by using radiogenic systems for which the parent and daughter elements have different volatility. Here we focus on the Rb-Sr and Mn-Cr isotopic systems and discuss the timescales and implications for the origin of volatile element depletion (solar nebula stage vs. planetary stage).

Volatilization and precipitation of tellurium by aerobic, tellurite-resistant marine microbes.

PubMed

Ollivier, Patrick R L; Bahrou, Andrew S; Marcus, Sarah; Cox, Talisha; Church, Thomas M; Hanson, Thomas E

2008-12-01

Microbial resistance to tellurite, an oxyanion of tellurium, is widespread in the biosphere, but the geochemical significance of this trait is poorly understood. As some tellurite resistance markers appear to mediate the formation of volatile tellurides, the potential contribution of tellurite-resistant microbial strains to trace element volatilization in salt marsh sediments was evaluated. Microbial strains were isolated aerobically on the basis of tellurite resistance and subsequently examined for their capacity to volatilize tellurium in pure cultures. The tellurite-resistant strains recovered were either yeasts related to marine isolates of Rhodotorula spp. or gram-positive bacteria related to marine strains within the family Bacillaceae based on rRNA gene sequence comparisons. Most strains produced volatile tellurides, primarily dimethyltelluride, though there was a wide range of the types and amounts of species produced. For example, the Rhodotorula spp. produced the greatest quantities and highest diversity of volatile tellurium compounds. All strains also produced methylated sulfur compounds, primarily dimethyldisulfide. Intracellular tellurium precipitates were a major product of tellurite metabolism in all strains tested, with nearly complete recovery of the tellurite initially provided to cultures as a precipitate. Different strains appeared to produce different shapes and sizes of tellurium containing nanostructures. These studies suggest that aerobic marine yeast and Bacillus spp. may play a greater role in trace element biogeochemistry than has been previously assumed, though additional work is needed to further define and quantify their specific contributions.

[Study on composition, antibiotic activity and antioxidant activity of volatile oils from uyghur medicine Althaea rosea].

PubMed

Munira, Abudukeremu; Muheta'er, Tu'erhong; Resalat, Yimin; Xia, Na

2015-04-01

Althaea rosea is a type of mallow plant. Its dry flowers are one of common herb in Uyghur medicines and recorded to have several efficacies such as external application for detumescence, moistening lung and arresting cough, sweating and relieving asthma, diminishing swelling and promoting eruption, soothing the nerves and strengthening heart. However, there are only fewer studies on effective components of A. rosea and no literature about its volatile oil and pharmacological activity. In this paper, the volatile oil of A. rosea was obtained by using the chemical distillation and extraction method. The individual chemical components were separated from the volatile oil and identified by the Gas Chromatograph-Mass Spectrometer technique (GC-MS). The antioxidant activity against free radicals was detected by the'ultraviolet and visible spectrophotometer method. The antibiotic activity was detected by the filter paper diffusion method. The experimental results showed nearly 70 compounds in the volatile oil, with complex chemical components. With a low content, most of the compounds were aromatic and aliphatic compounds and their derivatives. A. rosea had a better antibiotic activity for common microorganisms, with a wide antibacterial spectrum. According to the results, the volatile oil of A. rosea will have a good application value in medicine, food and cosmetic industries, which provided a scientific basis for the development of natural A. rosea resources.

Correlation and volatility in an Indian stock market: A random matrix approach

NASA Astrophysics Data System (ADS)

Kulkarni, Varsha; Deo, Nivedita

2007-11-01

We examine the volatility of an Indian stock market in terms of correlation of stocks and quantify the volatility using the random matrix approach. First we discuss trends observed in the pattern of stock prices in the Bombay Stock Exchange for the three-year period 2000 2002. Random matrix analysis is then applied to study the relationship between the coupling of stocks and volatility. The study uses daily returns of 70 stocks for successive time windows of length 85 days for the year 2001. We compare the properties of matrix C of correlations between price fluctuations in time regimes characterized by different volatilities. Our analyses reveal that (i) the largest (deviating) eigenvalue of C correlates highly with the volatility of the index, (ii) there is a shift in the distribution of the components of the eigenvector corresponding to the largest eigenvalue across regimes of different volatilities, (iii) the inverse participation ratio for this eigenvector anti-correlates significantly with the market fluctuations and finally, (iv) this eigenvector of C can be used to set up a Correlation Index, CI whose temporal evolution is significantly correlated with the volatility of the overall market index.

Identification of Key Root Volatiles Signaling Preference of Tomato Over Spinach by the Root Knot Nematode Meloidogyne incognita.

PubMed

Murungi, Lucy K; Kirwa, Hillary; Coyne, Danny; Teal, Peter E A; Beck, John J; Torto, Baldwyn

2018-06-25

The root knot nematode, Meloidogyne incognita (Kofoid and White) Chitwood, is a serious pest of tomato (Solanum lycopersicum) and spinach (Spinacea oleracea) in sub-Saharan Africa. In East Africa these two crops are economically important and are commonly intercropped by smallholder farmers. The role of host plant volatiles in M. incognita interactions with these two commodities is currently unknown. Here, we investigate the olfactory basis of attraction of tomato and spinach roots by the infective second stage juveniles (J2s) of M. incognita. In olfactometer assays, J2s were attracted to root volatiles from both crops over moist sand (control), but in choice tests using the two host plants, volatiles of tomato roots were more attractive than those released by spinach. Root volatiles sampled by solid phase micro-extraction (SPME) fiber and analysed by gas chromatography/mass spectrometry (GC/MS) identified a total of eight components, of which five (2-isopropyl-3-methoxypyrazine, 2-(methoxy)-3-(1-methylpropyl)pyrazine, tridecane, and α- and β-cedrene) occurred in the root-emitted volatiles of both plants, with three (δ-3-carene, sabinene and methyl salicylate) being specific to tomato root volatiles. In a series of bioassays, methyl salicylate contributed strongly to the attractiveness of tomato, whereas 2-isopropyl-3-methoxypyrazine and tridecane contributed to the attractiveness of spinach. M. incognita J2s were also more attracted to natural spinach root volatiles when methyl salicylate was combined, than to spinach volatiles alone, indicating that the presence of methyl salicylate in tomato volatiles strongly contributes to its preference over spinach. Our results indicate that since both tomato and spinach roots are attractive to M. incognita, identifying cultivars of these two plant species that are chemically less attractive can be helpful in the management of root knot nematodes.

Vertebrate pheromones and other semiochemicals: the potential for accommodating complexity in signalling by volatile compounds for vertebrate management

PubMed Central

Pickett, John A.; Barasa, Stephen; Birkett, Michael A.

2014-01-01

The interaction between volatile and non-volatile, e.g. proteinaceous, components of pheromone and other semiochemical-based signalling systems presents a daunting set of problems for exploitation in the management of vertebrates, good or bad. Aggravating this is the complexity of the mixtures involved with pheromones, not only by definition associated with each species, but also with individual members of that species and their positions within their immediate communities. Nonetheless, already in some contexts, particularly where signals are perceived at other trophic levels from those of the vertebrates, e.g. by arthropods, reductionist approaches can be applied whereby the integrity of complex volatile mixtures is maintained, but perturbed by augmentation with individual components. In the present article, this is illustrated for cattle husbandry, fish farming and human health. So far, crude formulations have been used to imitate volatile semiochemical interactions with non-volatile components, but new approaches must be developed to accommodate more sophisticated interactions and not least the activities of the non-volatile, particularly proteinaceous components, currently being deduced. PMID:25109967

An unusual and persistent contamination of drinking water by cutting oil.

PubMed

Rella, R; Sturaro, A; Parvoli, G; Ferrara, D; Doretti, L

2003-02-01

Drinking water contamination by materials, such as cutting oil, used to set up pipelines is an uncommon but possible event. This paper describes the analytical procedures used to identify the components of that contaminant in drinking water. Volatile and semi-volatile chemical species, responsible for an unpleasant taste and odour, were recognised by solid phase microextraction and GC/MS techniques. Among the volatile compounds, the presence of xylenes, bornyl acetate and diphenyl ether was confirmed by certificate standards and quantified in the most contaminated samples.

Electroantennographic and behavioral responses of the sphinx moth Manduca sexta to host plant headspace volatiles.

PubMed

Fraser, Ann M; Mechaber, Wendy L; Hildebrand, John G

2003-08-01

Coupled gas chromatography with electroantennographic detection (GC-EAD) using antennae of adult female Manduca sexta was employed to screen for olfactory stimulants present in headspace collections from four species of larval host plants belonging to two families: Solanaceae--Lycopersicon esculentum (tomato), Capiscum annuum (bell pepper), and Datura wrightii; and Martyniaceae--Pronboscideaparviflora. Headspace volatiles were collected from undamaged foliage of potted, living plants. GC-EAD revealed 23 EAD-active compounds, of which 15 were identified by GC-mass spectrometry. Identified compounds included aliphatic, aromatic, and terpenoid compounds bearing a range of functional groups. Nine EAD-active compounds were common to all four host plant species: (Z)-3-hexenyl acetate, nonanal, decanal, phenylacetaldehyde, methyl salicylate, benzyl alcohol, geranyl acetone, (E)-nerolidol, and one unidentified compound. Behavioral responses of female moths to an eight-component synthetic blend of selected tomato headspace volatiles were tested in a laboratory wind tunnel. Females were attracted to the blend. A comparison of responses from antennae of males and females to bell pepper headspace volatiles revealed that males responded to the same suite of volatiles as females, except for (Z)-3-hexenyl benzoate. EAD responses of males also were lower for (Z)-and (E)-nerolidol and one unidentified compound. Electroantennogram EAG dose-response curves for the 15 identified EAD-active volatiles were recorded. At the higher test doses (10-100 microg), female antennae yielded larger EAG responses to terpenoids and to aliphatic and aromatic esters. Male antennae did respond to the higher doses of (Z)-3-hexenyl benzoate, indicating that they can detect this compound. On the basis of ubiquity of the EAD-active volatiles identified to date in host plant headspace collections, we suggest that M. sexta uses a suite of volatiles to locate and identify appropriate host plants.

Martian impact crater ejecta morphologies and their potential as indicators of subsurface volatile distribution

NASA Technical Reports Server (NTRS)

Barlow, Nadine G.

1991-01-01

Many martian impact craters ejecta morphologies suggestive of fluidization during ejecta emplacement. Impact into subsurface volatile reserviors (i.e., water, ice, CO2, etc.) is the mechanism favored by many scientists, although acceptance of this mechanism is not unanimous. In recent years, a number of studies were undertaken to better understand possible relationships between ejecta morphology and latitude, longitude, crater diameter, and terrain. These results suggest that subsurface volatiles do influence the formation of specific ejecta morphologies and may provide clues to the vertical and horizontal distribution of volatiles in more localized regions of Mars. The location of these volatile reservoirs will be important to humans exploring and settling Mars in the future. Qualitative descriptions of ejecta morphology and quantitative analyses of ejecta sinuosity and ejecta lobe areal extent from the basis of the studies. Ejecta morphology studies indicate that morphology is correlated with crater diameter and latitude, and, using depth-diameter relationships, these correlations strongly suggest that changes in morphology are related to transition among subsurface layers with varying amounts of volatiles. Ejecta sinuosity studies reveal correlations between degree of sinuosity (lobateness) and crater morphology, diameter, latitude, and terrain. Lobateness, together with variations in areal extent of the lobate ejecta blanket with morphology and latitude, probably depends most directly on the ejecta emplacement process. The physical parameters measured here can be compared with those predicted by existing ejecta emplacement models. Some of these parameters are best reproduced by models requiring incorporation of volatiles within the ejecta. However, inconsistencies between other parameters and the models indicate that more detailed modeling is necessary before the location of volatile reservoirs can be confidently predicted based on ejecta morphology studies alone.

Qualitative and Quantitative Differences in Herbivore-Induced Plant Volatile Blends from Tomato Plants Infested by Either Tuta absoluta or Bemisia tabaci.

PubMed

Silva, Diego B; Weldegergis, Berhane T; Van Loon, Joop J A; Bueno, Vanda H P

2017-01-01

Plants release a variety of volatile organic compounds that play multiple roles in the interactions with other plants and animals. Natural enemies of plant-feeding insects use these volatiles as cues to find their prey or host. Here, we report differences between the volatile blends of tomato plants infested with the whitefly Bemisia tabaci or the tomato borer Tuta absoluta. We compared the volatile emission of: (1) clean tomato plants; (2) tomato plants infested with T. absoluta larvae; and (3) tomato plants infested with B. tabaci adults, nymphs, and eggs. A total of 80 volatiles were recorded of which 10 occurred consistently only in the headspace of T. absoluta-infested plants. Many of the compounds detected in the headspace of the two herbivory treatments were emitted at different rates. Plants damaged by T. absoluta emitted at least 10 times higher levels of many compounds compared to plants damaged by B. tabaci and intact plants. The multivariate separation of T. absoluta-infested plants from those infested with B. tabaci was due largely to the chorismate-derived compounds as well as volatile metabolites of C 18 -fatty acids and branched chain amino acids that had higher emission rates from T. absoluta-infested plants, whereas the cyclic sesquiterpenes α- and β-copaene, valencene, and aristolochene were emitted at significantly higher levels from B. tabaci-infested plants. Our findings imply that feeding by T. absoluta and B. tabaci induced emission of volatile blends that differ quantitatively and qualitatively, providing a chemical basis for the recently documented behavioral discrimination by two generalist predatory mirid species, natural enemies of T. absoluta and B. tabaci employed in biological control.

Model development and evaluation of methane potential from anaerobic co-digestion of municipal wastewater sludge and un-dewatered grease trap waste.

PubMed

Yalcinkaya, Sedat; Malina, Joseph F

2015-06-01

The performance of anaerobic co-digestion of municipal wastewater sludge with un-dewatered grease trap waste was assessed using modified biochemical methane potential tests under mesophilic conditions (35°C). Methane potentials, process inhibition and chemical behavior of the process were analyzed at different grease trap waste feed ratios on volatile solids basis. Nonlinear regression analyses of first order reaction and modified Gompertz equations were performed to assist in interpretation of the experimental results. Methane potential of un-dewatered grease trap waste was measured as 606 mL CH4/g VS(added), while methane potential of municipal wastewater sludge was only 223 mL CH4/g VS(added). The results indicated that anaerobic digestion of grease trap waste without dewatering yields less methane potential than concentrated/dewatered grease trap waste because of high wastewater content of un-dewatered grease trap waste. However, anaerobic co-digestion of municipal wastewater sludge and grease trap waste still yields over two times more methane potential and approximately 10% more volatile solids reduction than digestion of municipal wastewater sludge alone. The anaerobic co-digestion process inhibitions were reported at 70% and greater concentrated/dewatered grease trap waste additions on volatile solids basis in previous studies; however, no inhibition was observed at 100% un-dewatered grease trap waste digestion in the present study. These results indicate that anaerobic co-digestion of un-dewatered grease trap waste may reduce the inhibition risk compared to anaerobic co-digestion of concentrated/dewatered grease trap waste. In addition, a mathematical model was developed in this study for the first time to describe the relationship between grease trap waste feed ratio on volatile solids basis and resulting methane potential. Experimental data from the current study as well as previous biochemical methane potential studies were successfully fit to this relationship and allowed estimation of key performance parameters that provide additional insight into the factors affecting biochemical methane potential. Copyright © 2015 Elsevier Ltd. All rights reserved.

[Numerical modeling analysis of secondary organic aerosol (SOA) combined with the ground-based measurements in the Pearl River Delta region].

PubMed

Guo, Xiao-Shuang; Situ, Shu-Ping; Wang, Xue-Mei; Ding, Xiang; Wang, Xin-Ming; Yan, Cai-Qing; Li, Xiao-Ying; Zheng, Mei

2014-05-01

Two simulations were conducted with different secondary organic aerosol (SOA) methods-VBS (volatile basis set) approach and SORGAM (secondary organic aerosol model) , which have been coupled in the WRF/Chem (weather research and forecasting model with chemistry) model. Ground-based observation data from 18th to 25th November 2008 were used to examine the model performance of SOA in the Pearl River Delta(PRD)region. The results showed that VBS approach could better reproduce the temporal variation and magnitude of SOA compared with SORGAM, and the mean absolute deviation and correlation coefficient between the observed and the simulated data using VBS approach were -4.88 microg m-3 and 0.91, respectively, while they were -5.32 microg.m-3 and 0. 18 with SORGAM. This is mainly because the VBS approach considers SOA precursors with a wider volatility range and the process of chemical aging in SOA formation. Spatiotemporal distribution of SOA in the PRD from the VBS simulation was also analyzed. The results indicated that the SOA has a significant diurnal variation, and the maximal SOA concentration occurred at noon and in the early afternoon. Because of the transport and the considerable spatial distribution of O3 , the SOA concentrations were different in different PRD cities, and the highest concentration of SOA was observed in the downwind area, including Zhongshan, Zhuhai and Jiangmen.

Aviation fuel property effects on altitude relight

NASA Technical Reports Server (NTRS)

Venkataramani, K.

1987-01-01

The major objective of this experimental program was to investigate the effects of fuel property variation on altitude relight characteristics. Four fuels with widely varying volatility properties (JP-4, Jet A, a blend of Jet A and 2040 Solvent, and Diesel 2) were tested in a five-swirl-cup-sector combustor at inlet temperatures and flows representative of windmilling conditions of turbofan engines. The effects of fuel physical properties on atomization were eliminated by using four sets of pressure-atomizing nozzles designed to give the same spray Sauter mean diameter (50 + or - 10 micron) for each fuel at the same design fuel flow. A second series of tests was run with a set of air-blast nozzles. With comparable atomization levels, fuel volatility assumes only a secondary role for first-swirl-cup lightoff and complete blowout. Full propagation first-cup blowout were independent of fuel volatility and depended only on the combustor operating conditions.

[Power and everyday life in a lunatic asylum environment - a case example from Glasgow at the beginning of the 20th century].

PubMed

Gründler, Jens

In this article the focus of analysis lies on power relations in everyday life in one of Glasgow's Pauper Lunatic Asylums at the turn of the twentieth century. Taking a sample of patient case files I examine the daily processes of negotiation between inmates and their relatives, physicians, attendants and nurses as well as the poor law administration. Some cases especially exemplify the complex relationships between the actors. They show which opportunities and boundaries existed for "power brokering" for the more powerless. At the same time these cases illustrate the formal and practical limits of enforcement by doctors and nursing staff. Without turning a blind eve to hierarchies and power imbalances the analysis shows that even in settings like "total institutions" power remains volatile. Even there the more powerful actors have to actualize, seize and prevail on a regular basis.

Improving Secondary Organic Aerosol (SOA) Models using Global Sensitivity Analysis and by Comparison to Chamber Data.

NASA Astrophysics Data System (ADS)

Miller, D. O.; Brune, W. H.

2017-12-01

Accurate estimates of secondary organic aerosol (SOA) from atmospheric models is a major research challenge due to the complexity of the chemical and physical processes involved in the SOA formation and continuous aging. The primary uncertainties of SOA models include those associated with the formation of gas-phase products, the conversion between gas phase and particle phase, the aging mechanisms of SOA, and other processes related to the heterogeneous and particle-phase reactions. To address this challenge, we us a modular modeling framework that combines both simple and near-explicit gas-phase reactions and a two-dimensional volatility basis set (2D-VBS) to simulate the formation and evolution of SOA. Global sensitivity analysis is used to assess the relative importance of the model input parameters. In addition, the model is compared to the measurements from the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT).

Semi-continuous mass closure of the major components of fine particulate matter in Riverside, CA

NASA Astrophysics Data System (ADS)

Grover, Brett D.; Eatough, Norman L.; Woolwine, Woods R.; Cannon, Justin P.; Eatough, Delbert J.; Long, Russell W.

The application of newly developed semi-continuous aerosol monitors allows for the measurement of all the major species of PM 2.5 on a 1-h time basis. Temporal resolution of both non-volatile and semi-volatile species is possible. A suite of instruments to measure the major chemical species of PM 2.5 allows for semi-continuous mass closure. A newly developed dual-oven Sunset carbon monitor is used to measure non-volatile organic carbon, semi-volatile organic carbon and elemental carbon. Inorganic species, including sulfate and nitrate, can be measured with an ion chromatograph based sampler. Comparison of the sum of the major chemical species in an urban aerosol with mass measured by an FDMS resulted in excellent agreement. Linear regression analysis resulted in a zero-intercept slope of 0.98±0.01 with an R2=0.86. One-hour temporal resolution of the major species of PM 2.5 may reduce the uncertainty in receptor based source apportionment modeling, will allow for better forecasting of PM 2.5 episodes, and may lead to increased understanding of related health effects.

Thermodynamic constants for actinide oxides and oxyhydroxides relevant to actinide volatility calculations for thermal oxidation processes

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

Ebbinghaus, B.B.; Krikorian, O.H.

The purpose of this report is to provide input of thermodynamic data on actinide volatilities to EERC for use in their computer code for modeling of metal volatilities in incinerators. It is also anticipated that the data may be documented later in an EPA sponsored ``Metals Bible.`` It should be noted that only upper limits for the volatility of PuO{sub 2}(s) due to PuO{sub 3}(g) and PuO{sub 2}(OH){sub 2}(g) and the volatility of AmO{sub 2} in PuO{sub 2}(s) due to AmO{sub 3}(g) and AmO{sub 2}(OH){sub 2}(g) could be set. The data on the americium vapor species are intended for calculationsmore » where AmO{sub 2} is present as a solid solution in PuO{sub 2}(s).« less

Modeling and predicting historical volatility in exchange rate markets

NASA Astrophysics Data System (ADS)

Lahmiri, Salim

2017-04-01

Volatility modeling and forecasting of currency exchange rate is an important task in several business risk management tasks; including treasury risk management, derivatives pricing, and portfolio risk evaluation. The purpose of this study is to present a simple and effective approach for predicting historical volatility of currency exchange rate. The approach is based on a limited set of technical indicators as inputs to the artificial neural networks (ANN). To show the effectiveness of the proposed approach, it was applied to forecast US/Canada and US/Euro exchange rates volatilities. The forecasting results show that our simple approach outperformed the conventional GARCH and EGARCH with different distribution assumptions, and also the hybrid GARCH and EGARCH with ANN in terms of mean absolute error, mean of squared errors, and Theil's inequality coefficient. Because of the simplicity and effectiveness of the approach, it is promising for US currency volatility prediction tasks.

Characteristics of volatile organic compounds produced from five pathogenic bacteria by headspace-solid phase micro-extraction/gas chromatography-mass spectrometry.

PubMed

Chen, Juan; Tang, Junni; Shi, Hui; Tang, Cheng; Zhang, Rong

2017-03-01

The characteristics of volatile compounds from five different bacterial species, Escherichia coli O157:H7, Salmonella Enteritidis, Shigella flexneri, Staphylococcus aureus, and Listeria monocytogenes, growing, respectively, in trypticase soy broth were monitored by headspace solid-phase micro-extraction/gas chromatography-mass spectrometry. The results showed that most volatile organic compounds (VOCs) of five pathogens started to increase after the sixth to tenth hour. Methyl ketones and long chain alcohols were representative volatiles for three Gram-negative bacteria. The especially high production of indole was characterized to E. coli O157:H7. The production of 3-hydroxy-2-butanone was indicative of the presence of two Gram-positive bacteria. Both 3-methyl-butanoic acid and 3-methyl-butanal were unique biomarkers for S. aureus. The population dynamics of individual pathogen could be monitored using the accumulation of VOCs correlated with its growth. And these five pathogens could be distinguishable though principle component analysis of 18 volatile metabolites. Moreover, the mixed culture of S. aureus and E. coli O157:H7 was also investigated. The levels of 3-methyl-butanal and 3-methyl-butanoic acid were largely reduced; while the level of indole almost unchanged and correlated with E. coli O157:H7 growth very well. The characteristics of volatiles from the five foodborne pathogens could lay a fundamental basis for further research into pathogen contamination control by detecting volatile signatures of pathogens. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Basis sets for the calculation of core-electron binding energies

NASA Astrophysics Data System (ADS)

Hanson-Heine, Magnus W. D.; George, Michael W.; Besley, Nicholas A.

2018-05-01

Core-electron binding energies (CEBEs) computed within a Δ self-consistent field approach require large basis sets to achieve convergence with respect to the basis set limit. It is shown that supplementing a basis set with basis functions from the corresponding basis set for the element with the next highest nuclear charge (Z + 1) provides basis sets that give CEBEs close to the basis set limit. This simple procedure provides relatively small basis sets that are well suited for calculations where the description of a core-ionised state is important, such as time-dependent density functional theory calculations of X-ray emission spectroscopy.

Heritability of Attractiveness to Mosquitoes

PubMed Central

Fernández-Grandon, G. Mandela; Gezan, Salvador A.; Armour, John A. L.; Pickett, John A.; Logan, James G.

2015-01-01

Female mosquitoes display preferences for certain individuals over others, which is determined by differences in volatile chemicals produced by the human body and detected by mosquitoes. Body odour can be controlled genetically but the existence of a genetic basis for differential attraction to insects has never been formally demonstrated. This study investigated heritability of attractiveness to mosquitoes by evaluating the response of Aedes aegypti (=Stegomyia aegypti) mosquitoes to odours from the hands of identical and non-identical twins in a dual-choice assay. Volatiles from individuals in an identical twin pair showed a high correlation in attractiveness to mosquitoes, while non-identical twin pairs showed a significantly lower correlation. Overall, there was a strong narrow-sense heritability of 0.62 (SE 0.124) for relative attraction and 0.67 (0.354) for flight activity based on the average of ten measurements. The results demonstrate an underlying genetic component detectable by mosquitoes through olfaction. Understanding the genetic basis for attractiveness could create a more informed approach to repellent development. PMID:25901606

Fluidized bed combustion of high-volatile solid fuels: An assessment of char attrition and volatile matter segregation

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

Chirone, R.; Marzocchella, A.; Salatino, P.

1999-07-01

A simple lumped-parameter model of a bubbling fluidized bed combustor fueled with high-volatile solid fuels is presented. The combustor is divided into three sections: the dense bed, the splashing region and the freeboard. Material balances on fixed carbon, volatile matter and oxygen are set up, taking into account fuel particle fragmentation and attrition, volatile matter segregation as well as postcombustion of both carbon fines and volatiles escaping the bed. A basic assumption of the model is that the combustion pathway that foes from the raw fuel to the combustion products proceeds via the formation of three phases: volatile matter, relativelymore » large non-elutriable char particles and fine char particles of elutriable size. The study is complemented by a simplified thermal balance on the splashing zone taking into account volatiles and elutriated fines postcombustion and radiative and convective heat fluxes to the bed and the freeboard. Results from calculations with either low- or high-volatile solid fuels indicate that low-volatile bituminous coal combustion takes place essentially in the bed mostly via coarse char particles combustion, while high-volatile biomass fuel combustion occurs to comparable extents both in the bed and in the splashing region of the combustor. Depending on the extent of volatile matter segregation with respect to the bed, a significant fraction of the heat is released into the splashing region of the combustor and this results into an increase of temperature in this region. Extensive bed solids recirculation associated to bubble bursting/solids ejection at the bed surface together with effective gas-solids heat transfer promotes thermal feedback from this region to the bed of as much as 90% of the heat release by volatile matter and elutriated fines afterburning.« less

The role of semi-volatile organic compounds in the mesoscale evolution of biomass burning aerosol: a modelling case study of the 2010 mega-fire event in Russia

NASA Astrophysics Data System (ADS)

Konovalov, I. B.; Beekmann, M.; Berezin, E. V.; Petetin, H.; Mielonen, T.; Kuznetsova, I. N.; Andreae, M. O.

2015-03-01

Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidating possible reasons for discrepancies between them, which, "by default", are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data regarding atmospheric evolution of BB aerosol and by using the volatility basis set (VBS) approach to organic aerosol modeling along with a "conventional" approach, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. BB emissions of primary aerosol components were constrained with the PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the conventional approach (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimates values of ΔPM10/ΔCO observed in Kuopio (by almost a factor of two), the VBS approach is capable to bring the simulations to a reasonable agreement with the ground measurements both in Moscow and in Kuopio. Using the VBS instead of the conventional approach is also found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.

The role of semi-volatile organic compounds in the mesoscale evolution of biomass burning aerosol: a modeling case study of the 2010 mega-fire event in Russia

NASA Astrophysics Data System (ADS)

Konovalov, I. B.; Beekmann, M.; Berezin, E. V.; Petetin, H.; Mielonen, T.; Kuznetsova, I. N.; Andreae, M. O.

2015-12-01

Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidation of possible reasons for discrepancies between them, which, by default, are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data on the atmospheric evolution of BB aerosol and using the volatility basis set (VBS) framework for organic aerosol modeling, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. Biomass burning emissions of primary aerosol components were constrained with PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the simulations based on a "conventional" approach to BB aerosol modeling (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimated values of ΔPM10/ΔCO observed in Kuopio (by a factor of 2), employing the "advanced" representation of atmospheric processing of organic aerosol material resulted in bringing the simulations to a much closer agreement with the ground measurements. Furthermore, taking gas-particle partitioning and oxidation of SVOCs into account is found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.

Volatile properties of particles emitted by compressed natural gas and diesel buses during steady-state and transient driving modes.

PubMed

Jayaratne, E R; Meyer, N K; Ristovski, Z D; Morawska, L

2012-01-03

Volatile properties of particle emissions from four compressed natural gas (CNG) and four diesel buses were investigated under steady-state and transient driving modes on a chassis dynamometer. The exhaust was diluted utilizing a full-flow continuous volume sampling system and passed through a thermodenuder at controlled temperature. Particle number concentration and size distribution were measured with a condensation particle counter and a scanning mobility particle sizer, respectively. We show that while almost all the particles emitted by the CNG buses were in the nanoparticle size range, at least 85% and 98% were removed at 100 and 250 °C, respectively. Closer analysis of the volatility of particles emitted during transient cycles showed that volatilization began at around 40 °C, with the majority occurring by 80 °C. Particles produced during hard acceleration from rest exhibited lower volatility than those produced during other times of the cycle. On the basis of our results and the observation of ash deposits on the walls of the tailpipes, we suggest that these nonvolatile particles were composed mostly of ash from lubricating oil. Heating the diesel bus emissions to 100 °C removed ultrafine particle numbers by 69-82% when a nucleation mode was present and just 18% when it was not.

Rust and schreibersite in Apollo 16 highland rocks - Manifestations of volatile-element mobility

NASA Technical Reports Server (NTRS)

Hunter, R. H.; Taylor, L. A.

1982-01-01

Rust is a manifestation of halogen and volatile-metal mobility in the lunar environment. Schreibersite is stable as the primary phosphorus-bearing phase in the highland rocks, a consequence of the inherently low oxygen fugacity within impact-generated melts. Apatite and whitlockite are subordinate in these rocks. The partitioning of P into phosphide in impact-generated melts, and the failure of phosphate to crystallize, effects a decoupling of the halogens and phosphorus. Of the Apollo 16 rocks, 63% contain rust, 70% contain schreibersite, and 52% contain both phases, thereby establishing the pervasiveness of volatile-elements throughout the highland rocks. The major portion of these volatile-bearing phases occur in impact melt-rocks or in breccia matrices. Rhabdites of schreibersite in some of the FeNi grains indicate that there is a meteoritic contribution to the phosphorus in these rocks. Cl/P2O5 ratios in lunar highland rocks are a function of secondary effects, with any apparent Cl-P correlations being coincidential. The present observations preclude the validity of models based on such elemental ratios in these rocks. The presence of rust in the clast laden matrices of pristine rocks indicates fugitive element localization. Pristine clasts may have been contaminated. The basis for a pristine volatile chemistry is questioned.

Function of bacterial community dynamics in the formation of cadaveric semiochemicals during in situ carcass decomposition.

PubMed

Pascual, Javier; von Hoermann, Christian; Rottler-Hoermann, Ann-Marie; Nevo, Omer; Geppert, Alicia; Sikorski, Johannes; Huber, Katharina J; Steiger, Sandra; Ayasse, Manfred; Overmann, Jörg

2017-08-01

The decomposition of dead mammalian tissue involves a complex temporal succession of epinecrotic bacteria. Microbial activity may release different cadaveric volatile organic compounds which in turn attract other key players of carcass decomposition such as scavenger insects. To elucidate the dynamics and potential functions of epinecrotic bacteria on carcasses, we monitored bacterial communities developing on still-born piglets incubated in different forest ecosystems by combining high-throughput Illumina 16S rRNA sequencing with gas chromatography-mass spectrometry of volatiles. Our results show that the community structure of epinecrotic bacteria and the types of cadaveric volatile compounds released over the time course of decomposition are driven by deterministic rather than stochastic processes. Individual cadaveric volatile organic compounds were correlated with specific taxa during the first stages of decomposition which are dominated by bacteria. Through best-fitting multiple linear regression models, the synthesis of acetic acid, indole and phenol could be linked to the activity of Enterobacteriaceae, Tissierellaceae and Xanthomonadaceae, respectively. These conclusions are also commensurate with the metabolism described for the dominant taxa identified for these families. The predictable nature of in situ synthesis of cadaveric volatile organic compounds by epinecrotic bacteria provides a new basis for future chemical ecology and forensic studies. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

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

Papajak, Ewa; Truhlar, Donald G.

We present sets of convergent, partially augmented basis set levels corresponding to subsets of the augmented “aug-cc-pV(n+d)Z” basis sets of Dunning and co-workers. We show that for many molecular properties a basis set fully augmented with diffuse functions is computationally expensive and almost always unnecessary. On the other hand, unaugmented cc-pV(n+d)Z basis sets are insufficient for many properties that require diffuse functions. Therefore, we propose using intermediate basis sets. We developed an efficient strategy for partial augmentation, and in this article, we test it and validate it. Sequentially deleting diffuse basis functions from the “aug” basis sets yields the “jul”,more » “jun”, “may”, “apr”, etc. basis sets. Tests of these basis sets for Møller-Plesset second-order perturbation theory (MP2) show the advantages of using these partially augmented basis sets and allow us to recommend which basis sets offer the best accuracy for a given number of basis functions for calculations on large systems. Similar truncations in the diffuse space can be performed for the aug-cc-pVxZ, aug-cc-pCVxZ, etc. basis sets.« less

Migration from printing inks in multilayer food packaging materials by GC-MS analysis and pattern recognition with chemometrics.

PubMed

Clemente, Isabel; Aznar, Margarita; Nerín, Cristina; Bosetti, Osvaldo

2016-01-01

Inks and varnishes used in food packaging multilayer materials can contain different substances that are potential migrants when packaging is in contact with food. Although printing inks are applied on the external layer, they can migrate due to set-off phenomena. In order to assess food safety, migration tests were performed from two materials sets: set A based on paper and set B based on PET; both contained inks. Migration was performed to four food simulants (EtOH 50%, isooctane, EtOH 95% and Tenax(®)) and the volatile compounds profile was analysed by GC-MS. The effect of presence/absence of inks and varnishes and also their position in the material was studied. A total of 149 volatile compounds were found in migration from set A and 156 from set B materials, some of them came from inks. Quantitative analysis and a principal component analysis were performed in order to identify patterns among sample groups.

Estimating the CCSD basis-set limit energy from small basis sets: basis-set extrapolations vs additivity schemes

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

Spackman, Peter R.; Karton, Amir, E-mail: amir.karton@uwa.edu.au

Coupled cluster calculations with all single and double excitations (CCSD) converge exceedingly slowly with the size of the one-particle basis set. We assess the performance of a number of approaches for obtaining CCSD correlation energies close to the complete basis-set limit in conjunction with relatively small DZ and TZ basis sets. These include global and system-dependent extrapolations based on the A + B/L{sup α} two-point extrapolation formula, and the well-known additivity approach that uses an MP2-based basis-set-correction term. We show that the basis set convergence rate can change dramatically between different systems(e.g.it is slower for molecules with polar bonds and/ormore » second-row elements). The system-dependent basis-set extrapolation scheme, in which unique basis-set extrapolation exponents for each system are obtained from lower-cost MP2 calculations, significantly accelerates the basis-set convergence relative to the global extrapolations. Nevertheless, we find that the simple MP2-based basis-set additivity scheme outperforms the extrapolation approaches. For example, the following root-mean-squared deviations are obtained for the 140 basis-set limit CCSD atomization energies in the W4-11 database: 9.1 (global extrapolation), 3.7 (system-dependent extrapolation), and 2.4 (additivity scheme) kJ mol{sup –1}. The CCSD energy in these approximations is obtained from basis sets of up to TZ quality and the latter two approaches require additional MP2 calculations with basis sets of up to QZ quality. We also assess the performance of the basis-set extrapolations and additivity schemes for a set of 20 basis-set limit CCSD atomization energies of larger molecules including amino acids, DNA/RNA bases, aromatic compounds, and platonic hydrocarbon cages. We obtain the following RMSDs for the above methods: 10.2 (global extrapolation), 5.7 (system-dependent extrapolation), and 2.9 (additivity scheme) kJ mol{sup –1}.« less

Estimating the CCSD basis-set limit energy from small basis sets: basis-set extrapolations vs additivity schemes

NASA Astrophysics Data System (ADS)

Spackman, Peter R.; Karton, Amir

2015-05-01

Coupled cluster calculations with all single and double excitations (CCSD) converge exceedingly slowly with the size of the one-particle basis set. We assess the performance of a number of approaches for obtaining CCSD correlation energies close to the complete basis-set limit in conjunction with relatively small DZ and TZ basis sets. These include global and system-dependent extrapolations based on the A + B/Lα two-point extrapolation formula, and the well-known additivity approach that uses an MP2-based basis-set-correction term. We show that the basis set convergence rate can change dramatically between different systems(e.g.it is slower for molecules with polar bonds and/or second-row elements). The system-dependent basis-set extrapolation scheme, in which unique basis-set extrapolation exponents for each system are obtained from lower-cost MP2 calculations, significantly accelerates the basis-set convergence relative to the global extrapolations. Nevertheless, we find that the simple MP2-based basis-set additivity scheme outperforms the extrapolation approaches. For example, the following root-mean-squared deviations are obtained for the 140 basis-set limit CCSD atomization energies in the W4-11 database: 9.1 (global extrapolation), 3.7 (system-dependent extrapolation), and 2.4 (additivity scheme) kJ mol-1. The CCSD energy in these approximations is obtained from basis sets of up to TZ quality and the latter two approaches require additional MP2 calculations with basis sets of up to QZ quality. We also assess the performance of the basis-set extrapolations and additivity schemes for a set of 20 basis-set limit CCSD atomization energies of larger molecules including amino acids, DNA/RNA bases, aromatic compounds, and platonic hydrocarbon cages. We obtain the following RMSDs for the above methods: 10.2 (global extrapolation), 5.7 (system-dependent extrapolation), and 2.9 (additivity scheme) kJ mol-1.

40 CFR 60.704 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES Standards of Performance for Volatile Organic Compound Emissions From Synthetic Organic Chemical Manufacturing Industry (SOCMI) Reactor Processes § 60... basis of compound j in ppm, as measured for organics by Method 18 and measured for hydrogen and carbon...

REPLACEMENT OF HAZARDOUS MATERIAL IN WIDE WEB FLEXOGRAPHIC PRINTING PROCESS

EPA Science Inventory

This study examined on a technical and economic basis, the effect of substituting water-based inks in a flexographic printing process. o reduce volatile organic compound (VOC) emissions by switching from the use of solvent-based inks to water based inks, several equipment modific...

REPLACEMENT OF HAZARDOUS MATERIAL IN WIDE WEB FLEXOGRAPHIC PRINTING PROCESS

EPA Science Inventory

This study examined on a technical and economic basis, the effect of substituting water-based inks in a flexographic printing process. To reduce volatile organic compound (VOC) emissions by switching from the use of solvent-based inks to water based inks, several equipment modifi...

Market microstructure matters when imposing a Tobin tax-Evidence from the lab.

PubMed

Kirchler, Michael; Huber, Jürgen; Kleinlercher, Daniel

2011-12-01

TRADING IN FX MARKETS IS DOMINATED BY TWO MICROSTRUCTURES: exchanges with market makers and OTC-markets without market makers. Using laboratory experiments we test whether the impact of a Tobin tax is different in these two market microstructures. We find that (i) in markets without market makers an unilaterally imposed Tobin tax (i.e. a tax haven exists) increases volatility. (ii) In contrast, in markets with market makers we observe a decrease in volatility in unilaterally taxed markets. (iii) An encompassing Tobin tax has no impact on volatility in either setting. Efficiency does not vary significantly across tax regimes.

Deuterium enrichment in the primitive ices of the protosolar nebula

NASA Technical Reports Server (NTRS)

Lutz, Barry L.; Owen, Tobias; De Bergh, Catherine

1990-01-01

On the basis of CH3D/CH4-ratio observations in the outer planets, the present effort to estimate the D/H ratio of the protosolar nebula's primitive ices arrives at two simple, yet effectively limiting models which constrain the degree of dilution undergone by deuterated volatiles through mixing with the initial hydrogen envelopes. These volatiles would have been contributed to planetary atmospheres by evaporated primordial ices. Ice D/H ratio model results of 0.0001 to 0.001 are compared with values for other potentially primitive material-containing bodies in the solar system, as well as with D/H ratio values from interstellar polyatomic molecules.

Regulatory off-gas analysis from the evaporation of Hanford simulated waste spiked with organic compounds.

PubMed

Saito, Hiroshi H; Calloway, T Bond; Ferrara, Daro M; Choi, Alexander S; White, Thomas L; Gibson, Luther V; Burdette, Mark A

2004-10-01

After strontium/transuranics removal by precipitation followed by cesium/technetium removal by ion exchange, the remaining low-activity waste in the Hanford River Protection Project Waste Treatment Plant is to be concentrated by evaporation before being mixed with glass formers and vitrified. To provide a technical basis to permit the waste treatment facility, a relatively organic-rich Hanford Tank 241-AN-107 waste simulant was spiked with 14 target volatile, semi-volatile, and pesticide compounds and evaporated under vacuum in a bench-scale natural circulation evaporator fitted with an industrial stack off-gas sampler at the Savannah River National Laboratory. An evaporator material balance for the target organics was calculated by combining liquid stream mass and analytical data with off-gas emissions estimates obtained using U.S. Environmental Protection Agency (EPA) SW-846 Methods. Volatile and light semi-volatile organic compounds (<220 degrees C BP, >1 mm Hg vapor pressure) in the waste simulant were found to largely exit through the condenser vent, while heavier semi-volatiles and pesticides generally remain in the evaporator concentrate. An OLI Environmental Simulation Program (licensed by OLI Systems, Inc.) evaporator model successfully predicted operating conditions and the experimental distribution of the fed target organics exiting in the concentrate, condensate, and off-gas streams, with the exception of a few semi-volatile and pesticide compounds. Comparison with Henry's Law predictions suggests the OLI Environmental Simulation Program model is constrained by available literature data.

Pattern recognition and genetic algorithms for discrimination of orange juices and reduction of significant components from headspace solid-phase microextraction.

PubMed

Rinaldi, Maurizio; Gindro, Roberto; Barbeni, Massimo; Allegrone, Gianna

2009-01-01

Orange (Citrus sinensis L.) juice comprises a complex mixture of volatile components that are difficult to identify and quantify. Classification and discrimination of the varieties on the basis of the volatile composition could help to guarantee the quality of a juice and to detect possible adulteration of the product. To provide information on the amounts of volatile constituents in fresh-squeezed juices from four orange cultivars and to establish suitable discrimination rules to differentiate orange juices using new chemometric approaches. Fresh juices of four orange cultivars were analysed by headspace solid-phase microextraction (HS-SPME) coupled with GC-MS. Principal component analysis, linear discriminant analysis and heuristic methods, such as neural networks, allowed clustering of the data from HS-SPME analysis while genetic algorithms addressed the problem of data reduction. To check the quality of the results the chemometric techniques were also evaluated on a sample. Thirty volatile compounds were identified by HS-SPME and GC-MS analyses and their relative amounts calculated. Differences in composition of orange juice volatile components were observed. The chosen orange cultivars could be discriminated using neural networks, genetic relocation algorithms and linear discriminant analysis. Genetic algorithms applied to the data were also able to detect the most significant compounds. SPME is a useful technique to investigate orange juice volatile composition and a flexible chemometric approach is able to correctly separate the juices.

Volatilization and Precipitation of Tellurium by Aerobic, Tellurite-Resistant Marine Microbes▿ †

PubMed Central

Ollivier, Patrick R. L.; Bahrou, Andrew S.; Marcus, Sarah; Cox, Talisha; Church, Thomas M.; Hanson, Thomas E.

2008-01-01

Microbial resistance to tellurite, an oxyanion of tellurium, is widespread in the biosphere, but the geochemical significance of this trait is poorly understood. As some tellurite resistance markers appear to mediate the formation of volatile tellurides, the potential contribution of tellurite-resistant microbial strains to trace element volatilization in salt marsh sediments was evaluated. Microbial strains were isolated aerobically on the basis of tellurite resistance and subsequently examined for their capacity to volatilize tellurium in pure cultures. The tellurite-resistant strains recovered were either yeasts related to marine isolates of Rhodotorula spp. or gram-positive bacteria related to marine strains within the family Bacillaceae based on rRNA gene sequence comparisons. Most strains produced volatile tellurides, primarily dimethyltelluride, though there was a wide range of the types and amounts of species produced. For example, the Rhodotorula spp. produced the greatest quantities and highest diversity of volatile tellurium compounds. All strains also produced methylated sulfur compounds, primarily dimethyldisulfide. Intracellular tellurium precipitates were a major product of tellurite metabolism in all strains tested, with nearly complete recovery of the tellurite initially provided to cultures as a precipitate. Different strains appeared to produce different shapes and sizes of tellurium containing nanostructures. These studies suggest that aerobic marine yeast and Bacillus spp. may play a greater role in trace element biogeochemistry than has been previously assumed, though additional work is needed to further define and quantify their specific contributions. PMID:18849455

Characterising Biomass Burning Aerosol in WRF-Chem using the Volatility Basis Set, with Evaluation against SAMBBA Flight Data

NASA Astrophysics Data System (ADS)

Lowe, D.; Topping, D. O.; Archer-Nicholls, S.; Darbyshire, E.; Morgan, W.; Liu, D.; Allan, J. D.; Coe, H.; McFiggans, G.

2015-12-01

The burning of forests in the Amazonia region is a globally significant source of carbonaceous aerosol, containing both absorbing and scattering components [1]. In addition biomass burning aerosol (BBA) are also efficient cloud condensation nuclei (CCN), modifying cloud properties and influencing atmospheric circulation and precipitation tendencies [2]. The impacts of BBA are highly dependent on their size distribution and composition. A bottom-up emissions inventory, the Brazilian Biomass Burning Emissions Model (3BEM) [3], utilising satellite products to generate daily fire emission maps is used. Injection of flaming emissions within the atmospheric column is simulated using both a sub-grid plume-rise parameterisation [4], and simpler schemes, within the Weather Research and Forecasting Model with Chemistry (WRF-Chem, v3.4.1) [5]. Aerosol dynamics are simulated using the sectional MOSAIC scheme [6], incorporating a volatility basis set (VBS) treatment of organic aerosol [7]. For this work we have modified the 9-bin VBS to use the biomass burning specific scheme developed by May et al. [8]. The model has been run for September 2012 over South America (at a 25km resolution). We will present model results evaluating the modelled aerosol vertical distribution, size distribution, and composition against measurements taken by the FAAM BAe-146 research aircraft during the SAMBBA campaign. The main focus will be on investigating the factors controlling the vertical gradient of the organic mass to black carbon ratio of the measured aerosol. This work is supported by the Nature Environment Research Council (NERC) as part of the SAMBBA project under grant NE/J010073/1. [1] D. G. Streets et al., 2004, J. Geophys. Res., 109, D24212. [2] M. O. Andreae et al., 2004, Science, 303, 1337-1342. [3] K. Longo et al., 2010, Atmos. Chem. Phys., 10, 5,785-5,795. [4] S. Freitas et al., 2007, Atmos. Chem. Phys., 7, 3,385-3,398. [5] S. Archer-Nicholls et al., 2015, Geosci. Model Dev., 8, 549-577 [6] R. Zavari et al., 2008, J. Geophys. Res., 113, D132024. [7] M. Shrivastava et al., 2011, Atmos. Chem. Phys., 11, 6639-6662 [8] A. May et al., 2013, J. Geophys. Res., 118, 11,327-11,338

Characterisation of volatile profiles in 50 native Peruvian chili pepper using solid phase microextraction-gas chromatography mass spectrometry (SPME-GCMS).

PubMed

Patel, Kirti; Ruiz, Candy; Calderon, Rosa; Marcelo, Mavel; Rojas, Rosario

2016-11-01

The volatiles were characterised by headspace solid phase micro extraction (HS-SPME), gas chromatography mass spectrometry (GC-FID/MS). A total of 127 compounds were identified with terpenes (including mono terpenes and sesquiterpenes - a total of 45 compounds), esters (31 compounds) and hydrocarbons (20 compounds) were the predominant volatile compounds. Principal component analysis (PCA) of the volatile compounds yielded 2 significant PC's, which together accounted for 90.3% of the total variance in the data set and the scatter plot generated between PC1 and PC2 successfully segregated the 50 chili pepper samples into 7 groups. Clusters of hydrocarbons, esters, terpenes, aldehyde and ketones formed the major determinants of the difference. Copyright © 2016 Elsevier Ltd. All rights reserved.

Volatile Outputs From Subduction-Related Magmatism in the Oregon Cascades Estimated From Melt Inclusions, Spring Discharges, Heat Flow Data and Geochronology

NASA Astrophysics Data System (ADS)

Wallace, P.; Ruscitto, D.; Rowe, M.; Kent, A.

2008-12-01

Estimates of volatile fluxes provide a primary test for models of magmatism and volatile cycling during subduction in the endmember "hot and dry" Cascadia subduction zone, which is caused by slow convergence (4 cm/a) of the young (~10-12 Ma) Juan de Fuca plate with Western North America. Intra- arc rifting in the Central Oregon segment of the Cascade arc during the past 2 Ma has caused this region to have the highest mafic output along the arc. However, estimates of major volatile (H2O, CO2, S, Cl) fluxes and comparisons with other arcs (e.g. Central America) are not straightforward because there are no passively degassing volcanoes in the area. We estimate volatile outputs for the Central Oregon Cascades by combining data for olivine-hosted melt inclusions with regional heat flow (e.g. Ingebritsen, 1989; Blackwell,1990) and geochronological (Sherrod and Smith, 1990) studies. These flux estimates can be compared with those obtained from spring water studies (e.g. James, 1999; Hurwitz, 2005). This multidisciplinary approach allows us to more accurately constrain volatile fluxes, given that uncertainties in all methods are large and difficult to evaluate. Reported fluxes for Central Oregon springs are 3.4E5 CO2 and 1.5E4 Cl kg/yr/km of arc (James, 1999; Hurwitz, 2005). Melt inclusion data indicate primitive basaltic magmas in the Central Oregon Cascades have 1.0-3.5 wt% H2O, 800-1900 ppm S, and 300-1100 ppm Cl. Assuming global arc magma CO2 contents of ~1 wt% (Wallace, 2005), we estimate H2O/CO2 (1.0-3.5), S/CO2 (0.08-0.19), and Cl/CO2 (0.03-0.11) in magmas, which when combined with spring CO2 estimates, yield an H2O flux of 0.34-1.2E6, a S flux of 2.6-6.5E4, and a Cl flux of 1.0-3.7E4 kg/yr/km of arc. Alternatively, by combining melt inclusion data with magma flux estimates (14-38 km3/Myr/km of arc; Ingebritsen et al. 1989; Sherrod and Smith 1990) we estimate volatile fluxes for H2O: 0.39-5.4E6; S: 0.39-3.9E5; and Cl: 0.16- 2.3E5 kg/yr/km of arc. Given the uncertainties involved, these are highly consistent with the estimates based on spring data. For comparison, Central Oregon S and CO2 fluxes are 6-31% and 13-80%, respectively, of the fluxes estimated for the Central American arc on a kg/yr/km of arc basis (Sadofsky, 2008; Hilton, 1992). Comparison of Central Oregon volatile outputs with slab inputs (Ito, 1983; Hilton, 1992; Jarrard, 2003) suggests low recycling efficiencies via magmatism for H2O (3-26%) and S (1-7%) and more variable recycling efficiencies for CO2 (9-55%) and Cl (9-87%). Low volatile recycling efficiencies via magmatism are consistent with both the high temperatures estimated for the subducted slab beneath the Cascades and the presence of a shallow reservoir for early devolatilized material in the serpentinized forearc mantle wedge. Low but non-zero recycling efficiencies could indicate that 1) slab devolatilization beneath the forearc is incomplete and/or 2) downdragging of the serpentinized forearc mantle by corner flow in the mantle wedge is significant in this hot arc setting.

FORMULATING ULTRA-LOW-VOC WOOD FURNITURE COATINGS

EPA Science Inventory

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

History and development of food-based attractants

USDA-ARS?s Scientific Manuscript database

Adult tephrids require sugar and protein for survival and for development of eggs, and volatile chemicals from these substances are the basis for food-based lures developed as baits for these pests. In this chapter, we discuss food-based lures that mimic food sources for adults other than host fruit...

Relative congener scaling of Polychlorinated dibenzo-p-dioxins and dibenzofurans to estimate building fire contributions in air, surface wipes, and dust samples.

PubMed

Pleil, Joachim D; Lorber, Matthew N

2007-11-01

The United States Environmental Protection Agency collected ambient air samples in lower Manhattan for about 9 months following the September 11, 2001 World Trade Center (WTC) attacks. Measurements were made of a host of airborne contaminants including volatile organic compounds, polycyclic aromatic hydrocarbons, asbestos, lead, and other contaminants of concern. The present study focuses on the broad class of polychlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) with specific emphasis on the 17 CDD/CDF congeners that exhibit mammalian toxicity. This work is a statistical study comparing the internal patterns of CDD/CDFs using data from an unambiguous fire event (WTC) and other data sets to help identify their sources. A subset of 29 samples all taken between September 16 and October 31, 2001 were treated as a basis set known to be heavily impacted by the WTC building fire source. A second basis set was created using data from Los Angeles and Oakland, CA as published by the California Air Resources Board (CARB) and treated as the archetypical background pattern for CDD/CDFs. The CARB data had a congener profile appearing similar to background air samples from different locations in America and around the world and in different matrices, such as background soils. Such disparate data would normally be interpreted with a qualitative pattern recognition based on congener bar graphs or other forms of factor or cluster analysis that group similar samples together graphically. The procedure developed here employs aspects of those statistical methods to develop a single continuous output variable per sample. Specifically, a form of variance structure-based cluster analysis is used to group congeners within samples to reduce collinearity in the basis sets, new variables are created based on these groups, and multivariate regression is applied to the reduced variable set to determine a predictive equation. This equation predicts a value for an output variable, OPT: the predicted value of OPT is near zero (0.00) for a background congener profile and near one (1.00) forthe profile characterized by the WTC air profile. Although this empirical method is calibrated with relatively small sets of airborne samples, it is shown to be generalizable to other WTC, fire source, and background air samples as well as other sample matrices including soils, window films and other dust wipes, and bulk dusts. However, given the limited data set examined, the method does not allow further discrimination between the WTC data and the other fire sources. This type of analysis is demonstrated to be useful for complex trace-level data sets with limited data and some below-detection entries.

Volatile dynamics in crystal-rich magma bodies, perspectives from laboratory experiments and theory

NASA Astrophysics Data System (ADS)

Faroughi, S.; Parmigiani, A.; Huber, C.

2013-12-01

The amount of volatiles and the dynamics of bubbles play a significant role on the transition between different volcanic eruption behaviors. The transport of exsolved volatiles through zoned magma chambers is complex and remains poorly constrained. Here we focus on the different transport of volatiles under two end member regimes: crystal-poor systems (bubbles form a suspension) versus crystal-rich reservoirs (multiphase porous media flow). We present a combination of multiphase flow laboratory experiments (using silicon oil and water) and a theoretical argument based on Stokes flow streamfunctions to contrast the differences between the transport of exsolved volatiles in both regimes. The first set of experiments involves the buoyant migration of water droplets in silicon oil in the absence of glass beads. We measure the non-linear hydrodynamic interaction between bubbles and its effect on slowing down the average flux of water droplets as the water volume fraction increases. Our experimental results are compared to a theoretical argument in which a streamfunction formulation is used to estimate the effect of a suspension on bubble migration. We find a good agreement between the new theory and our experimental results. The second set of experiments focuses on the transport of water (non-wetting fluid) in porous media saturated with viscous silicon oils. Contrary to suspension dynamics, in multiphase porous media, an increase in the saturation of non-wetting fluid leads to a non-linear increase in its volumetric flux. The steady-state migration of non-wetting fluid is controlled by the formation of viscous fingering instability that greatly enhances transport. We propose that the regime of energy dissipation during the migration of bubbles in heterogeneous magma reservoirs can change, leading to bubble accumulation in crystal-poor regions as fingering becomes unstable and volatiles form a disperse bubble suspension.

Relationships between volatile compounds and sensory characteristics in virgin olive oil by analytical and chemometric approaches.

PubMed

Procida, Giuseppe; Cichelli, Angelo; Lagazio, Corrado; Conte, Lanfranco S

2016-01-15

The volatile fraction of virgin olive oil is characterised by low molecular weight compounds that vaporise at room temperature. In order to obtain an aroma profile similar to natural olfactory perception, the composition of the volatile compounds was determined by applying dynamic headspace gas chromatography, performed at room temperature, with a cryogenic trap directly connected to a gas chromatograph-mass spectrometer system. Samples were also evaluated according to European Union and International Olive Council official methods for sensory evaluation. In this paper, the composition of the volatile fraction of 25 extra virgin olive oils from different regions of Italy was analysed and some preliminary considerations on relationships between chemical composition of volatile fraction and sensory characteristics are reported. Forty-two compounds were identified by means of the particular analytical technique used. All the analysed samples, classified as extra virgin by the panel test, never present peaks whose magnitude is important enough in defected oils. The study was focused on the evaluation of volatile compounds responsible for the positive impact on olive odour properties ('green-fruity' and 'sweet') and olfactory perception. Chemometric evaluation of data, obtained through headspace analysis and the panel test evaluation, showed a correlation between chemical compounds and sensory properties. On the basis of the results, the positive attributes of virgin olive oil are divided into two separated groups: sweet types or green types. Sixteen volatile compounds with known positive impact on odour properties were extracted and identified. In particular, eight compounds seem correlated with sweet properties whereas the green sensation appears to be correlated with eight other different substances. The content of the compounds at six carbon atoms proves to be very important in defining positive attributes of extra virgin olive oils and sensory evaluation. © 2015 Society of Chemical Industry.

Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO

NASA Astrophysics Data System (ADS)

Tsimpidi, A. P.; Karydis, V. A.; Zavala, M.; Lei, W.; Bei, N.; Molina, L.; Pandis, S. N.

2010-11-01

Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites was encouraging. The average predicted PM1 OA concentration in T0, T1, and T2 was 18 μg m-3, 11.7 μg m-3, and 10.5 μg m-3 respectively, while the corresponding measured values were 17.2 μg m-3, 11 μg m-3, and 9 μg m-3. The average predicted fresh primary OA concentrations were 4.4 μg m-3 at T0, 1.2 μg m-3 at T1 and 1.7 μg m-3 at PTP in reasonably good agreement with the corresponding PMF analysis estimates based on the AMS observations of 4.5, 1.3, and 2.9 μg m-3 respectively. The model reproduced reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m-3 predicted versus 7.5 μg m-3 measured), in T1 (6.3 μg m-3 predicted versus 4.6 μg m-3 measured) and in PTP (6.6 μg m-3 predicted versus 5.9 μg m-3 measured). Inside Mexico City, the locally produced OA is predicted to be on average 53% fresh primary (POA), 11% semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 36% traditional SOA from the oxidation of VOCs (V-SOA). The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.

Thermo-chemical modelling of a village cookstove for design improvement

NASA Astrophysics Data System (ADS)

Honkalaskar, Vijay H.; Sohoni, Milind; Bhandarkar, Upendra V.

2014-05-01

Cookstove operation comprises three basic processes, namely combustion of firewood, natural air draft due to the buoyancy induced by the temperature difference between the hearth and its surroundings, and heat transfer to the pot, stove body and surrounding atmosphere. Owing to the heterogenous and unsteady burning of solid fuel, there exist nonlinear and dynamic interrelationships among these process parameters. A steady-state analytical model of the cookstove operation is developed for its design improvement by splitting the hearth into three zones to study char combustion, volatile combustion and heat transfer to the pot bottom separately. It comprises a total of seven relations corresponding to a thorough analysis of the three basic processes. A novel method is proposed to model the combustion of wood to mimic the realities closely. Combustion space above the fuel bed is split into 1000 discrete parts to study the combustion of volatiles by considering a set of representative volatile gases. Model results are validated by comparing them with a set of water boiling tests carried on a traditional cookstove in the laboratory. It is found that the major thrust areas to improve the thermal performance are combustion of volatiles and the heat transfer to the pot. It is revealed that the existing design dimensions of the traditional cookstove are close to their optimal values. Addition of twisted-tape inserts in the hearth of the cookstove shows an improvement in the thermal performance due to increase in the heat transfer coefficient to the pot bottom and improved combustion of volatiles.

An Unusual Complication With the Administration of a Volatile Anesthetic Agent for Status Asthmaticus in the Pediatric Intensive Care Unit: Case Report and Review of the Literature.

PubMed

Shutes, Brittany; Frazier, W Joshua; Tobias, Joseph D

2017-07-01

In severe cases of status asthmaticus, when conventional therapies fail, volatile anesthetic agents remain a therapeutic option. When delivered outside of the operating room setting, specialized delivery techniques are needed to ensure the safe and effective use of volatile anesthetic agents. We present a 16-year-old adolescent with status asthmaticus who required the therapeutic administration of the volatile anesthetic agent, sevoflurane, in the pediatric intensive care unit (PICU). Although initially effective in reducing bronchospasm, progressive hypercarbia developed due to defective functioning of the carbon dioxide absorber of the anesthesia machine. This failure occurred as the soda lime compartment filled with water accumulated from circuit humidification and continuous albuterol therapy. The role of volatile anesthetic agents in the treatment of status asthmaticus in the PICU is discussed, options for delivery outside of the operating room presented, and potential problems with delivery reviewed.

Features of spillover networks in international financial markets: Evidence from the G20 countries

NASA Astrophysics Data System (ADS)

Liu, Xueyong; An, Haizhong; Li, Huajiao; Chen, Zhihua; Feng, Sida; Wen, Shaobo

2017-08-01

The objective of this study is to investigate volatility spillover transmission systematically in stock markets across the G20 countries. To achieve this objective, we combined GARCH-BEKK model with complex network theory using the linkages of spillovers. GARCH-BEKK model was used to capture volatility spillover between stock markets. Then, an information spillover network was built. The data encompass the main stock indexes from 19 individual countries in the G20. To consider the dynamic spillover, the full data set was divided into several sub-periods. The main contribution of this paper is considering the volatility spillover relationships as the edges of a complex network, which can capture the propagation path of volatility spillovers. The results indicate that the volatility spillovers among the stock markets of the G20 countries constitute a holistic associated network, another finding is that Korea acts a role of largest sender in long-term, while Brazil is the largest long-term recipient in the G20 spillover network.

Analysis of honeybush tea (Cyclopia spp.) volatiles by comprehensive two-dimensional gas chromatography using a single-stage thermal modulator.

PubMed

Ntlhokwe, Gaalebalwe; Tredoux, Andreas G J; Górecki, Tadeusz; Edwards, Matthew; Vestner, Jochen; Muller, Magdalena; Erasmus, Lené; Joubert, Elizabeth; Christel Cronje, J; de Villiers, André

2017-07-01

The applicability of comprehensive two-dimensional gas chromatography (GC×GC) using a single-stage thermal modulator was explored for the analysis of honeybush tea (Cyclopia spp.) volatile compounds. Headspace solid phase micro-extraction (HS-SPME) was used in combination with GC×GC separation on a non-polar × polar column set with flame ionisation (FID) detection for the analysis of fermented Cyclopia maculata, Cyclopia subternata and Cyclopia genistoides tea infusions of a single harvest season. Method optimisation entailed evaluation of the effects of several experimental parameters on the performance of the modulator, the choice of columns in both dimensions, as well as the HS-SPME extraction fibre. Eighty-four volatile compounds were identified by co-injection of reference standards. Principal component analysis (PCA) showed clear differentiation between the species based on their volatile profiles. Due to the highly reproducible separations obtained using the single-stage thermal modulator, multivariate data analysis was simplified. The results demonstrate both the complexity of honeybush volatile profiles and the potential of GC×GC separation in combination with suitable data analysis techniques for the investigation of the relationship between sensory properties and volatile composition of these products. The developed method therefore offers a fast and inexpensive methodology for the profiling of honeybush tea volatiles. Graphical abstract Surface plot obtained for the GC×GC-FID analysis of honeybush tea volatiles.

Correlation consistent basis sets for the atoms In–Xe

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

Mahler, Andrew; Wilson, Angela K., E-mail: akwilson@unt.edu

In this work, the correlation consistent family of Gaussian basis sets has been expanded to include all-electron basis sets for In–Xe. The methodology for developing these basis sets is described, and several examples of the performance and utility of the new sets have been provided. Dissociation energies and bond lengths for both homonuclear and heteronuclear diatomics demonstrate the systematic convergence behavior with respect to increasing basis set quality expected by the family of correlation consistent basis sets in describing molecular properties. Comparison with recently developed correlation consistent sets designed for use with the Douglas-Kroll Hamiltonian is provided.

Model risk for European-style stock index options.

PubMed

Gençay, Ramazan; Gibson, Rajna

2007-01-01

In empirical modeling, there have been two strands for pricing in the options literature, namely the parametric and nonparametric models. Often, the support for the nonparametric methods is based on a benchmark such as the Black-Scholes (BS) model with constant volatility. In this paper, we study the stochastic volatility (SV) and stochastic volatility random jump (SVJ) models as parametric benchmarks against feedforward neural network (FNN) models, a class of neural network models. Our choice for FNN models is due to their well-studied universal approximation properties of an unknown function and its partial derivatives. Since the partial derivatives of an option pricing formula are risk pricing tools, an accurate estimation of the unknown option pricing function is essential for pricing and hedging. Our findings indicate that FNN models offer themselves as robust option pricing tools, over their sophisticated parametric counterparts in predictive settings. There are two routes to explain the superiority of FNN models over the parametric models in forecast settings. These are nonnormality of return distributions and adaptive learning.

Comparative analysis of volatiles in traditionally cured Bourbon and Ugandan vanilla bean ( Vanilla planifolia ) extracts.

PubMed

Zhang, Suying; Mueller, Christoph

2012-10-24

Traditionally cured vanilla beans ( Vanilla planifolia ) from Madagascar and Uganda were extracted with organic solvents, and the volatiles were separated from the nonvolatile fraction using the solvent assisted flavor evaporation (SAFE) technique. Concentrated vanilla bean extracts were analyzed using GC-MS and GC-O. Two hundred and forty-six volatile compounds were identified using the Automated Mass Spectral Deconvolution and Identification System (AMDIS) software, of which 13 were confirmed with authentic compounds from commercial sources and the others were tentatively identified on the basis of calibrated linear retention indices and the comparison of deconvoluted mass spectra with the in-house and/or NIST spectra databases. Vanillin was the most abundant constituent followed by guaiacol. The total concentration of the volatile compounds, excluding vanillin, was 301 mg/kg for Bourbon and 398 mg/kg for Ugandan vanilla bean extracts. Analytical comparison between the two vanilla bean extracts was discussed. Seventy-eight compounds were identified as odor-active compounds in the vanilla bean extracts with 10 confirmed with authentic references. It was found that there were substantial analytical differences in the odor-active compounds of the two extracts.

Market microstructure matters when imposing a Tobin tax—Evidence from the lab☆

PubMed Central

Kirchler, Michael; Huber, Jürgen; Kleinlercher, Daniel

2011-01-01

Trading in FX markets is dominated by two microstructures: exchanges with market makers and OTC-markets without market makers. Using laboratory experiments we test whether the impact of a Tobin tax is different in these two market microstructures. We find that (i) in markets without market makers an unilaterally imposed Tobin tax (i.e. a tax haven exists) increases volatility. (ii) In contrast, in markets with market makers we observe a decrease in volatility in unilaterally taxed markets. (iii) An encompassing Tobin tax has no impact on volatility in either setting. Efficiency does not vary significantly across tax regimes. PMID:22210970

Gallium isotopic evidence for extensive volatile loss from the Moon during its formation

PubMed Central

Kato, Chizu; Moynier, Frédéric

2017-01-01

The distribution and isotopic composition of volatile elements in planetary materials holds a key to the characterization of the early solar system and the Moon’s formation. The Moon and Earth are chemically and isotopically very similar. However, the Moon is highly depleted in volatile elements and the origin of this depletion is still debated. We present gallium isotopic and elemental measurements in a large set of lunar samples to constrain the origin of this volatile depletion. We show that while Ga has a geochemical behavior different from zinc, both elements show a systematic enrichment in the heavier isotopes in lunar mare basalts and Mg-suite rocks compared to the silicate Earth, pointing to a global-scale depletion event. On the other hand, the ferroan anorthosites are isotopically heterogeneous, suggesting a secondary distribution of Ga at the surface of the Moon by volatilization and condensation. The isotopic difference of Ga between Earth and the Moon and the isotopic heterogeneity of the crustal ferroan anorthosites suggest that the volatile depletion occurred following the giant impact and during the lunar magma ocean phase. These results point toward a Moon that has lost its volatile elements during a whole-scale evaporation event and that is now relatively dry compared to Earth. PMID:28782027

Plant volatiles induced by herbivore egg deposition affect insects of different trophic levels.

PubMed

Fatouros, Nina E; Lucas-Barbosa, Dani; Weldegergis, Berhane T; Pashalidou, Foteini G; van Loon, Joop J A; Dicke, Marcel; Harvey, Jeffrey A; Gols, Rieta; Huigens, Martinus E

2012-01-01

Plants release volatiles induced by herbivore feeding that may affect the diversity and composition of plant-associated arthropod communities. However, the specificity and role of plant volatiles induced during the early phase of attack, i.e. egg deposition by herbivorous insects, and their consequences on insects of different trophic levels remain poorly explored. In olfactometer and wind tunnel set-ups, we investigated behavioural responses of a specialist cabbage butterfly (Pieris brassicae) and two of its parasitic wasps (Trichogramma brassicae and Cotesia glomerata) to volatiles of a wild crucifer (Brassica nigra) induced by oviposition of the specialist butterfly and an additional generalist moth (Mamestra brassicae). Gravid butterflies were repelled by volatiles from plants induced by cabbage white butterfly eggs, probably as a means of avoiding competition, whereas both parasitic wasp species were attracted. In contrast, volatiles from plants induced by eggs of the generalist moth did neither repel nor attract any of the tested community members. Analysis of the plant's volatile metabolomic profile by gas chromatography-mass spectrometry and the structure of the plant-egg interface by scanning electron microscopy confirmed that the plant responds differently to egg deposition by the two lepidopteran species. Our findings imply that prior to actual feeding damage, egg deposition can induce specific plant responses that significantly influence various members of higher trophic levels.

Volatiles from the xylarialean fungus Hypoxylon invadens.

PubMed

Dickschat, Jeroen S; Wang, Tao; Stadler, Marc

2018-01-01

The volatiles emitted by agar plate cultures of the xylarialean fungus Hypoxylon invadens were investigated by use of a closed loop stripping apparatus in combination with GC-MS. Several aromatic compounds were found that could only be identified by comparison to all possible constitutional isomers with different ring substitution patterns. For the set of identified compounds a plausible biosynthetic scheme was suggested that gives further support for the assigned structures.

Interlinking showy traits: co-engineering of scent and colour biosynthesis in flowers.

PubMed

Ben Zvi, Michal Moyal; Negre-Zakharov, Florence; Masci, Tania; Ovadis, Marianna; Shklarman, Elena; Ben-Meir, Hagit; Tzfira, Tzvi; Dudareva, Natalia; Vainstein, Alexander

2008-05-01

The phenylpropanoid pathway gives rise to metabolites that determine floral colour and fragrance. These metabolites are one of the main means used by plants to attract pollinators, thereby ensuring plant survival. A lack of knowledge about factors regulating scent production has prevented the successful enhancement of volatile phenylpropanoid production in flowers. In this study, the Production of Anthocyanin Pigment1 (Pap1) Myb transcription factor from Arabidopsis thaliana, known to regulate the production of non-volatile phenylpropanoids, including anthocyanins, was stably introduced into Petunia hybrida. In addition to an increase in pigmentation, Pap1-transgenic petunia flowers demonstrated an increase of up to tenfold in the production of volatile phenylpropanoid/benzenoid compounds. The dramatic increase in volatile production corresponded to the native nocturnal rhythms of volatile production in petunia. The application of phenylalanine to Pap1-transgenic flowers led to an increase in the otherwise negligible levels of volatiles emitted during the day to nocturnal levels. On the basis of gene expression profiling and the levels of pathway intermediates, it is proposed that both increased metabolic flux and transcriptional activation of scent and colour genes underlie the enhancement of petunia flower colour and scent production by Pap1. The co-ordinated regulation of metabolic steps within or between pathways involved in vital plant functions, as shown here for two showy traits determining plant-pollinator interactions, provides a clear advantage for plant survival. The use of a regulatory factor that activates scent production creates a new biotechnological strategy for the metabolic architecture of fragrance, leading to the creation of novel genetic variability for breeding purposes.

Feature selection and recognition from nonspecific volatile profiles for discrimination of apple juices according to variety and geographical origin.

PubMed

Guo, Jing; Yue, Tianli; Yuan, Yahong

2012-10-01

Apple juice is a complex mixture of volatile and nonvolatile components. To develop discrimination models on the basis of the volatile composition for an efficient classification of apple juices according to apple variety and geographical origin, chromatography volatile profiles of 50 apple juice samples belonging to 6 varieties and from 5 counties of Shaanxi (China) were obtained by headspace solid-phase microextraction coupled with gas chromatography. The volatile profiles were processed as continuous and nonspecific signals through multivariate analysis techniques. Different preprocessing methods were applied to raw chromatographic data. The blind chemometric analysis of the preprocessed chromatographic profiles was carried out. Stepwise linear discriminant analysis (SLDA) revealed satisfactory discriminations of apple juices according to variety and geographical origin, provided respectively 100% and 89.8% success rate in terms of prediction ability. Finally, the discriminant volatile compounds selected by SLDA were identified by gas chromatography-mass spectrometry. The proposed strategy was able to verify the variety and geographical origin of apple juices involving only a reduced number of discriminate retention times selected by the stepwise procedure. This result encourages the similar procedures to be considered in quality control of apple juices. This work presented a method for an efficient discrimination of apple juices according to apple variety and geographical origin using HS-SPME-GC-MS together with chemometric tools. Discrimination models developed could help to achieve greater control over the quality of the juice and to detect possible adulteration of the product. © 2012 Institute of Food Technologists®

Review of methods for determination of ammonia volatilization in farmland

NASA Astrophysics Data System (ADS)

Yang, J.; Jiao, Y.; Yang, W. Z.; Gu, P.; Bai, S. G.; Liu, L. J.

2018-02-01

Ammonia is one of the most abundant alkaline trace gases in the atmosphere, which is one of the important factors affecting atmospheric quality. Excessive application of nitrogen fertilizer is the main source of global ammonia emissions, which not only exacerbate greenhouse gas emissions, but also leads to eutrophication of water bodies. In this paper, the basic principle, the operation process, the advantages and disadvantages, and the previous research results of the method are summarized in detail, including the enclosure method, the venting method, the continuous airflow enclosure method, the wind tunnel method and the micro-meteorological method. So as to provide a theoretical basis for selecting the appropriate method for determination of ammonia volatilization.

Volatile organic compounds in a residential and commercial urban area with a diesel, compressed natural gas and oxygenated gasoline vehicular fleet.

PubMed

Martins, Eduardo Monteiro; Arbilla, Graciela; Gatti, Luciana Vanni

2010-02-01

Air samples were collected in a typical residential and commercial area in Rio de Janeiro, Brazil, where buses and trucks use diesel and light duty vehicles use compressed natural gas, ethanol, and gasohol (gasoline blended with ethanol) as fuel. A total of 66 C3-C12 volatile organic compounds (VOCs) were identified. The most abundant compounds, on a mass concentration basis, included propane, isobutane, i-pentane, m,p-xylene, 1,3,5-trimethylbenzene, toluene, styrene, ethylbenzene, isopropylbenzene, o-xylene and 1,2,4-trimethylbenzene. Two VOCs photochemical reactivity rankings are presented: one involves reaction with OH and the other involves production of ozone.

Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

NASA Astrophysics Data System (ADS)

Witte, Jonathon; Neaton, Jeffrey B.; Head-Gordon, Martin

2016-05-01

With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen's pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

Methodology to estimate particulate matter emissions from certified commercial aircraft engines.

PubMed

Wayson, Roger L; Fleming, Gregg G; Lovinelli, Ralph

2009-01-01

Today, about one-fourth of U.S. commercial service airports, including 41 of the busiest 50, are either in nonattainment or maintenance areas per the National Ambient Air Quality Standards. U.S. aviation activity is forecasted to triple by 2025, while at the same time, the U.S. Environmental Protection Agency (EPA) is evaluating stricter particulate matter (PM) standards on the basis of documented human health and welfare impacts. Stricter federal standards are expected to impede capacity and limit aviation growth if regulatory mandated emission reductions occur as for other non-aviation sources (i.e., automobiles, power plants, etc.). In addition, strong interest exists as to the role aviation emissions play in air quality and climate change issues. These reasons underpin the need to quantify and understand PM emissions from certified commercial aircraft engines, which has led to the need for a methodology to predict these emissions. Standardized sampling techniques to measure volatile and nonvolatile PM emissions from aircraft engines do not exist. As such, a first-order approximation (FOA) was derived to fill this need based on available information. FOA1.0 only allowed prediction of nonvolatile PM. FOA2.0 was a change to include volatile PM emissions on the basis of the ratio of nonvolatile to volatile emissions. Recent collaborative efforts by industry (manufacturers and airlines), research establishments, and regulators have begun to provide further insight into the estimation of the PM emissions. The resultant PM measurement datasets are being analyzed to refine sampling techniques and progress towards standardized PM measurements. These preliminary measurement datasets also support the continued refinement of the FOA methodology. FOA3.0 disaggregated the prediction techniques to allow for independent prediction of nonvolatile and volatile emissions on a more theoretical basis. The Committee for Aviation Environmental Protection of the International Civil Aviation Organization endorsed the use of FOA3.0 in February 2007. Further commitment was made to improve the FOA as new data become available, until such time the methodology is rendered obsolete by a fully validated database of PM emission indices for today's certified commercial fleet. This paper discusses related assumptions and derived equations for the FOA3.0 methodology used worldwide to estimate PM emissions from certified commercial aircraft engines within the vicinity of airports.

A strategic approach for the design and operation of two-phase partitioning bioscrubbers for the treatment of volatile organic compounds.

PubMed

Yeom, Sung Ho; Daugulis, Andrew J; Nielsen, David R

2010-01-01

A strategic approach for the design of two-phase partitioning bioscrubbers (TPPBs) has been formulated using, as a basis, a re-evaluation of extensive literature data available for the degradation of benzene by Achromobacter xylosoxidans Y234 in TPPBs with n-hexadecane as the partitioning phase. Using a previously determined maintenance coefficient for benzene, we determined that an inlet benzene loading rate of 100 mg/h requires 5,928 mg cell mass at biological steady state and 243.0 mg O(2) /h. The total oxygen-transfer rates (TOTRs) into the TPPB increased by 83.5% with 33.3% of organic phase compared with a single aqueous phase and were significantly influenced by gas flow rate, whereas agitation has a minor affect. The fraction of organic phase used was suggested to be the primary parameter with which the TOTR into the TPPB may be altered. Although the presence of an organic solvent in the TPPB remarkably increased the TOTR, the total benzene transfer rate into the TPPB remained largely insensitive due to the intrinsic low Henry's law constant (or relatively high solubility) of benzene in water. Finally, we have integrated the elements of this analysis into a set of heuristic criteria that can serve as a guideline for the design of TPPB systems for future volatile organic compound treatment applications. Copyright © 2010 American Institute of Chemical Engineers (AIChE).

Seasonal cycle of indoor-VOCs: comparison of apartments and cities

NASA Astrophysics Data System (ADS)

Schlink, U.; Rehwagen, M.; Damm, M.; Richter, M.; Borte, M.; Herbarth, O.

On the basis of 2103 measurements of volatile organic compounds (VOCs) in indoor air we study the intensity of a seasonal pattern. The data are representative for the German population and were gathered in different cities (Leipzig, München, Köln), in rooms of different type (children's, living, sleeping rooms, and other rooms), and in households of smokers and non-smokers. In addition to the randomly selected different apartments that were sampled each month, we repeatedly measured in a fixed set of 10 apartments. The analysis comprised concentrations of 30 VOCs belonging to the groups of alkanes, cycloalkanes, aromatics, volatile halogenated hydrocarbons, and terpenes. The annual cycle for total VOC concentrations was observed at every site. Seasonality proved to be the most dominant pattern, but it may be modified by further factors, such as the city, the considered VOC component, and the type of the considered room. Highest concentrations occurred during the winter months and amount to approximately three to four times the summer burden. As seasonality may bias the results of health effect studies we fit a seasonal model to our measurements and develop a procedure for seasonal adjustment, which enables to roughly estimate the annual peak concentration utilizing one monthly observation. The seasonal pattern proved to be a general feature of indoor VOC concentrations and, therefore, this adjustment procedure may be generally applicable. For Leipzig, München, and Köln we present site-specific adjustment factors for indoor concentrations of aromatics, terpenes, and alkanes.

Benthos and plankton community data for selected rivers and harbors along the western Lake Michigan shoreline, 2014

USGS Publications Warehouse

Scudder Eikenberry, Barbara C.; Burns, Daniel J.; Olds, Hayley T.; Bell, Amanda H.; Mapel, Kassidy T.

2016-06-15

Benthos (benthic invertebrates) and plankton (zooplankton and phytoplankton) communities were sampled in 2014 at 10 Wisconsin rivers and harbors, including 4 sites in Great Lakes Areas of Concern and 6 less degraded comparison sites with similar physical and chemical characteristics, including climate, latitude, geology, and land use. Previous U.S. Geological Survey sampling was completed in 2012, but because of ongoing sediment remediation at three of the Areas of Concern (AOCs) and unusually hot and dry conditions in many areas during 2012, additional sampling was added in 2014. Comparable sampling methods were used in 2012 and 2014. Benthos were collected by using Hester-Dendy artificial substrate samplers and composite Ponar grab samples of bottom sediment; zooplankton were collected by using tows from depth to the surface with a 63-micrometer mesh plankton net; phytoplankton were collected by using whole water samples composited from set depth intervals. This report describes the study areas and field sampling methods for 2014, and it presents data on taxonomic identification and abundance of benthos and plankton that can serve as a basis for evaluation of related Beneficial Use Impairments (BUIs) at the AOCs. Physical and chemical data were sampled concurrently (specific conductance, temperature, pH, dissolved oxygen, chlorophyll a, total and volatile suspended solids in water samples; particle size and volatile-on-ignition of sediment in benthic grab samples). The results of field quality assurance-quality control are also presented.

Development of a novel optical remote sensing monitor for fenceline monitoring and enhancement of existing leak detection and repair programs

EPA Science Inventory

Manual leak detection and repair (LDAR) programs are currently implemented on a regular basis at refinery sites to limit fugitive emissions of volatile organic compounds (VOC). However, LDAR surveys can be time-consuming and are not always cost-effective. Fence line monitoring of...

The Difficult Parent: An Educator's Guide to Handling Aggressive Behavior

ERIC Educational Resources Information Center

Jaksec, Charles M., III

2004-01-01

Parents are a vital source of support for our schools. School personnel interact with parents on a daily basis and fortunately, most of these interactions are pleasant and helpful, keeping students' needs in mind. Instances of parental aggression, however, do occur. Volatile or confrontational parents present many unique challenges for educators…

75 FR 57390 - Approval and Promulgation of Implementation Plans; Alabama: Volatile Organic Compounds

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-21

... Tropospheric ozone, commonly known as smog, occurs when VOCs and nitrogen oxides (NO X ) react in the... contribution to tropospheric ozone formation. EPA is approving revisions to the Alabama SIP submitted on March... the VOC definition on the basis that these compounds make a negligible contribution to tropospheric...

Tests Of Protective Coats For Carbon Steel

NASA Technical Reports Server (NTRS)

Macdowell, Louis G., III

1995-01-01

Report describes laboratory and field tests of candidate paints (primers, tie coats, and topcoats) for use in protecting carbon-steel structures against corrosion in seaside environment at Kennedy Space Center. Coating materials selected because of utility in preventing corrosion, also on basis of legal requirements, imposed in several urban areas, for reduction of volatile organic contents.

Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

DOE PAGES

Zheng, Y.; Unger, N.; Hodzic, A.; ...

2015-12-08

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO x = NO + NO 2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NO x-dependent SOA yields and aging parameterizations. Small differences aremore » found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NO x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO x can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NO x pathways, O 3 versus NO 3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

Vertical Profiles of Cloud Condensation Nuclei, Condensation Nuclei, Optical Aerosol, Aerosol Optical Properties, and Aerosol Volatility Measured from Balloons

NASA Technical Reports Server (NTRS)

Deshler, T.; Snider, J. R.; Vali, G.

1998-01-01

Under the support of this grant a balloon-borne gondola containing a variety of aerosol instruments was developed and flown from Laramie, Wyoming, (41 deg N, 105 deg W) and from Lauder, New Zealand (45 deg S, 170 deg E). The gondola includes instruments to measure the concentrations of condensation nuclei (CN), cloud condensation nuclei (CCN), optically detectable aerosol (OA.) (r greater than or equal to 0.15 - 2.0 microns), and optical scattering properties using a nephelometer (lambda = 530 microns). All instruments sampled from a common inlet which was heated to 40 C on ascent and to 160 C on descent. Flights with the CN counter, OA counter, and nephelometer began in July 1994. The CCN counter was added in November 1994, and the engineering problems were solved by June 1995. Since then the flights have included all four instruments, and were completed in January 1998. Altogether there were 20 flights from Laramie, approximately 5 per year, and 2 from Lauder. Of these there were one or more engineering problems on 6 of the flights from Laramie, hence the data are somewhat limited on those 6 flights, while a complete data set was obtained from the other 14 flights. Good CCN data are available from 12 of the Laramie flights. The two flights from Lauder in January 1998 were successful for all measurements. The results from these flights, and the development of the balloon-bome CCN counter have formed the basis for five conference presentations. The heated and unheated CN and OA measurements have been used to estimate the mass fraction of the aerosol volatile, while comparisons of the nephelometer measurements were used to estimate the light scattering, associated with the volatile aerosol. These estimates were calculated for 0.5 km averages of the ascent and descent data between 2.5 km and the tropopause, near 11.5 km.

Sensitivity of Aerosol Mass and Microphysics to varying treatments of Condensational Growth of Secondary Organic Compounds in a regional model

NASA Astrophysics Data System (ADS)

Lowe, Douglas; Topping, David; McFiggans, Gordon

2017-04-01

Gas to particle partitioning of atmospheric compounds occurs through disequilibrium mass transfer rather than through instantaneous equilibrium. However, it is common to treat only the inorganic compounds as partitioning dynamically whilst organic compounds, represented by the Volatility Basis Set (VBS), are partitioned instantaneously. In this study we implement a more realistic dynamic partitioning of organic compounds in a regional framework and assess impact on aerosol mass and microphysics. It is also common to assume condensed phase water is only associated with inorganic components. We thus also assess sensitivity to assuming all organics are hygroscopic according to their prescribed molecular weight. For this study we use WRF-Chem v3.4.1, focusing on anthropogenic dominated North-Western Europe. Gas-phase chemistry is represented using CBM-Z whilst aerosol dynamics are simulated using the 8-section MOSAIC scheme, including a 9-bin VBS treatment of organic aerosol. Results indicate that predicted mass loadings can vary significantly. Without gas phase ageing of higher volatility compounds, dynamic partitioning always results in lower mass loadings downwind of emission sources. The inclusion of condensed phase water in both partitioning models increases the predicted PM mass, resulting from a larger contribution from higher volatility organics, if present. If gas phase ageing of VBS compounds is allowed to occur in a dynamic model, this can often lead to higher predicted mass loadings, contrary to expected behaviour from a simple non-reactive gas phase box model. As descriptions of aerosol phase processes improve within regional models, the baseline descriptions of partitioning should retain the ability to treat dynamic partitioning of organics compounds. Using our simulations, we discuss whether derived sensitivities to aerosol processes in existing models may be inherently biased. This work was supported by the Natural Environment Research Council within the RONOCO (NE/F004656/1) and CCN-Vol (NE/L007827/1) projects.

Can volatile organic metabolites be used to simultaneously assess microbial and mite contamination level in cereal grains and coffee beans?

PubMed

Salvador, Angelo C; Baptista, Inês; Barros, António S; Gomes, Newton C M; Cunha, Angela; Almeida, Adelaide; Rocha, Silvia M

2013-01-01

A novel approach based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToFMS) was developed for the simultaneous screening of microbial and mite contamination level in cereals and coffee beans. The proposed approach emerges as a powerful tool for the rapid assessment of the microbial contamination level (ca. 70 min versus ca. 72 to 120 h for bacteria and fungi, respectively, using conventional plate counts), and mite contamination (ca. 70 min versus ca. 24 h). A full-factorial design was performed for optimization of the SPME experimental parameters. The methodology was applied to three types of rice (rough, brown, and white rice), oat, wheat, and green and roasted coffee beans. Simultaneously, microbiological analysis of the samples (total aerobic microorganisms, moulds, and yeasts) was performed by conventional plate counts. A set of 54 volatile markers was selected among all the compounds detected by GC×GC-ToFMS. Principal Component Analysis (PCA) was applied in order to establish a relationship between potential volatile markers and the level of microbial contamination. Methylbenzene, 3-octanone, 2-nonanone, 2-methyl-3-pentanol, 1-octen-3-ol, and 2-hexanone were associated to samples with higher microbial contamination level, especially in rough rice. Moreover, oat exhibited a high GC peak area of 2-hydroxy-6-methylbenzaldehyde, a sexual and alarm pheromone for adult mites, which in the other matrices appeared as a trace component. The number of mites detected in oat grains was correlated to the GC peak area of the pheromone. The HS-SPME/GC×GC-ToFMS methodology can be regarded as the basis for the development of a rapid and versatile method that can be applied in industry to the simultaneous assessment the level of microbiological contamination and for detection of mites in cereals grains and coffee beans.

Can Volatile Organic Metabolites Be Used to Simultaneously Assess Microbial and Mite Contamination Level in Cereal Grains and Coffee Beans?

PubMed Central

Salvador, Ângelo C.; Baptista, Inês; Barros, António S.; Gomes, Newton C. M.; Cunha, Ângela; Almeida, Adelaide; Rocha, Silvia M.

2013-01-01

A novel approach based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC×GC–ToFMS) was developed for the simultaneous screening of microbial and mite contamination level in cereals and coffee beans. The proposed approach emerges as a powerful tool for the rapid assessment of the microbial contamination level (ca. 70 min versus ca. 72 to 120 h for bacteria and fungi, respectively, using conventional plate counts), and mite contamination (ca. 70 min versus ca. 24 h). A full-factorial design was performed for optimization of the SPME experimental parameters. The methodology was applied to three types of rice (rough, brown, and white rice), oat, wheat, and green and roasted coffee beans. Simultaneously, microbiological analysis of the samples (total aerobic microorganisms, moulds, and yeasts) was performed by conventional plate counts. A set of 54 volatile markers was selected among all the compounds detected by GC×GC–ToFMS. Principal Component Analysis (PCA) was applied in order to establish a relationship between potential volatile markers and the level of microbial contamination. Methylbenzene, 3-octanone, 2-nonanone, 2-methyl-3-pentanol, 1-octen-3-ol, and 2-hexanone were associated to samples with higher microbial contamination level, especially in rough rice. Moreover, oat exhibited a high GC peak area of 2-hydroxy-6-methylbenzaldehyde, a sexual and alarm pheromone for adult mites, which in the other matrices appeared as a trace component. The number of mites detected in oat grains was correlated to the GC peak area of the pheromone. The HS-SPME/GC×GC–ToFMS methodology can be regarded as the basis for the development of a rapid and versatile method that can be applied in industry to the simultaneous assessment the level of microbiological contamination and for detection of mites in cereals grains and coffee beans. PMID:23613710

Mars atmospheric D/H - Consistent with polar volatile theory?

NASA Technical Reports Server (NTRS)

Jakosky, Bruce M.

1990-01-01

Current theories on the Martian water history are discussed on the basis of data for the D/H ratio in the Martian atmosphere (which was found to be enhanced by a factor of 6 + or - relative to the value on earth). In particular, the calculations of Yung et al. (1988), on the basis of their photochemical model, are found to be inconsistent with current theories for the evolution of the polar deposits on Mars. While the photochemical model predicts that about 95 percent of the Martian water has escaped over geologic time and the nonatmospheric reservoir is now only 02 m thick, the polar volatile theory suggest that polar deposits contain the equivalent of tens of meters of water, requiring a more rapid escape of H and D to space than predicted by the photochemical model to match the observed D/H ratio. The paper examines the behavior of the polar caps and the atmospheric water vapor over geologic time and the loss of H and D to space. It is concluded that, at present, it is premature to accept a specific history for water on Mars.

Difference in the volatile composition of pine-mushrooms (Tricholoma matsutake Sing.) according to their grades.

PubMed

Cho, In Hee; Choi, Hyung-Kyoon; Kim, Young-Suk

2006-06-28

The differences in volatile components of pine-mushrooms (Tricholoma matsutake Sing.) according to their grades were observed by applying multivariate statistical methods to GC-MS data sets. A total of 35 and 37 volatile components were identified in raw and cooked pine-mushrooms, respectively. The volatile components in pine-mushrooms were primarily composed of C8 species, such as 3-octanol, 1-octen-3-ol, 1-octanol, (E)-2-octen-1-ol, 3-octanone, 1-octen-3-one, (E)-2-octenal, and octanoic acid. The levels of ethyl octanoate, junipene, and 3-methyl-3-buten-2-one were much higher in raw pine-mushroom of higher grades, whereas the reverse was true for C8 components. On the other hand, furfuryl alcohol, benzyl alcohol, phenylethyl alcohol, dihydro-5-methyl-2(3H)-furanone, 2(5H)-furanone, (E)-2-methyl-2-butenal, furfural, phenylacetaldehyde, benzoic acid methyl ester, camphene, and beta-pinene were the major components of cooked mushrooms. These volatile components formed by various thermal reactions could be mainly responsible for the difference in volatile components of cooked pine-mushrooms according to their grades.

The impact of an urban-industrial region on the magnitude and variability of persistent organic pollutant deposition to Lake Michigan.

PubMed

Hornbuckle, Keri C; Green, Mark L

2003-09-01

A predictive model for gas-phase PCBs and trans-nonachlor over Lake Michigan has been constructed and the resulting data examined for trends. In this paper, we describe the model results to show how the magnitude and variability of a plume of contaminants from the Chicago area contributes to a highly variable region of net contaminant deposition over the entire lake. For the whole lake, gross annual deposition of PCBs is approximately 3200 kg, although the net annual gas exchange is not significantly different from zero. The data-driven model illustrates that on a daily basis, the net exchange of persistent organic pollutants (POPs) can change from net deposition to net volatilization depending on the area of plume impact. These findings suggest that i) control of urban areas can accelerate the rate of volatilization from lakes; and ii) release of POPs from urban areas is largely a result of volatilization processes.

Production of Substitute Natural Gas from Coal

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

Andrew Lucero

2009-01-31

The goal of this research program was to develop and demonstrate a novel gasification technology to produce substitute natural gas (SNG) from coal. The technology relies on a continuous sequential processing method that differs substantially from the historic methanation or hydro-gasification processing technologies. The thermo-chemistry relies on all the same reactions, but the processing sequences are different. The proposed concept is appropriate for western sub-bituminous coals, which tend to be composed of about half fixed carbon and about half volatile matter (dry ash-free basis). In the most general terms the process requires four steps (1) separating the fixed carbon frommore » the volatile matter (pyrolysis); (2) converting the volatile fraction into syngas (reforming); (3) reacting the syngas with heated carbon to make methane-rich fuel gas (methanation and hydro-gasification); and (4) generating process heat by combusting residual char (combustion). A key feature of this technology is that no oxygen plant is needed for char combustion.« less

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

Witte, Jonathon; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720; Neaton, Jeffrey B.

With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methodsmore » and systems examined, the most complete basis is Jensen’s pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.« less

Accuracy of Lagrange-sinc functions as a basis set for electronic structure calculations of atoms and molecules

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

Choi, Sunghwan; Hong, Kwangwoo; Kim, Jaewook

2015-03-07

We developed a self-consistent field program based on Kohn-Sham density functional theory using Lagrange-sinc functions as a basis set and examined its numerical accuracy for atoms and molecules through comparison with the results of Gaussian basis sets. The result of the Kohn-Sham inversion formula from the Lagrange-sinc basis set manifests that the pseudopotential method is essential for cost-effective calculations. The Lagrange-sinc basis set shows faster convergence of the kinetic and correlation energies of benzene as its size increases than the finite difference method does, though both share the same uniform grid. Using a scaling factor smaller than or equal tomore » 0.226 bohr and pseudopotentials with nonlinear core correction, its accuracy for the atomization energies of the G2-1 set is comparable to all-electron complete basis set limits (mean absolute deviation ≤1 kcal/mol). The same basis set also shows small mean absolute deviations in the ionization energies, electron affinities, and static polarizabilities of atoms in the G2-1 set. In particular, the Lagrange-sinc basis set shows high accuracy with rapid convergence in describing density or orbital changes by an external electric field. Moreover, the Lagrange-sinc basis set can readily improve its accuracy toward a complete basis set limit by simply decreasing the scaling factor regardless of systems.« less

Volatile Compound Profiling by HS-SPME/GC-MS-FID of a Core Olive Cultivar Collection as a Tool for Aroma Improvement of Virgin Olive Oil.

PubMed

García-Vico, Lourdes; Belaj, Angjelina; Sánchez-Ortiz, Araceli; Martínez-Rivas, José M; Pérez, Ana G; Sanz, Carlos

2017-01-14

Virgin olive oil (VOO) is the only food product requiring official sensory analysis to be classified in commercial categories, in which the evaluation of the aroma plays a very important role. The selection of parents, with the aim of obtaining new cultivars with improved oil aroma, is of paramount importance in olive breeding programs. We have assessed the volatile fraction by headspace-solid-phase microextraction/gas chromatography-mass spectrometry-flame ionization detection (HS-SPME/GC-MS-FID) and the deduced aroma properties of VOO from a core set of olive cultivars (Core-36) which possesses most of the genetic diversity found in the World Olive Germplasm Collection (IFAPA Alameda del Obispo) located in Cordoba, Spain. The VOO volatile fractions of Core-36 cultivars display a high level of variability. It is mostly made of compounds produced from polyunsaturated fatty acids through the lipoxygenase pathway, which confirms to be a general characteristic of the olive species ( Olea europaea L.). The main group of volatile compounds in the oils was six straight-chain carbon compounds derived from linolenic acid, some of them being the main contributors to the aroma of the olive oils according to their odor activity values (OAV). The high level of variability found for the volatile fraction of the oils from Core-36 and, therefore, for the aroma odor notes, suggest that this core set may be a very useful tool for the choice of optimal parents in olive breeding programs in order to raise new cultivars with improved VOO aroma.

Optimization of selected molecular orbitals in group basis sets.

PubMed

Ferenczy, György G; Adams, William H

2009-04-07

We derive a local basis equation which may be used to determine the orbitals of a group of electrons in a system when the orbitals of that group are represented by a group basis set, i.e., not the basis set one would normally use but a subset suited to a specific electronic group. The group orbitals determined by the local basis equation minimize the energy of a system when a group basis set is used and the orbitals of other groups are frozen. In contrast, under the constraint of a group basis set, the group orbitals satisfying the Huzinaga equation do not minimize the energy. In a test of the local basis equation on HCl, the group basis set included only 12 of the 21 functions in a basis set one might ordinarily use, but the calculated active orbital energies were within 0.001 hartree of the values obtained by solving the Hartree-Fock-Roothaan (HFR) equation using all 21 basis functions. The total energy found was just 0.003 hartree higher than the HFR value. The errors with the group basis set approximation to the Huzinaga equation were larger by over two orders of magnitude. Similar results were obtained for PCl(3) with the group basis approximation. Retaining more basis functions allows an even higher accuracy as shown by the perfect reproduction of the HFR energy of HCl with 16 out of 21 basis functions in the valence basis set. When the core basis set was also truncated then no additional error was introduced in the calculations performed for HCl with various basis sets. The same calculations with fixed core orbitals taken from isolated heavy atoms added a small error of about 10(-4) hartree. This offers a practical way to calculate wave functions with predetermined fixed core and reduced base valence orbitals at reduced computational costs. The local basis equation can also be used to combine the above approximations with the assignment of local basis sets to groups of localized valence molecular orbitals and to derive a priori localized orbitals. An appropriately chosen localization and basis set assignment allowed a reproduction of the energy of n-hexane with an error of 10(-5) hartree, while the energy difference between its two conformers was reproduced with a similar accuracy for several combinations of localizations and basis set assignments. These calculations include localized orbitals extending to 4-5 heavy atoms and thus they require to solve reduced dimension secular equations. The dimensions are not expected to increase with increasing system size and thus the local basis equation may find use in linear scaling electronic structure calculations.

Tricks, tips, and literature review on the adapted vaporize system to deliver volatile agents during cardiopulmonary bypass

PubMed Central

Nigro Neto, Caetano; De Simone, Francesco; Cassarà, Luigi; Dos Santos Silva, Carlos Gustavo; Maranhão Cardoso, Thiago Augusto Almeida; Carcò, Francesco; Zangrillo, Alberto; Landoni, Giovanni

2016-01-01

Background: Recently, evidence of cardio-protection and reduction in mortality due to the use of volatile agents during cardiac surgery led to an increase in their use during cardiopulmonary bypass (CPB). These findings seem to be enhanced when the volatile agents are used during all the surgical procedure, including the CPB period. Aims: Since the administration of volatile agents through CPB can be beneficial to the patients, we decided to review the use of volatile agents vaporized in the CPB circuit and to summarize some tricks and tips of this technique using our 10-year experience of Brazilian and Italian centers with a large volume of cardiac surgeries. Study Setting: Hospital. Methods: A literature review. Results: During the use of the volatile agents in CPB, it is very important to analyze all gases that come in and go out of the membrane oxygenators. The proper monitoring of inhaled and exhaled fraction of the gas allows not only monitoring of anesthesia level, but also the detection of possible leakage in the circuit. Any volatile agent in the membrane oxygenator is supposed to pollute the operating theater. This is the major reason why proper scavenging systems are always necessary when this technique is used. Conclusion: While waiting for industry upgrades, we recommend that volatile agents should be used during CPB only by skilled perfusionists and physicians with the aim to reduce postoperative morbidity and mortality. PMID:27052063

Which is the better forecasting model? A comparison between HAR-RV and multifractality volatility

NASA Astrophysics Data System (ADS)

Ma, Feng; Wei, Yu; Huang, Dengshi; Chen, Yixiang

2014-07-01

In this paper, by taking the 5-min high frequency data of the Shanghai Composite Index as example, we compare the forecasting performance of HAR-RV and Multifractal volatility, Realized volatility, Realized Bipower Variation and their corresponding short memory model with rolling windows forecasting method and the Model Confidence Set which is proved superior to SPA test. The empirical results show that, for six loss functions, HAR-RV outperforms other models. Moreover, to make the conclusions more precise and robust, we use the MCS test to compare the performance of their logarithms form models, and find that the HAR-log(RV) has a better performance in predicting future volatility. Furthermore, by comparing the two models of HAR-RV and HAR-log(RV), we conclude that, in terms of performance forecasting, the HAR-log(RV) model is the best model among models we have discussed in this paper.

Breath Tests in Respiratory and Critical Care Medicine: From Research to Practice in Current Perspectives

PubMed Central

Cheepsattayakorn, Attapon; Cheepsattayakorn, Ruangrong

2013-01-01

Today, exhaled nitric oxide has been studied the most, and most researches have now focusd on asthma. More than a thousand different volatile organic compounds have been observed in low concentrations in normal human breath. Alkanes and methylalkanes, the majority of breath volatile organic compounds, have been increasingly used by physicians as a novel method to diagnose many diseases without discomforts of invasive procedures. None of the individual exhaled volatile organic compound alone is specific for disease. Exhaled breath analysis techniques may be available to diagnose and monitor the diseases in home setting when their sensitivity and specificity are improved in the future. PMID:24151617

Accurate Methods for Large Molecular Systems (Preprint)

DTIC Science & Technology

2009-01-06

tensor, EFP calculations are basis set dependent. The smallest recommended basis set is 6- 31++G( d , p )52 The dependence of the computational cost of...and second order perturbation theory (MP2) levels with the 6-31G( d , p ) basis set. Additional SFM tests are presented for a small set of alpha...helices using the 6-31++G( d , p ) basis set. The larger 6-311++G(3df,2p) basis set is employed for creating all EFPs used for non- bonded interactions, since

EqualChance: Addressing Intra-set Write Variation to Increase Lifetime of Non-volatile Caches

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

Mittal, Sparsh; Vetter, Jeffrey S

To address the limitations of SRAM such as high-leakage and low-density, researchers have explored use of non-volatile memory (NVM) devices, such as ReRAM (resistive RAM) and STT-RAM (spin transfer torque RAM) for designing on-chip caches. A crucial limitation of NVMs, however, is that their write endurance is low and the large intra-set write variation introduced by existing cache management policies may further exacerbate this problem, thereby reducing the cache lifetime significantly. We present EqualChance, a technique to increase cache lifetime by reducing intra-set write variation. EqualChance works by periodically changing the physical cache-block location of a write-intensive data item withinmore » a set to achieve wear-leveling. Simulations using workloads from SPEC CPU2006 suite and HPC (high-performance computing) field show that EqualChance improves the cache lifetime by 4.29X. Also, its implementation overhead is small, and it incurs very small performance and energy loss.« less

Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: the case of LiH.

PubMed

Usvyat, Denis; Civalleri, Bartolomeo; Maschio, Lorenzo; Dovesi, Roberto; Pisani, Cesare; Schütz, Martin

2011-06-07

The atomic orbital basis set limit is approached in periodic correlated calculations for solid LiH. The valence correlation energy is evaluated at the level of the local periodic second order Møller-Plesset perturbation theory (MP2), using basis sets of progressively increasing size, and also employing "bond"-centered basis functions in addition to the standard atom-centered ones. Extended basis sets, which contain linear dependencies, are processed only at the MP2 stage via a dual basis set scheme. The local approximation (domain) error has been consistently eliminated by expanding the orbital excitation domains. As a final result, it is demonstrated that the complete basis set limit can be reached for both HF and local MP2 periodic calculations, and a general scheme is outlined for the definition of high-quality atomic-orbital basis sets for solids. © 2011 American Institute of Physics

An expanded calibration study of the explicitly correlated CCSD(T)-F12b method using large basis set standard CCSD(T) atomization energies.

PubMed

Feller, David; Peterson, Kirk A

2013-08-28

The effectiveness of the recently developed, explicitly correlated coupled cluster method CCSD(T)-F12b is examined in terms of its ability to reproduce atomization energies derived from complete basis set extrapolations of standard CCSD(T). Most of the standard method findings were obtained with aug-cc-pV7Z or aug-cc-pV8Z basis sets. For a few homonuclear diatomic molecules it was possible to push the basis set to the aug-cc-pV9Z level. F12b calculations were performed with the cc-pVnZ-F12 (n = D, T, Q) basis set sequence and were also extrapolated to the basis set limit using a Schwenke-style, parameterized formula. A systematic bias was observed in the F12b method with the (VTZ-F12/VQZ-F12) basis set combination. This bias resulted in the underestimation of reference values associated with small molecules (valence correlation energies <0.5 E(h)) and an even larger overestimation of atomization energies for bigger systems. Consequently, caution should be exercised in the use of F12b for high accuracy studies. Root mean square and mean absolute deviation error metrics for this basis set combination were comparable to complete basis set values obtained with standard CCSD(T) and the aug-cc-pVDZ through aug-cc-pVQZ basis set sequence. However, the mean signed deviation was an order of magnitude larger. Problems partially due to basis set superposition error were identified with second row compounds which resulted in a weak performance for the smaller VDZ-F12/VTZ-F12 combination of basis sets.

Plant Volatiles Induced by Herbivore Egg Deposition Affect Insects of Different Trophic Levels

PubMed Central

Fatouros, Nina E.; Lucas-Barbosa, Dani; Weldegergis, Berhane T.; Pashalidou, Foteini G.; van Loon, Joop J. A.; Dicke, Marcel; Harvey, Jeffrey A.; Gols, Rieta; Huigens, Martinus E.

2012-01-01

Plants release volatiles induced by herbivore feeding that may affect the diversity and composition of plant-associated arthropod communities. However, the specificity and role of plant volatiles induced during the early phase of attack, i.e. egg deposition by herbivorous insects, and their consequences on insects of different trophic levels remain poorly explored. In olfactometer and wind tunnel set-ups, we investigated behavioural responses of a specialist cabbage butterfly (Pieris brassicae) and two of its parasitic wasps (Trichogramma brassicae and Cotesia glomerata) to volatiles of a wild crucifer (Brassica nigra) induced by oviposition of the specialist butterfly and an additional generalist moth (Mamestra brassicae). Gravid butterflies were repelled by volatiles from plants induced by cabbage white butterfly eggs, probably as a means of avoiding competition, whereas both parasitic wasp species were attracted. In contrast, volatiles from plants induced by eggs of the generalist moth did neither repel nor attract any of the tested community members. Analysis of the plant’s volatile metabolomic profile by gas chromatography-mass spectrometry and the structure of the plant-egg interface by scanning electron microscopy confirmed that the plant responds differently to egg deposition by the two lepidopteran species. Our findings imply that prior to actual feeding damage, egg deposition can induce specific plant responses that significantly influence various members of higher trophic levels. PMID:22912893

Development of a self-contained device for rapid detection of volatile impurities in the oil system of a turbine

NASA Astrophysics Data System (ADS)

Starostin, A. A.; Shangin, V. V.; Bukhman, V. G.; Volosnikov, D. V.; Skripov, P. V.

2016-08-01

The research is devoted to development of a self-contained device for rapid detection of volatile impurities in the oil system of a turbine and testing it using the operating equipment. The device consists of a remote sensor, whose sensitive element is a 3-5-mm long wire probe 20 microns in diameter, and a measurement unit that comprises a microcontroller with a set of peripherals. The design of the device enables automation of the measurement procedure with a minimum number of preset settings and real-time output of information to the operator console. The software of the device provides two-stage pulse heating of the wire probe and a resistance temperature detector. The two-stage mode proves to be the most sensitive to appearance in the system of moisture, including its trace amounts. The characteristic time of the heating is of the order of 10 ms. The measurement procedure is based on a method that consists in automatic search for spontaneous boiling-up temperature of the oil accompanied by a characteristic response signal. The results were interpreted by formal correlation of the measured values with an array of calibration data obtained in similar experiments with well-defined oil samples. An experimental method for application of the device has been developed that takes into account technological factors, such as comparatively high values of the flow rate and the temperature of the oil in locations of the oil drain from bearings, the variability of these values, and the variety of noise types that accompany the operation of the thermal power equipment that complicate the online measurements. Tests of the device were carried out in locations of oil drain from supporting bearings. The test results have demonstrated the possibility of applying the device directly in the oil system of a turbine and provided a practical basis for development of a system of multipoint control of the technological scheme in real time.

Spectromicroscopic insights for rational design of redox-based memristive devices

PubMed Central

Baeumer, Christoph; Schmitz, Christoph; Ramadan, Amr H. H.; Du, Hongchu; Skaja, Katharina; Feyer, Vitaliy; Müller, Philipp; Arndt, Benedikt; Jia, Chun-Lin; Mayer, Joachim; De Souza, Roger A.; Michael Schneider, Claus; Waser, Rainer; Dittmann, Regina

2015-01-01

The demand for highly scalable, low-power devices for data storage and logic operations is strongly stimulating research into resistive switching as a novel concept for future non-volatile memory devices. To meet technological requirements, it is imperative to have a set of material design rules based on fundamental material physics, but deriving such rules is proving challenging. Here, we elucidate both switching mechanism and failure mechanism in the valence-change model material SrTiO3, and on this basis we derive a design rule for failure-resistant devices. Spectromicroscopy reveals that the resistance change during device operation and failure is indeed caused by nanoscale oxygen migration resulting in localized valence changes between Ti4+ and Ti3+. While fast reoxidation typically results in retention failure in SrTiO3, local phase separation within the switching filament stabilizes the retention. Mimicking this phase separation by intentionally introducing retention-stabilization layers with slow oxygen transport improves retention times considerably. PMID:26477940

Return volatility interval analysis of stock indexes during a financial crash

NASA Astrophysics Data System (ADS)

Li, Wei-Shen; Liaw, Sy-Sang

2015-09-01

We investigate the interval between return volatilities above a certain threshold q for 10 countries data sets during the 2008/2009 global financial crisis, and divide these data into several stages according to stock price tendencies: plunging stage (stage 1), fluctuating or rebounding stage (stage 2) and soaring stage (stage 3). For different thresholds q, the cumulative distribution function always satisfies a power law tail distribution. We find the absolute value of the power-law exponent is lowest in stage 1 for various types of markets, and increases monotonically from stage 1 to stage 3 in emerging markets. The fractal dimension properties of the return volatility interval series provide some surprising results. We find that developed markets have strong persistence and transform to weaker correlation in the plunging and soaring stages. In contrast, emerging markets fail to exhibit such a transformation, but rather show a constant-correlation behavior with the recurrence of extreme return volatility in corresponding stages during a crash. We believe this long-memory property found in recurrence-interval series, especially for developed markets, plays an important role in volatility clustering.

Triticale crisp bread enriched with selected bioactive additives: volatile profile, physical characteristics, sensory and nutritional properties.

PubMed

Makowska, Agnieszka; Majcher, Małgorzata; Mildner-Szkudlarz, Sylwia; Jedrusek-Golinska, Anna; Przygoński, Krzysztof

2017-09-01

The effect of selected plant additives (couch grass, artichoke, kale, nettle, ground buckwheat husks, broad beans, fenugreek seeds, and extracts of yellow tea and mulberry leaf) on the volatile compounds, color, texture, sensory attributes, polyphenols, and antioxidant properties of triticale crisp bread was studied. The volatile profile of control bread was dominated by lipid oxidation products with hexanal and (E)-2-nonenal predominant. The additives strongly modified the volatile profile of the extruded crisp bread. The greatest differences were recorded in the case of products with artichoke and kale additions, which had respectively about 12 and 8 times higher levels of total volatile compounds than the control crisp bread. The samples containing kale, buckwheat, and fenugreek as well as yellow tea extract characterized high levels of sulfur compounds, with methanethiol predominant. The additives, especially kale, nettle, and artichoke affected the color of the crisp breads, in most cases making them darker. In terms of texture only the crisp bread with addition of buckwheat husk was significantly harder than the control sample. On the basis of sensory evaluation it was stated that among all the additives, the artichoke and fenugreek resulted in dramatic deterioration in the extruded product taste. The used additives also affected the antioxidant properties of triticale crisp bread. The greatest content of total phenolic compounds and the highest antioxidant activity were observed for the bread with yellow tea extract addition (3.5- and 6.5-fold higher, respectively, than in control sample).

Learning the Hard Way: The Poor Environment of America's Schools.

ERIC Educational Resources Information Center

Wakefield, Julie

2002-01-01

This article asserts that a significant number of schoolchildren and teachers in the United States are exposed on an almost daily basis to environmental hazards including volatile organic chemicals, airborne lead and asbestos, and noise pollution while they are at school. Some school hazards are linked to the aging of many of the nation's schools,…

77 FR 37610 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of trans-1,3,3,3...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-22

... through atmospheric photochemical reactions. Different VOCs have different levels of reactivity--that is...: (i) The reaction rate constant (known as k OH ) with the hydroxyl radical (OH); (ii) the maximum... per mole basis. Differences between these three metrics are discussed below. The k OH is the reaction...

78 FR 21653 - Self-Regulatory Organizations; NASDAQ OMX BX, Inc.; Order Approving, on an Accelerated Basis...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-11

... time period before suddenly reversing to prices consistent with their pre-decline levels.\\5\\ This... implemented through a series of rule filings by the equity exchanges and by FINRA.\\6\\ The single-stock circuit breaker was designed to reduce extraordinary market volatility in NMS stocks by imposing a five-minute...

Modeling the formation and aging of secondary organic aerosols during CalNex 2010

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ortega, A. M.; Ahmadov, R.; McKeen, S. A.; Washenfelder, R. A.; Alvarez, S.; Rappenglueck, B.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Zotter, P.; Prevot, A. S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

2012-12-01

Several traditional and recently proposed models are applied to predict the concentrations and properties of secondary organic aerosols (SOA) and organic gases at the Pasadena ground site during the CalNex campaign. The models are constrained with and compared against results from available observations. The CalNex campaign and specifically the Pasadena ground site featured a large and sophisticated suite of aerosol and gas phase instrumentation, and thus, it provides a unique opportunity to test SOA models under conditions of strong urban emissions at a range of low photochemical ages. The oxidation of volatile organic compounds (VOCs) using an updated traditional model cannot explain the observed ambient SOA, and under-predicts the measurements by a factor of ~40. Similarly, after accounting for the multi-generation oxidation of VOCs using a volatility basis set (VBS) approach as described by Tsimpidi et al. (2010), SOA is still under-predicted by a factor of ~8. For SOA formed from VOCs (V-SOA) the dominant precursors are aromatics (xylenes, toluene, and trimethylbenzenes). The model SOA formed from the oxidation of primary semivolatile and intermediate volatility organic compounds (P-S/IVOCs, producing SI-SOA) is also predicted using the parameterizations of Robinson et al. (2007) and Grieshop et al. (2009), and the properties of V-SOA + SI-SOA are compared against the measured O:C and volatility. We also compare the results of the different models against fossil/non-fossil carbon measurements as well as tracers of different SOA precursors. Potential Aerosol Mass (PAM) measurements of the SOA forming potential of the Pasadena air masses are also compared against that predicted by the models. The PAM analysis allows for model/measurement comparisons of SOA properties over a range of photochemical ages spanning almost two weeks. Using the V-SOA model, at low photochemical ages (< 1 day) the modeled PAM V-SOA is less than the measured PAM SOA, similar to the ambient results. In contrast, at high photochemical ages (i.e., more than about three days) the modeled PAM V-SOA is substantially greater than that measured, which is likely due fragmentation reactions that are not included in that model. We derive a parameterization of the measured PAM SOA as a function of the input photochemical age and the PAM photochemical age that serves as a comparison with other SOA models.

Estimation of the Age and Amount of Brown Rice Plant Hoppers Based on Bionic Electronic Nose Use

PubMed Central

Xu, Sai; Zhou, Zhiyan; Lu, Huazhong; Luo, Xiwen; Lan, Yubin; Zhang, Yang; Li, Yanfang

2014-01-01

The brown rice plant hopper (BRPH), Nilaparvata lugens (Stal), is one of the most important insect pests affecting rice and causes serious damage to the yield and quality of rice plants in Asia. This study used bionic electronic nose technology to sample BRPH volatiles, which vary in age and amount. Principal component analysis (PCA), linear discrimination analysis (LDA), probabilistic neural network (PNN), BP neural network (BPNN) and loading analysis (Loadings) techniques were used to analyze the sampling data. The results indicate that the PCA and LDA classification ability is poor, but the LDA classification displays superior performance relative to PCA. When a PNN was used to evaluate the BRPH age and amount, the classification rates of the training set were 100% and 96.67%, respectively, and the classification rates of the test set were 90.67% and 64.67%, respectively. When BPNN was used for the evaluation of the BRPH age and amount, the classification accuracies of the training set were 100% and 48.93%, respectively, and the classification accuracies of the test set were 96.67% and 47.33%, respectively. Loadings for BRPH volatiles indicate that the main elements of BRPHs' volatiles are sulfur-containing organics, aromatics, sulfur- and chlorine-containing organics and nitrogen oxides, which provide a reference for sensors chosen when exploited in specialized BRPH identification devices. This research proves the feasibility and broad application prospects of bionic electronic noses for BRPH recognition. PMID:25268913

Optimized auxiliary basis sets for density fitted post-Hartree-Fock calculations of lanthanide containing molecules

NASA Astrophysics Data System (ADS)

Chmela, Jiří; Harding, Michael E.

2018-06-01

Optimised auxiliary basis sets for lanthanide atoms (Ce to Lu) for four basis sets of the Karlsruhe error-balanced segmented contracted def2 - series (SVP, TZVP, TZVPP and QZVPP) are reported. These auxiliary basis sets enable the use of the resolution-of-the-identity (RI) approximation in post Hartree-Fock methods - as for example, second-order perturbation theory (MP2) and coupled cluster (CC) theory. The auxiliary basis sets are tested on an enlarged set of about a hundred molecules where the test criterion is the size of the RI error in MP2 calculations. Our tests also show that the same auxiliary basis sets can be used together with different effective core potentials. With these auxiliary basis set calculations of MP2 and CC quality can now be performed efficiently on medium-sized molecules containing lanthanides.

New constraints on subduction inputs and volatile outputs along the Aleutian Arc

NASA Astrophysics Data System (ADS)

Lopez, T. M.; Fischer, T. P.; Plank, T. A.; Rizzo, A. L.; Rasmussen, D. J.; Cottrell, E.; Werner, C. A.; Kern, C.; Ilanko, T.; Buff, L.; Andrys, J.; Kelley, K. A.

2017-12-01

Volatile cycling drives volcanism in subduction zone settings. At arcs, volatiles can originate from the subducted slab, mantle wedge and/or crust. Each region has characteristic isotopic signatures, which can be used to fingerprint volatile provenance. We speculate that differences in subduction parameters, such as convergence angle, plate coupling and subducted sediment fluxes, may lead to differences in volatile provenance, which may in turn influence volcanic eruption style and frequency. Here we combine updated constraints on subduction inputs and volatile outputs to provide new insights into volatile cycling within the Aleutian Arc. The high proportion of organic carbon (80-100% to total carbon) in sediments subducting at the Aleutian trench stands out globally and predicts a light carbon isotopic composition of recycled volcanic fluids. We assess volatile outputs on volcanic timescales and along the arc by combining carbon (C), nitrogen (N) and helium (He) isotopic compositions of volcanic gases and new analyses of He and, where possible, C isotopes in olivine-hosted fluid inclusions. From our preliminary isotopic analyses of volcanic gases, we find a greater proportion of mantle-derived volatiles released from the Western segment of the Aleutian Arc (>40% mantle) compared with other volcanic arcs around the world (<30% mantle), where volatiles are sourced primarily from subducted or upper crustal carbonates. This trend may be due to the oblique convergence and low subducted sediment input in this region. The Aleutian Arc also exhibits among the lightest carbon isotope ratios of arcs worldwide (δ13C = -10 to -15‰), especially in the central part of the arc, where organic-bearing terrigneous sediment fills the trench and the convergence rate is high. New constraints on subduction inputs and outputs presented here will help discriminate between upper crustal and subducted carbon sources, and provide further insights into volatile cycling and subduction processes within the Aleutian Arc.

Mapping fault-controlled volatile migration in equatorial layered deposits on Mars

NASA Astrophysics Data System (ADS)

Okubo, C. H.

2006-12-01

Research in terrestrial settings shows that clastic sedimentary deposits are productive host rocks for underground volatile reservoirs because of their high porosity and permeability. Within such reservoirs, faults play an important role in controlling pathways for volatile migration, because faults act as either barriers or conduits. Therefore faults are important volatile concentrators, which means that evidence of geochemical, hydrologic and biologic processes are commonly concentrated at these locations. Accordingly, faulted sedimentary deposits on Mars are plausible areas to search for evidence of past volatile activity and associated processes. Indeed, evidence for volatile migration through layered sedimentary deposits on Mars has been documented in detail by the Opportunity rover in Meridiani Planum. Thus evidence for past volatile- driven processes that could have occurred within the protective depths of these deposits may now exposed at the surface and more likely found around faults. Owing to the extensive distribution of layered deposits on Mars, a major challenge in looking for and investigating evidence of past volatile processes in these deposits is identifying and prioritizing study areas. Toward this end, this presentation details initial results of a multiyear project to develop quantitative maps of latent pathways for fault-controlled volatile migration through the layered sedimentary deposits on Mars. Available MOC and THEMIS imagery are used to map fault traces within equatorial layered deposits, with an emphasis on proposed regions for MSL landing sites. These fault maps define regions of interest for stereo imaging by HiRISE and identify areas to search for existing MOC stereo coverage. Stereo coverage of identified areas of interest allows for the construction of digital elevation models and ultimately extraction of fault plane and displacement vector orientations. These fault and displacement data will be fed through numerical modeling techniques that are developed for exploring terrestrial geologic reservoirs. This will yield maps of latent pathways for volatile migration through the faulted layered deposits and provide insight into the geologic history of volatiles on Mars.

Nonvolatile, semivolatile, or volatile: redefining volatile for volatile organic compounds.

PubMed

Võ, Uyên-Uyén T; Morris, Michael P

2014-06-01

Although widely used in air quality regulatory frameworks, the term "volatile organic compound" (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and US. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products. The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.

Mechanisms involved in cardiac sensitization by volatile anesthetics: general applicability to halogenated hydrocarbons?

PubMed

Himmel, Herbert M

2008-01-01

An increased sensitivity of the heart to catecholamines or cardiac sensitization is a recognized risk during acute human exposure to halogenated hydrocarbons used as solvents, foam-blowing or fire-extinguishing agents, refrigerants, and aerosol propellants. Although cardiac sensitization to such "industrial" halocarbons can result in serious arrhythmia and death, research into its mechanistic basis has been limited, whereas the literature on volatile anesthetics (e.g., halothane, chloroform) is comparably extensive. A review of the literature on halocarbons and related volatile anesthetics was conducted. The available experimental evidence suggests that volatile anesthetics at physiologically relevant concentrations interact predominantly with the main repolarizing cardiac potassium channels hERG and I(Ks), as well as with calcium and sodium channels at slightly higher concentrations. On the level of the heart, inhibition of these ion channels is prone to alter both action potential shape (triangulation) and electrical impulse conduction, which may facilitate arrhythmogenesis by volatile anesthetics per se and is potentiated by catecholamines. Action potential triangulation by regionally heterogeneous inhibition of calcium and potassium channels will facilitate catecholamine-induced afterdepolarizations, triggered activity, and enhanced automaticity. Inhibition of cardiac sodium channels will reduce conduction velocity and alter refractory period; this is potentiated by catecholamines and promotes reentry arrhythmias. Other cardiac and/or neuronal mechanisms might also contribute to arrhythmogenesis. The few scattered in vitro data available for halocarbons (e.g., FC-12, halon 1301, trichloroethylene) suggest inhibition of cardiac sodium (conduction), calcium and potassium channels (triangulation), extraneuronal catecholamine reuptake, and various neuronal ion channels. Therefore, it is hypothesized that halocarbons promote cardiac sensitization by similar mechanisms as volatile anesthetics. Experimental approaches for further investigation of these sensitization mechanisms by selected halocarbons are suggested.

Evaluation of the separation characteristics of application-specific (volatile organic compounds) open-tubular columns for gas chromatography.

PubMed

Poole, Colin F; Qian, Jing; Kiridena, Waruna; Dekay, Colleen; Koziol, Wladyslaw W

2006-11-17

The solvation parameter model is used to characterize the separation characteristics of two application-specific open-tubular columns (Rtx-Volatiles and Rtx-VGC) and a general purpose column for the separation of volatile organic compounds (DB-WAXetr) at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and retention factor correlation plots are then used to determine selectivity differences between the above columns and their closest neighbors in a large database of system constants and retention factors for forty-four open-tubular columns. The Rtx-Volatiles column is shown to have separation characteristics predicted for a poly(dimethyldiphenylsiloxane) stationary phase containing about 16% diphenylsiloxane monomer. The Rtx-VGC column has separation properties similar to the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 14% cyanopropylphenylsiloxane monomer DB-1701 for non-polar and dipolar/polarizable compounds but significantly different characteristics for the separation of hydrogen-bond acids. For all practical purposes the DB-WAXetr column is shown to be selectivity equivalent to poly(ethylene glycol) columns prepared using different chemistries for bonding and immobilizing the stationary phase. Principal component analysis and cluster analysis are then used to classify the system constants for the above columns and a sub-database of eleven open-tubular columns (DB-1, HP-5, DB-VRX, Rtx-20, DB-35, Rtx-50, Rtx-65, DB-1301, DB-1701, DB-200, and DB-624) commonly used for the separation of volatile organic compounds. A rationale basis for column selection based on differences in intermolecular interactions is presented as an aid to method development for the separation of volatile organic compounds.

Electroantennogram Responses to Plant Volatiles Associated with Fenvalerate Resistance in the Diamondback Moth, Plutella xylostella (Lepidoptera: Plutellidae).

PubMed

Houjun, Tian; Lin, Shuo; Chen, Yong; Chen, Yixin; Zhao, Jianwei; Gu, Xiaojun; Wei, Hui

2018-05-28

The diamondback moth (DBM), Plutella xylostella (L.) (Lepidoptera: Plutellidae), is the main destructive insect pest of brassica vegetables around the world, and has developed resistance to numerous insecticides. Although host plant volatiles are important in pest control, the mechanism of low-level insecticide resistance in P. xylostella due to plant volatiles has not been examined. Here, electroantennograms (EAGs) were used to compare the responses of adult male and female DBMs of a susceptible strain (S-strain) and a derived resistant strain, Fen-R-strain (6.52-fold more resistant than the S-strain), to different concentrations of nine plant volatiles. We found significantly different relative EAG responses between S-strain and Fen-R-strain males to different concentrations of methyl jasmonate, methyl salicylate, and octanal. The relative EAG responses of S-strain and Fen-R-strain females to different concentrations of β-myrcene, methyl jasmonate, methyl salicylate, and allyl isothiocyanate were significantly different. Fen-R-strain females showed lower EAG responses to most of the tested plant volatiles (at concentrations of 1:10) than males, except for allyl isothiocyanate. A larger difference in relative EAG response to α-farnesene and β-myrcene was found between S-strain and Fen-R-strain females than between males of the two strains. A larger difference in relative EAG response to octanal, nonanal, and octan-1-ol was found between S-strain and Fen-R-strain males than between females of the two strains. These results illustrate the relationship between the function of plant volatiles and resistance in an insect pest species, and provide a scientific basis for resistance evolutionary theory in pest management research.

Response of predatory mites to a herbivore-induced plant volatile: genetic variation for context-dependent behaviour.

PubMed

Sznajder, Beata; Sabelis, Maurice W; Egas, Martijn

2010-07-01

Plants infested with herbivores release specific volatile compounds that are known to recruit natural enemies. The response of natural enemies to these volatiles may be either learned or genetically determined. We asked whether there is genetic variation in the response of the predatory mite Phytoseiulus persimilis to methyl salicylate (MeSa). MeSa is a volatile compound consistently produced by plants being attacked by the two-spotted spider mite, the prey of P. persimilis. We predicted that predators express genetically determined responses during long-distance migration where previously learned associations may have less value. Additionally, we asked whether these responses depend on odors from uninfested plants as a background to MeSa. To infer a genetic basis, we analyzed the variation in response to MeSa among iso-female lines of P. persimilis by using choice-tests that involved either (1) MeSa presented as a single compound or (2) MeSa with background-odor from uninfested lima bean plants. These tests were conducted for starved and satiated predators, i.e., two physiological states, one that approximates migration and another that mimics local patch exploration. We found variation among iso-female lines in the responses to MeSa, thus showing genetic variation for this behavior. The variation was more pronounced in the starved predators, thus indicating that P. persimilis relies on innate preferences when migrating. Background volatiles of uninfested plants changed the predators' responses to MeSa in a manner that depended on physiological state and iso-female line. Thus, it is possible to select for context-dependent behavioral responses of natural enemies to plant volatiles.

Response of Predatory Mites to a Herbivore-Induced Plant Volatile: Genetic Variation for Context-Dependent Behaviour

PubMed Central

Sabelis, Maurice W.; Egas, Martijn

2010-01-01

Plants infested with herbivores release specific volatile compounds that are known to recruit natural enemies. The response of natural enemies to these volatiles may be either learned or genetically determined. We asked whether there is genetic variation in the response of the predatory mite Phytoseiulus persimilis to methyl salicylate (MeSa). MeSa is a volatile compound consistently produced by plants being attacked by the two-spotted spider mite, the prey of P. persimilis. We predicted that predators express genetically determined responses during long-distance migration where previously learned associations may have less value. Additionally, we asked whether these responses depend on odors from uninfested plants as a background to MeSa. To infer a genetic basis, we analyzed the variation in response to MeSa among iso-female lines of P. persimilis by using choice-tests that involved either (1) MeSa presented as a single compound or (2) MeSa with background-odor from uninfested lima bean plants. These tests were conducted for starved and satiated predators, i.e., two physiological states, one that approximates migration and another that mimics local patch exploration. We found variation among iso-female lines in the responses to MeSa, thus showing genetic variation for this behavior. The variation was more pronounced in the starved predators, thus indicating that P. persimilis relies on innate preferences when migrating. Background volatiles of uninfested plants changed the predators’ responses to MeSa in a manner that depended on physiological state and iso-female line. Thus, it is possible to select for context-dependent behavioral responses of natural enemies to plant volatiles. PMID:20574785

Quantification of the volatile organic compounds in the smoke from prescribed burning and comparison with the occupational exposure limits

NASA Astrophysics Data System (ADS)

Barboni, T.; Santoni, P.-A.

2013-11-01

Prescribed burning represents a serious threat to the personnel fighting fires because of smoke inhalation. This study aims to increase the knowledge about foresters exposure to the prescribed burning smoke by focusing on exposure to volatile organic compounds (VOCs). We initially assessed the methodology for smoke sampling. Then, we identified potentially dangerous molecules among the VOCs identified at 4 prescribed burning sites located around Corsica. The values measured were very high, exceeding the exposure limits, particularly for benzene, phenol, and furfural, whose concentrations were above short-term exposure limit (STEL) values. In conclusion, obvious but necessary recommendations were made for the protection of the personnel involved in fighting fires on a professional basis.

From Secure Memories to Smart Card Security

NASA Astrophysics Data System (ADS)

Handschuh, Helena; Trichina, Elena

Non-volatile memory is essential in most embedded security applications. It will store the key and other sensitive materials for cryptographic and security applications. In this chapter, first an overview is given of current flash memory architectures. Next the standard security features which form the basis of so-called secure memories are described in more detail. Smart cards are a typical embedded application that is very vulnerable to attacks and that at the same time has a high need for secure non-volatile memory. In the next part of this chapter, the secure memories of so-called flash-based high-density smart cards are described. It is followed by a detailed analysis of what the new security challenges for such objects are.

Ab Initio Density Fitting: Accuracy Assessment of Auxiliary Basis Sets from Cholesky Decompositions.

PubMed

Boström, Jonas; Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland

2009-06-09

The accuracy of auxiliary basis sets derived by Cholesky decompositions of the electron repulsion integrals is assessed in a series of benchmarks on total ground state energies and dipole moments of a large test set of molecules. The test set includes molecules composed of atoms from the first three rows of the periodic table as well as transition metals. The accuracy of the auxiliary basis sets are tested for the 6-31G**, correlation consistent, and atomic natural orbital basis sets at the Hartree-Fock, density functional theory, and second-order Møller-Plesset levels of theory. By decreasing the decomposition threshold, a hierarchy of auxiliary basis sets is obtained with accuracies ranging from that of standard auxiliary basis sets to that of conventional integral treatments.

Scaling and long-range dependence in option pricing V: Multiscaling hedging and implied volatility smiles under the fractional Black-Scholes model with transaction costs

NASA Astrophysics Data System (ADS)

Wang, Xiao-Tian

2011-05-01

This paper deals with the problem of discrete time option pricing using the fractional Black-Scholes model with transaction costs. Through the ‘anchoring and adjustment’ argument in a discrete time setting, a European call option pricing formula is obtained. The minimal price of an option under transaction costs is obtained. In addition, the relation between scaling and implied volatility smiles is discussed.

Characterization of Volatiles in Rambutan Fruit (Nephelium lappaceum L.).

PubMed

Ong; Acree; Lavin

1998-02-16

The volatile compounds from the red-skinned cultivar of rambutan, Jitlee (Nephelium lappaceumL.), a tropical fruit native to Southeast Asia, were extracted using both Freon 113 and ethyl acetate solvents. Isolation and characterization of odor-active compounds present in the fruit were mediated by gas chromatography/olfactory (GC/O), chromatography, and spectrometry. Authentic standards were used to determine mass spectral, retention index, and odor match. Of over 100 volatiles detected by GC/MS, twice as many polar volatiles were detected in the ethyl acetate extract as in the nonpolar Freon extract. GC/O analysis also detected more odor-active compounds in the polar extracts. Over 60 compounds in the extracts had some odor activity. The 20 most potent odorants included beta-damascenone, (E)-4,5-epoxy-(E)-2-decenal, vanillin, (E)-2-nonenal, phenylacetic acid, cinnamic acid, unknown 1 (sweaty), ethyl 2-methylbutyrate, and delta-decalactone. On the basis of calculated odor activity values, beta-damascenone, ethyl 2-methylbutyrate, 2,6-nonadienal, (E)-2-nonenal, and nonanal were determined to be the main contributors to the fruit aroma. Taken together, these results indicate that the exotic aroma character of rambutan is the interaction of fruity-sweet and fatty-green odors, with the possible contribution of "civet-like"-sweaty, spicy, and woody notes.

Volatile Biomarkers in Breath Associated With Liver Cirrhosis — Comparisons of Pre- and Post-liver Transplant Breath Samples

PubMed Central

Fernández del Río, R.; O'Hara, M.E.; Holt, A.; Pemberton, P.; Shah, T.; Whitehouse, T.; Mayhew, C.A.

2015-01-01

Background The burden of liver disease in the UK has risen dramatically and there is a need for improved diagnostics. Aims To determine which breath volatiles are associated with the cirrhotic liver and hence diagnostically useful. Methods A two-stage biomarker discovery procedure was used. Alveolar breath samples of 31 patients with cirrhosis and 30 healthy controls were mass spectrometrically analysed and compared (stage 1). 12 of these patients had their breath analysed after liver transplant (stage 2). Five patients were followed longitudinally as in-patients in the post-transplant period. Results Seven volatiles were elevated in the breath of patients versus controls. Of these, five showed statistically significant decrease post-transplant: limonene, methanol, 2-pentanone, 2-butanone and carbon disulfide. On an individual basis limonene has the best diagnostic capability (the area under a receiver operating characteristic curve (AUROC) is 0.91), but this is improved by combining methanol, 2-pentanone and limonene (AUROC curve 0.95). Following transplant, limonene shows wash-out characteristics. Conclusions Limonene, methanol and 2-pentanone are breath markers for a cirrhotic liver. This study raises the potential to investigate these volatiles as markers for early-stage liver disease. By monitoring the wash-out of limonene following transplant, graft liver function can be non-invasively assessed. PMID:26501124

Use of the Endophytic Fungus Daldinia cf. concentrica and Its Volatiles as Bio-Control Agents

PubMed Central

Liarzi, Orna; Bar, Einat; Lewinsohn, Efraim; Ezra, David

2016-01-01

Endophytic fungi are organisms that spend most of their life cycle within plant tissues without causing any visible damage to the host plant. Many endophytes were found to secrete specialized metabolites and/or emit volatile organic compounds (VOCs), which may be biologically active and assist fungal survival inside the plant as well as benefit their hosts. We report on the isolation and characterization of a VOCs-emitting endophytic fungus, isolated from an olive tree (Olea europaea L.) growing in Israel; the isolate was identified as Daldinia cf. concentrica. We found that the emitted VOCs were active against various fungi from diverse phyla. Results from postharvest experiments demonstrated that D. cf. concentrica prevented development of molds on organic dried fruits, and eliminated Aspergillus niger infection in peanuts. Gas chromatography–mass spectrometry analysis of the volatiles led to identification of 27 VOCs. On the basis of these VOCs we prepared two mixtures that displayed a broad spectrum of antifungal activity. In postharvest experiments these mixtures prevented development of molds on wheat grains, and fully eliminated A. niger infection in peanuts. In light of these findings, we suggest use of D. cf. concentrica and/or its volatiles as an alternative approach to controlling phytopathogenic fungi in the food industry and in agriculture. PMID:27977739

Volatile profile analysis and quality prediction of Longjing tea (Camellia sinensis) by HS-SPME/GC-MS

PubMed Central

Lin, Jie; Dai, Yi; Guo, Ya-nan; Xu, Hai-rong; Wang, Xiao-chang

2012-01-01

This study aimed to analyze the volatile chemical profile of Longjing tea, and further develop a prediction model for aroma quality of Longjing tea based on potent odorants. A total of 21 Longjing samples were analyzed by headspace solid phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Pearson’s linear correlation analysis and partial least square (PLS) regression were applied to investigate the relationship between sensory aroma scores and the volatile compounds. Results showed that 60 volatile compounds could be commonly detected in this famous green tea. Terpenes and esters were two major groups characterized, representing 33.89% and 15.53% of the total peak area respectively. Ten compounds were determined to contribute significantly to the perceived aroma quality of Longjing tea, especially linalool (0.701), nonanal (0.738), (Z)-3-hexenyl hexanoate (−0.785), and β-ionone (−0.763). On the basis of these 10 compounds, a model (correlation coefficient of 89.4% and cross-validated correlation coefficient of 80.4%) was constructed to predict the aroma quality of Longjing tea. Summarily, this study has provided a novel option for quality prediction of green tea based on HS-SPME/GC-MS technique. PMID:23225852

GC-MS analyses of the volatiles of Houttuynia cordata Thunb.

PubMed

Yang, Zhan-Nan; Luo, Shi-Qiong; Ma, Jing; Wu, Dan; Hong, Liang; Yu, Zheng-Wen

2016-09-01

GC-MS is the basis of analysis of plant volatiles. Several protocols employed for the assay have resulted in inconsistent results in the literature. We developed a GC-MS method, which were applied to analyze 25 volatiles (α-pinene, camphene, β-pinene, 2-methyl-2-pentenal, myrcene, (+)-limonene, eucalyptol, trans-2-hexenal, γ-terpinene, cis-3-hexeneyl-acetate, 1-hexanol, α-pinene oxide, cis-3-hexen-1-ol, trans-2-hexen-1-ol, decanal, linalool, acetyl-borneol, β-caryophyllene, 2-undecanone, 4-terpineol, borneol, decanol, eugenol, isophytol and phytol) of Houttuynia cordata Thunb. Linear behaviors for all analytes were observed with a linear regression relationship (r2>0.9991) at the concentrations tested. Recoveries of the 25 analytes were 98.56-103.77% with RSDs <3.0%. Solution extraction (SE), which involved addition of an internal standard, could avoid errors for factors in sample preparation by steam distillation (SD) and solidphase micro extraction (SPME). Less sample material (≍0.05g fresh leaves of H. cordata) could be used to determine the contents of 25 analytes by our proposed method and, after collection, did not affect the normal physiological activity or growth of H. cordata. This method can be used to monitor the metabolic accumulation of H. cordata volatiles.

Volatile compounds in cryptic species of the Aneura pinguis complex and Aneura maxima (Marchantiophyta, Metzgeriidae).

PubMed

Wawrzyniak, Rafał; Wasiak, Wiesław; Bączkiewicz, Alina; Buczkowska, Katarzyna

2014-09-01

Aneura pinguis is one of the liverwort species complexes that consist of several cryptic species. Ten samples collected from different regions in Poland are in the focus of our research. Eight of the A. pinguis complex belonging to four cryptic species (A, B, C, E) and two samples of closely related species Aneura maxima were tested for the composition of volatile compounds. The HS-SPME technique coupled to GC/FID and GC/MS analysis has been applied. The fiber coated with DVB/CAR/PDMS has been used. The results of the present study, revealed the qualitative and quantitative differences in the composition of the volatile compounds between the studied species. Mainly they are from the group of sesquiterpenoids, oxygenated sesquiterpenoids and aliphatic hydrocarbons. The statistical methods (CA and PCA) showed that detected volatile compounds allow to distinguish cryptic species of A. pinguis. All examined cryptic species of the A. pinguis complex differ from A. maxima. Species A and E of A. pinguis, in CA and PCA, form separate clusters remote from two remaining cryptic species of A. pinguis (B and C) and A. maxima. Relationship between the cryptic species appeared from the chemical studies are in accordance with that revealed on the basis of DNA sequences. Copyright © 2014 Elsevier Ltd. All rights reserved.

Volatile elements - water, carbon, nitrogen, noble gases - on Earth

NASA Astrophysics Data System (ADS)

Marty, B.

2017-12-01

Understanding the origin and evolution of life-bearing volatile elements (water, carbon, nitrogen) on Earth is a fruitful and debated area of research. In his pioneering work, W.W. Rubey inferred that the terrestrial atmosphere and the oceans formed from degassing of the mantle through geological periods of time. Early works on noble gas isotopes were consistent with this view and proposed a catastrophic event of mantle degassing early in Earth's history. We now have evidence, mainly from noble gas isotopes, that several cosmochemical sources contributed water and other volatiles at different stages of Earth's accretion. Potential contributors include the protosolar nebula gas that equilibrated with magma oceans, inner solar system bodies now represented by chondrites, and comets. Stable isotope ratios suggest volatiles where primarily sourced by planetary bodies from the inner solar system. However, recent measurements by the European Space Agency Rosetta probe on the coma of Comet 67P/Churyumov-Gerasimenko permit to set quantitative constraints on the cometary contribution to the surface of our planet. The surface and mantle reservoirs volatile elements exchanged volatile elements through time, with rates that are still uncertain. Some mantle regions remained isolated from whole mantle convection within the first tens to hundreds million years after start of solar system formation. These regions, now sampled by some mantle plumes (e.g., Iceland, Eifel) preserved their volatile load, as indicated by extinct and extant radioactivity systems. The abundance of volatile elements in the mantle is still not well known. Different approaches, such as high pressure experimental petrology, noble gas geochemistry, modelling, resulted in somewhat contrasted estimates, varying over one order of magnitude for water. Comparative planetology, that is, the study of volatiles on the Moon, Venus, Mars, Vesta, will shed light on the sources and strengths of these elements in the inner solar system.

Authentication of vegetable oils on the basis of their physico-chemical properties with the aid of chemometrics.

PubMed

Zhang, Guowen; Ni, Yongnian; Churchill, Jane; Kokot, Serge

2006-09-15

In food production, reliable analytical methods for confirmation of purity or degree of spoilage are required by growers, food quality assessors, processors, and consumers. Seven parameters of physico-chemical properties, such as acid number, colority, density, refractive index, moisture and volatility, saponification value and peroxide value, were measured for quality and adulterated soybean, as well as quality and rancid rapeseed oils. Chemometrics methods were then applied for qualitative and quantitative discrimination and prediction of the oils by methods such exploratory principal component analysis (PCA), partial least squares (PLS), radial basis function-artificial neural networks (RBF-ANN), and multi-criteria decision making methods (MCDM), PROMETHEE and GAIA. In general, the soybean and rapeseed oils were discriminated by PCA, and the two spoilt oils behaved differently with the rancid rapeseed samples exhibiting more object scatter on the PC-scores plot, than the adulterated soybean oil. For the PLS and RBF-ANN prediction methods, suitable training models were devised, which were able to predict satisfactorily the category of the four different oil samples in the verification set. Rank ordering with the use of MCDM models indicated that the oil types can be discriminated on the PROMETHEE II scale. For the first time, it was demonstrated how ranking of oil objects with the use of PROMETHEE and GAIA could be utilized as a versatile indicator of quality performance of products on the basis of a standard selected by the stakeholder. In principle, this approach provides a very flexible method for assessment of product quality directly from the measured data.

Inhibitory effects of sevoflurane on pacemaking activity of sinoatrial node cells in guinea-pig heart

PubMed Central

Kojima, Akiko; Kitagawa, Hirotoshi; Omatsu-Kanbe, Mariko; Matsuura, Hiroshi; Nosaka, Shuichi

2012-01-01

BACKGROUND AND PURPOSE The volatile anaesthetic sevoflurane affects heart rate in clinical settings. The present study investigated the effect of sevoflurane on sinoatrial (SA) node automaticity and its underlying ionic mechanisms. EXPERIMENTAL APPROACH Spontaneous action potentials and four ionic currents fundamental for pacemaking, namely, the hyperpolarization-activated cation current (If), T-type and L-type Ca2+ currents (ICa,T and ICa,L, respectively), and slowly activating delayed rectifier K+ current (IKs), were recorded in isolated guinea-pig SA node cells using perforated and conventional whole-cell patch-clamp techniques. Heart rate in guinea-pigs was recorded ex vivo in Langendorff mode and in vivo during sevoflurane inhalation. KEY RESULTS In isolated SA node cells, sevoflurane (0.12–0.71 mM) reduced the firing rate of spontaneous action potentials and its electrical basis, diastolic depolarization rate, in a qualitatively similar concentration-dependent manner. Sevoflurane (0.44 mM) reduced spontaneous firing rate by approximately 25% and decreased If, ICa,T, ICa,L and IKs by 14.4, 31.3, 30.3 and 37.1%, respectively, without significantly affecting voltage dependence of current activation. The negative chronotropic effect of sevoflurane was partly reproduced by a computer simulation of SA node cell electrophysiology. Sevoflurane reduced heart rate in Langendorff-perfused hearts, but not in vivo during sevoflurane inhalation in guinea-pigs. CONCLUSIONS AND IMPLICATIONS Sevoflurane at clinically relevant concentrations slowed diastolic depolarization and thereby reduced pacemaking activity in SA node cells, at least partly due to its inhibitory effect on If, ICa,T and ICa,L. These findings provide an important electrophysiological basis of alterations in heart rate during sevoflurane anaesthesia in clinical settings. PMID:22356456

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

Rossi, Tuomas P., E-mail: tuomas.rossi@alumni.aalto.fi; Sakko, Arto; Puska, Martti J.

We present an approach for generating local numerical basis sets of improving accuracy for first-principles nanoplasmonics simulations within time-dependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semi-core d-electrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussian-type orbitals generated by the completeness-optimization scheme, which is applied to the photoabsorption spectra of homoatomic metal atom dimers. We obtain basis sets of improving accuracy up to the complete basis set limit and demonstrate thatmore » the performance of the basis sets transfers to simulations of larger nanoparticles and nanoalloys as well as to calculations with various exchange-correlation functionals. This work promotes the use of the local basis set approach of controllable accuracy in first-principles nanoplasmonics simulations and beyond.« less

Estimates of the organic aerosol volatility in a boreal forest using two independent methods

NASA Astrophysics Data System (ADS)

Hong, Juan; Äijälä, Mikko; Häme, Silja A. K.; Hao, Liqing; Duplissy, Jonathan; Heikkinen, Liine M.; Nie, Wei; Mikkilä, Jyri; Kulmala, Markku; Prisle, Nønne L.; Virtanen, Annele; Ehn, Mikael; Paasonen, Pauli; Worsnop, Douglas R.; Riipinen, Ilona; Petäjä, Tuukka; Kerminen, Veli-Matti

2017-03-01

The volatility distribution of secondary organic aerosols that formed and had undergone aging - i.e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase - was characterized in a boreal forest environment of Hyytiälä, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40 % of the organics in particles were semi-volatile, 34 % were low-volatility organics and 26 % were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (ΔHVAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol-1 were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m/z 43 (f43) and m/z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when ΔHVAP = 80 kJ mol-1 was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16 % (R2) of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.

Ammonia volatilization from crop residues and frozen green manure crops

NASA Astrophysics Data System (ADS)

de Ruijter, F. J.; Huijsmans, J. F. M.; Rutgers, B.

2010-09-01

Agricultural systems can lose substantial amounts of nitrogen (N). To protect the environment, the European Union (EU) has adopted several directives that set goals to limit N losses. National Emission Ceilings (NEC) are prescribed in the NEC directive for nitrogen oxides and ammonia. Crop residues may contribute to ammonia volatilization, but sufficient information on their contribution to the national ammonia volatilization is lacking. Experiments were carried out with the aim to assess the ammonia volatilization of crop residues left on the soil surface or incorporated into the soil under the conditions met in practice in the Netherlands during late autumn and winter. Ammonia emission from residues of broccoli, leek, sugar beet, cut grass, fodder radish (fresh and frozen) and yellow mustard (frozen) was studied during two winter seasons using volatilization chambers. Residues were either placed on top of soil or mixed with soil. Mixing residues with soil gave insignificant ammonia volatilization, whereas volatilization was 5-16 percent of the N content of residues when placed on top of soil. Ammonia volatilization started after at least 4 days. Total ammonia volatilization was related to C/N-ratio and N concentration of the plant material. After 37 days, cumulative ammonia volatilization was negligible from plant material with N concentration below 2 percent, and was 10 percent of the N content of plant material with 4 percent N. These observations can be explained by decomposition of plant material by micro-organisms. After an initial built up of the microbial population, NH 4+ that is not needed for their own growth is released and can easily emit as NH 3 at the soil surface. The results of the experiments were used to estimate the contribution of crop residues to ammonia volatilization in the Netherlands. Crop residues of arable crops and residues of pasture topping may contribute more than 3 million kg NH 3-N to the national ammonia volatilization of the Netherlands, being more than 3 percent of the national emissions in 2005. This contribution should therefore be considered when focusing on the national ceilings for ammonia emissions.

Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

NASA Astrophysics Data System (ADS)

Witte, Jonathon; Neaton, Jeffrey B.; Head-Gordon, Martin

2017-06-01

With the aim of mitigating the basis set error in density functional theory (DFT) calculations employing local basis sets, we herein develop two empirical corrections for basis set superposition error (BSSE) in the def2-SVPD basis, a basis which—when stripped of BSSE—is capable of providing near-complete-basis DFT results for non-covalent interactions. Specifically, we adapt the existing pairwise geometrical counterpoise (gCP) approach to the def2-SVPD basis, and we develop a beyond-pairwise approach, DFT-C, which we parameterize across a small set of intermolecular interactions. Both gCP and DFT-C are evaluated against the traditional Boys-Bernardi counterpoise correction across a set of 3402 non-covalent binding energies and isomerization energies. We find that the DFT-C method represents a significant improvement over gCP, particularly for non-covalently-interacting molecular clusters. Moreover, DFT-C is transferable among density functionals and can be combined with existing functionals—such as B97M-V—to recover large-basis results at a fraction of the cost.

78 FR 11101 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of trans

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-15

... form of encryption and be free of any defects or viruses. For additional information about the EPA's... radical (OH); (ii) the maximum incremental reactivity (MIR) on a reactivity per unit mass basis; and (iii... discussed below. The k OH is the reaction rate constant of the compound with the OH radical in the air. This...

78 FR 11583 - Approval and Promulgation of Implementation Plans Tennessee: Revisions to Volatile Organic...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-19

... exclusion list for VOC on the basis that they have a negligible effect on tropospheric ozone formation. Tropospheric ozone, commonly known as smog, occurs when VOC and nitrogen oxide (NO X ) react in the atmosphere. Because of the harmful health effects of ozone, EPA limits the amount of VOC and NO X that can be released...

Org Areo Boreal Forest Sources, compositions and properties of newly formed and regional organic aerosol in a boreal forest during the Biogenic Aerosol: Effects on Clouds and Climate Campaign

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

Thornton, Joel A

The major goals of this project were to make unique measurements, as part of the DOE sponsored Biogenic Aerosol Effects on Clouds and Climate (BAECC) campaign, of the volatility and molecular composition of organic aerosol, as well as gas-phase concentrations of oxygenated organic compounds that interact and affect organic aerosol. In addition, we aimed to conduct a similar set of measurements as part of a collaborative set of environmental simulation chamber experiments at PNNL, the aim of which was to simulate the atmospheric oxidation of key biogenic volatile organic compounds (BVOC) and study the associated formation and evolution of secondarymore » organic aerosol (SOA). The target BVOC were a set of monoterpenes, isoprene, and related intermediates such as IEPOX. The ultimate goal of such measurements are to develop a more detailed mechanistic understanding of the sensitivity of SOA mass formation and lifetime to precursor and environmental conditions. Molecular composition and direct volatility measurements provide robust tracers of chemical processing and properties. As such, meeting these goals will allow for stronger constraints on the types of processes and their fundamental descriptions needed to simulate aerosol particle number and size, and cloud nucleating ability in regional and global earth system models.« less

[Effects of sulphur compounds on the volatile characteristics of heavy metals in fly ash from the MSW and sewage sludge co-combustion plant during the disposal process with higher temperature].

PubMed

Liu, Jing-Yong; Sun, Shui-Yu

2012-11-01

Fly ash sample was collected from a MSW co-combustion with sewage sludge plant and the volatilization of heavy metals Pb, Cd, Cu and Zn was investigated before and after the water washing of fly ash, meanwhile, the influence of adding different sulphur compounds (S, NaS, Na2 SO3, Na2 SO4) on the volatilization of heavy metals was studied. The results showed that the contents of Zn, Pb and Mn were high, the Ni content was low and the Cd content reached 29.4 mg x kg(1). The contents of Pb, Cu, Zn increased, while that of Cd reduced in the fly ash after water washing. TG-DTG curves of fly ash showed highest weight loss in ranges of 579-732 degrees C and 949-1 200 degrees C, with 690 degrees C and 1 154 degrees C as the inflection point temperatures. The volatilization of different heavy metals showed great difference in the volatilization rate, following the order of Pb > Cd > Zn > Cu, in which the volatilization rate of Pb was more than 80% and that of Cu was less than 30%. After water washing, the volatilization of different heavy metals showed great difference in the volatilization rate, with the order of Zn > Pb > Cd > Cu, in which the volatilization rate of Zn was more than 20%. With the pretreatment of adding Na2 SO3 and Na2 SO4, the evaporation rates of heavy metals (Cu, Pb, Zn, Cd) were significantly decreased. After adding S, the evaporation rate of Zn was reduced, whereas the addition of Na2S reduced the evaporation rates of Cd and Zn. The evaporation rates of the four heavy metals were all reduced after adding Na2S in the washed fly ash. The evaporation rates of Cu and Zn were reduced with addition of S and Na2SO3 and the evaporation rate of Cd was reduced by adding the four sulfides. The results can provide a basis for the harmless disposal and maximized resource utilization and recycling of fly ash.

Intermediate Volatility Organic Compound Emissions from On-Road Diesel Vehicles: Chemical Composition, Emission Factors, and Estimated Secondary Organic Aerosol Production.

PubMed

Zhao, Yunliang; Nguyen, Ngoc T; Presto, Albert A; Hennigan, Christopher J; May, Andrew A; Robinson, Allen L

2015-10-06

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.

Volatile constituents of roasted tigernut oil (Cyperus esculentus L.).

PubMed

Lasekan, Ola

2013-03-30

Volatile compounds play a key role in determining the sensory appreciation of vegetable oils. In this study a systematic evaluation of odorants responsible for the characteristic flavour of roasted tigernut oil was carried out. A total of 75 odour-active volatiles were identified. From these, 13 aroma compounds showing high flavour dilution factors in the range of 16 to 128 were quantified by their odour activity values (OAVs). On the basis of high OAVs in oil, the following aroma compounds [vanillin (chocolate, sweet vanilla), 5-ethylfurfural (caramel, spicy), 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (caramel), phenyl acetaldehyde (honey-like), ethanone, 1-(4-hydroxy-3-methoxyphenyl) (faint vanilla)] were elucidated as important contributors to the overall chocolate, sweet vanilla, butterscotch aroma of the oil. Odorants with high concentrations in the roasted tigernut oil such as 5-hydroxymethylfurfural, ethyl hexadecanoate, n-propyl-9,12-octadecadienoate gave relatively low OAVs, so their contributions to the overall orthonasal aroma impression of roasted tigernut oil can be assumed to be low. © 2012 Society of Chemical Industry.

Quantum Dynamics with Short-Time Trajectories and Minimal Adaptive Basis Sets.

PubMed

Saller, Maximilian A C; Habershon, Scott

2017-07-11

Methods for solving the time-dependent Schrödinger equation via basis set expansion of the wave function can generally be categorized as having either static (time-independent) or dynamic (time-dependent) basis functions. We have recently introduced an alternative simulation approach which represents a middle road between these two extremes, employing dynamic (classical-like) trajectories to create a static basis set of Gaussian wavepackets in regions of phase-space relevant to future propagation of the wave function [J. Chem. Theory Comput., 11, 8 (2015)]. Here, we propose and test a modification of our methodology which aims to reduce the size of basis sets generated in our original scheme. In particular, we employ short-time classical trajectories to continuously generate new basis functions for short-time quantum propagation of the wave function; to avoid the continued growth of the basis set describing the time-dependent wave function, we employ Matching Pursuit to periodically minimize the number of basis functions required to accurately describe the wave function. Overall, this approach generates a basis set which is adapted to evolution of the wave function while also being as small as possible. In applications to challenging benchmark problems, namely a 4-dimensional model of photoexcited pyrazine and three different double-well tunnelling problems, we find that our new scheme enables accurate wave function propagation with basis sets which are around an order-of-magnitude smaller than our original trajectory-guided basis set methodology, highlighting the benefits of adaptive strategies for wave function propagation.

Polarization functions for the modified m6-31G basis sets for atoms Ga through Kr.

PubMed

Mitin, Alexander V

2013-09-05

The 2df polarization functions for the modified m6-31G basis sets of the third-row atoms Ga through Kr (Int J Quantum Chem, 2007, 107, 3028; Int J. Quantum Chem, 2009, 109, 1158) are proposed. The performances of the m6-31G, m6-31G(d,p), and m6-31G(2df,p) basis sets were examined in molecular calculations carried out by the density functional theory (DFT) method with B3LYP hybrid functional, Møller-Plesset perturbation theory of the second order (MP2), quadratic configuration interaction method with single and double substitutions and were compared with those for the known 6-31G basis sets as well as with the other similar 641 and 6-311G basis sets with and without polarization functions. Obtained results have shown that the performances of the m6-31G, m6-31G(d,p), and m6-31G(2df,p) basis sets are better in comparison with the performances of the known 6-31G, 6-31G(d,p) and 6-31G(2df,p) basis sets. These improvements are mainly reached due to better approximations of different electrons belonging to the different atomic shells in the modified basis sets. Applicability of the modified basis sets in thermochemical calculations is also discussed. © 2013 Wiley Periodicals, Inc.

The Quench Control of Water Estimates in Convergent Margin Magmas

NASA Astrophysics Data System (ADS)

Gavrilenko, M.; Krawczynski, M.; Ruprecht, P.

2017-12-01

Mineral-hosted glassy melt inclusions (MIs) have been used to quantify magma volatile contents for several decades. Despite the growing number of volatile studies utilizing MIs, it has not been tested whether there is a physical limit on how much dissolved volatiles a glassy MI can contain. We explored the limits of MIs as hydrous magma recorders in an experimental study, showing that there is a limit of dissolved H2O that glassy MIs cannot exceed. These results show there is potential bias in the glassy MI data set; they can only faithfully record pre-eruptive H2O contents in the upper-most part of the Earth's crust where H2O-solubility is low. The current MI database cannot be used to robustly estimate the full range of arc magmas and therefore assess volatile budgets in primitive or evolved compositions. Such magmas may contain much larger amounts of H2O than currently recognized and the diversity of magma evolutionary pathways in subduction zones is likely being significantly underappreciated.

Characterization and geographical discrimination of commercial Citrus spp. honeys produced in different Mediterranean countries based on minerals, volatile compounds and physicochemical parameters, using chemometrics.

PubMed

Karabagias, Ioannis K; Louppis, Artemis P; Karabournioti, Sofia; Kontakos, Stavros; Papastephanou, Chara; Kontominas, Michael G

2017-02-15

The objective of the present study was: i) to characterize Mediterranean citrus honeys based on conventional physicochemical parameter values, volatile compounds, and mineral content ii) to investigate the potential of above parameters to differentiate citrus honeys according to geographical origin using chemometrics. Thus, 37 citrus honey samples were collected during harvesting periods 2013 and 2014 from Greece, Egypt, Morocco, and Spain. Conventional physicochemical and CIELAB colour parameters were determined using official methods of analysis and the Commission Internationale de l' Eclairage recommendations, respectively. Minerals were determined using ICP-OES and volatiles using SPME-GC/MS. Results showed that honey samples analyzed, met the standard quality criteria set by the EU and were successfully classified according to geographical origin. Correct classification rates were 97.3% using 8 physicochemical parameter values, 86.5% using 15 volatile compound data and 83.8% using 13 minerals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Membrane inlet mass spectrometry of volatile organohalogen compounds in drinking water.

PubMed

Bocchini, P; Pozzi, R; Andalò, C; Galletti, G C

1999-01-01

The analysis of organic pollutants in drinking water is a topic of wide interest, reflecting on public health and life quality. Many different methodologies have been developed and are currently employed in this context, but they often require a time-consuming sample pre-treatment. This step affects the recovery of the highly volatile compounds. Trace analysis of volatile organic pollutants in water can be performed 'on-line' by membrane inlet mass spectrometry (MIMS). In MIMS, the sample is separated from the vacuum of the mass spectrometer by a thin polymeric hollow-fibre membrane. Gases and organic volatile compounds diffuse and concentrate from the sample into the hollow-fibre membrane, and from there into the mass spectrometer. The main advantages of the technique are that no pre-treatment of samples before analysis is needed and that it has fast response times and on-line monitoring capabilities. This paper reports the set-up of the analytical conditions for the analysis of volatile organohalogen compounds (chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride). Linearity of response, repeatability, detection limits, and spectra quality are evaluated. Copyright 1999 John Wiley & Sons, Ltd.

Detection of Volatile Indicators of Illicit Substances by the Olfactory Receptors of Drosophila melanogaster

PubMed Central

Marshall, Brenton; Warr, Coral G.

2010-01-01

Insects can detect a large range of odors with a numerically simple olfactory system that delivers high sensitivity and accurate discrimination. Therefore, insect olfactory receptors hold great promise as biosensors for detection of volatile organic chemicals in a range of applications. The array of olfactory receptor neurons of Drosophila melanogaster is rapidly becoming the best-characterized natural nose. We have investigated the suitability of Drosophila receptors as detectors for volatiles with applications in law enforcement, emergency response, and security. We first characterized responses of the majority of olfactory neuron types to a set of diagnostic odorants. Being thus able to correctly identify neurons, we then screened for responses from 38 different types of neurons to 35 agents. We identified 13 neuron types with responses to 13 agents. As individual Drosophila receptor genes have been mapped to neuron types, we can infer which genes confer responsiveness to the neurons. The responses were confirmed for one receptor by expressing it in a nonresponsive neuron. The fly olfactory system is mainly adapted to detect volatiles from fermenting fruits. However, our findings establish that volatiles associated with illicit substances, many of which are of nonnatural origin, are also detected by Drosophila receptors. PMID:20530374

Intraplate mantle oxidation by volatile-rich silicic magmas

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

Martin, Audrey M.; Médard, Etienne; Righter, Kevin

The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365–286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N–S Rhenohercynian subduction, and (2)more » < 30 Ma old magmatism related to W–E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.« less

Adherence of volatile propofol to various types of plastic tubing.

PubMed

Maurer, F; Lorenz, D J; Pielsticker, G; Volk, T; Sessler, D I; Baumbach, J I; Kreuer, S

2017-01-23

Propofol is an intravenous anesthetic. Currently, it is not possible to routinely measure blood concentration of the drug in real time. However, multi-capillary column ion-mobility spectrometry of exhaled gas can estimate blood propofol concentration. Unfortunately, adhesion of volatile propofol on plastic materials complicates measurements. Therefore, it is necessary to consider the extent to which volatile propofol adheres to various plastics used in sampling tubing. Perfluoralkoxy (PFA), polytetrafluorethylene (PTFE), polyurethane (PUR), silicone, and Tygon tubing were investigated in an experimental setting using a calibration gas generator (HovaCAL). Propofol gas was measured for one hour at 26 °C, 50 °C, and 90 °C tubing temperature. Test tubing segments were then flushed with N 2 to quantify desorption. PUR and Tygon sample tubing absorbed all volatile propofol. The silicone tubing reached the maximum propofol concentration after 119 min which was 29 min after propofol gas exposure stopped. The use of PFA or PTFE tubing produced comparable and reasonably accurate propofol measurements. The desaturation time for the PFA was 10 min shorter at 26 °C than for PTFE. PFA tubing thus seems most suitable for measurement of volatile propofol, with PTFE as an alternative.

Volatiles released from Vaccinium corymbosum were attractive to Aegorhinus superciliosus (Coleoptera: Curculionidae) in an olfactometric bioassay.

PubMed

Parra, Leonardo; Mutis, Ana; Ceballos, Ricardo; Lizama, Marcelo; Pardo, Fernando; Perich, Fernando; Quiroz, Andrés

2009-06-01

The objective of this study was to evaluate the role of host volatiles in the relationship between a blueberry plant Vaccinium corymbosum L. and the raspberry weevil Aegorhinus superciliosus (Guérin) (Coleoptera: Curculionidae), the principal pest of blueberry in the south of Chile. Volatiles from the aerial part of different phenological stages of the host were collected on Porapak Q and analyzed by coupled gas chromatography-mass spectrometry (GC-MS). Several chemical groups were identified including green leaf volatiles, aromatic compounds, and terpenes. The olfactometric responses of A. superciliosus toward different odor sources were studied in a four-arm olfactometer. Blueberry shoots at the phenological stages of fruit set, and blue-pink fruit color elicited the greatest behavioral responses from weevils. Five compounds (2-nonanone, eucalyptol, R- and S-limonene, and 4-ethyl benzaldehyde) elicited an attractant behavioral response from A. superciliosus. The results suggest the host location behavior of A. superciliosus could be mediated by volatiles derived from V. corymbosum. This work has identified a number of compounds with which it is possible to develop a lure for the principal pest of blueberry in southern Chile.

Changes in Volatile and Non-Volatile Flavor Chemicals of “Valencia” Orange Juice over the Harvest Seasons

PubMed Central

Bai, Jinhe; Baldwin, Elizabeth A.; McCollum, Greg; Plotto, Anne; Manthey, John A.; Widmer, Wilbur W.; Luzio, Gary; Cameron, Randall

2016-01-01

Florida “Valencia” oranges have a wide harvest window, covering four months after first reaching the commercial maturity. However, the influence of harvest time on juice flavor chemicals is not well documented, with the exception of sugars and acids. Therefore, we investigated the major flavor chemicals, volatile (aroma), non-volatile (taste) and mouth feel attributes, in the two harvest seasons (March to June in 2007 and February to May in 2012). Bitter limonoid compounds, limonin and nomilin, decreased gradually. Out of a total of 94 volatiles, 32 increased, 47 peaked mid to late season, and 15 decreased. Juice insoluble solids and pectin content increased over the season; however, pectin methylesterase activity remained unchanged. Fruit harvested in the earlier months had lower flavor quality. Juice from later harvests had a higher sugar/acid ratio with less bitterness, while, many important aroma compounds occurred at the highest concentrations in the middle to late season, but occurred at lower concentrations at the end of the season. The results provide information to the orange juice processing industry for selection of optimal harvest time and for setting of precise blending strategy. PMID:28231099

Sulfur isotopic evidence for sources of volatiles in Siberian Traps magmas

NASA Astrophysics Data System (ADS)

Black, Benjamin A.; Hauri, Erik H.; Elkins-Tanton, Linda T.; Brown, Stephanie M.

2014-05-01

The Siberian Traps flood basalts transferred a large mass of volatiles from the Earth's mantle and crust to the atmosphere. The eruption of the large igneous province temporally overlapped with the end-Permian mass extinction. Constraints on the sources of Siberian Traps volatiles are critical for determining the overall volatile budget, the role of crustal assimilation, the genesis of Noril'sk ore deposits, and the environmental effects of magmatism. We measure sulfur isotopic ratios ranging from -10.8‰ to +25.3‰ Vienna Cañon Diablo Troilite (V-CDT) in melt inclusions from Siberian Traps basaltic rocks. Our measurements, which offer a snapshot of sulfur cycling far from mid-ocean ridge and arc settings, suggest the δ34S of the Siberian Traps mantle melt source was close to that of mid-ocean ridge basalts. In conjunction with previously published whole rock measurements from Noril'sk, our sulfur isotopic data indicate that crustal contamination was widespread and heterogeneous—though not universal—during the emplacement of the Siberian Traps. Incorporation of crustal materials likely increased the total volatile budget of the large igneous province, thereby contributing to Permian-Triassic environmental deterioration.

Changes in Volatile and Non-Volatile Flavor Chemicals of "Valencia" Orange Juice over the Harvest Seasons.

PubMed

Bai, Jinhe; Baldwin, Elizabeth A; McCollum, Greg; Plotto, Anne; Manthey, John A; Widmer, Wilbur W; Luzio, Gary; Cameron, Randall

2016-01-04

Florida "Valencia" oranges have a wide harvest window, covering four months after first reaching the commercial maturity. However, the influence of harvest time on juice flavor chemicals is not well documented, with the exception of sugars and acids. Therefore, we investigated the major flavor chemicals, volatile (aroma), non-volatile (taste) and mouth feel attributes, in the two harvest seasons (March to June in 2007 and February to May in 2012). Bitter limonoid compounds, limonin and nomilin, decreased gradually. Out of a total of 94 volatiles, 32 increased, 47 peaked mid to late season, and 15 decreased. Juice insoluble solids and pectin content increased over the season; however, pectin methylesterase activity remained unchanged. Fruit harvested in the earlier months had lower flavor quality. Juice from later harvests had a higher sugar/acid ratio with less bitterness, while, many important aroma compounds occurred at the highest concentrations in the middle to late season, but occurred at lower concentrations at the end of the season. The results provide information to the orange juice processing industry for selection of optimal harvest time and for setting of precise blending strategy.

Intraplate mantle oxidation by volatile-rich silicic magmas

NASA Astrophysics Data System (ADS)

Martin, Audrey M.; Médard, Etienne; Righter, Kevin; Lanzirotti, Antonio

2017-11-01

The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365-286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N-S Rhenohercynian subduction, and (2) < 30 Ma old magmatism related to W-E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.

Birds Bug on Indirect Plant Defenses to Locate Insect Prey.

PubMed

Hiltpold, Ivan; Shriver, W Gregory

2018-06-01

It has long been thought that most birds do not use volatile cues to perceive their environment. Aside from some scavenging birds, this large group of vertebrates was believed to mostly rely on highly developed vision while foraging and there are relatively few studies exploring bird response to volatile organic compounds. In response to insect herbivory, plants release volatile organic compounds to attract parasitoids and predators of the pests. To test if insectivorous birds use herbivore-induced plant volatiles (HIPV), dispensers emitting a synthetic blend of HIPV typically emitted after insect herbivory were deployed in a maize field along with imitation clay caterpillars. Significantly more imitation insects were attacked by birds when located close to dispensers releasing HIPV than close to dispenser with organic solvent only. Seven times more peck marks, an index of avian predation, were counted on caterpillars in the vicinity of the HIPV dispensers than on insects close to control dispensers. This is the first field demonstration that insectivorous birds cue on HIPV to locate prey in agricultural settings. These results support the growing evidence that foraging birds exploit volatile cues. This more accurate understanding of their behavior will be important when implementing pest management program involving insectivorous birds.

Mercury's Weather-Beaten Surface: Understanding Mercury in the Context of Lunar and Asteroidal Space Weathering Studies

NASA Technical Reports Server (NTRS)

Domingue, Deborah L.; Chapman, Clark. R.; Killen, Rosemary M.; Zurbuchen, Thomas H.; Gilbert, Jason A.; Sarantos, Menelaos; Benna, Mehdi; Slavin, James A.; Schriver, David; Travnicek, Pavel M.;

Early MAVEN Deep Dip campaign reveals thermosphere and ionosphere variability.

PubMed

Bougher, S; Jakosky, B; Halekas, J; Grebowsky, J; Luhmann, J; Mahaffy, P; Connerney, J; Eparvier, F; Ergun, R; Larson, D; McFadden, J; Mitchell, D; Schneider, N; Zurek, R; Mazelle, C; Andersson, L; Andrews, D; Baird, D; Baker, D N; Bell, J M; Benna, M; Brain, D; Chaffin, M; Chamberlin, P; Chaufray, J-Y; Clarke, J; Collinson, G; Combi, M; Crary, F; Cravens, T; Crismani, M; Curry, S; Curtis, D; Deighan, J; Delory, G; Dewey, R; DiBraccio, G; Dong, C; Dong, Y; Dunn, P; Elrod, M; England, S; Eriksson, A; Espley, J; Evans, S; Fang, X; Fillingim, M; Fortier, K; Fowler, C M; Fox, J; Gröller, H; Guzewich, S; Hara, T; Harada, Y; Holsclaw, G; Jain, S K; Jolitz, R; Leblanc, F; Lee, C O; Lee, Y; Lefevre, F; Lillis, R; Livi, R; Lo, D; Ma, Y; Mayyasi, M; McClintock, W; McEnulty, T; Modolo, R; Montmessin, F; Morooka, M; Nagy, A; Olsen, K; Peterson, W; Rahmati, A; Ruhunusiri, S; Russell, C T; Sakai, S; Sauvaud, J-A; Seki, K; Steckiewicz, M; Stevens, M; Stewart, A I F; Stiepen, A; Stone, S; Tenishev, V; Thiemann, E; Tolson, R; Toublanc, D; Vogt, M; Weber, T; Withers, P; Woods, T; Yelle, R

2015-11-06

The Mars Atmosphere and Volatile Evolution (MAVEN) mission, during the second of its Deep Dip campaigns, made comprehensive measurements of martian thermosphere and ionosphere composition, structure, and variability at altitudes down to ~130 kilometers in the subsolar region. This altitude range contains the diffusively separated upper atmosphere just above the well-mixed atmosphere, the layer of peak extreme ultraviolet heating and primary reservoir for atmospheric escape. In situ measurements of the upper atmosphere reveal previously unmeasured populations of neutral and charged particles, the homopause altitude at approximately 130 kilometers, and an unexpected level of variability both on an orbit-to-orbit basis and within individual orbits. These observations help constrain volatile escape processes controlled by thermosphere and ionosphere structure and variability. Copyright © 2015, American Association for the Advancement of Science.

Machine learning for the meta-analyses of microbial pathogens' volatile signatures.

PubMed

Palma, Susana I C J; Traguedo, Ana P; Porteira, Ana R; Frias, Maria J; Gamboa, Hugo; Roque, Ana C A

2018-02-20

Non-invasive and fast diagnostic tools based on volatolomics hold great promise in the control of infectious diseases. However, the tools to identify microbial volatile organic compounds (VOCs) discriminating between human pathogens are still missing. Artificial intelligence is increasingly recognised as an essential tool in health sciences. Machine learning algorithms based in support vector machines and features selection tools were here applied to find sets of microbial VOCs with pathogen-discrimination power. Studies reporting VOCs emitted by human microbial pathogens published between 1977 and 2016 were used as source data. A set of 18 VOCs is sufficient to predict the identity of 11 microbial pathogens with high accuracy (77%), and precision (62-100%). There is one set of VOCs associated with each of the 11 pathogens which can predict the presence of that pathogen in a sample with high accuracy and precision (86-90%). The implemented pathogen classification methodology supports future database updates to include new pathogen-VOC data, which will enrich the classifiers. The sets of VOCs identified potentiate the improvement of the selectivity of non-invasive infection diagnostics using artificial olfaction devices.

Studies on transient characteristics of unipolar resistive switching processes in TiO2 thin film grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Sahu, Vikas Kumar; Das, Amit K.; Ajimsha, R. S.; Misra, P.

2018-05-01

The transient characteristics of resistive switching processes have been investigated in TiO2 thin films grown by atomic layer deposition (ALD) to study the temporal evolution of the switching processes and measure the switching times. The reset and set switching times of unipolar Au/TiO2/Pt devices were found to be ~250 µs and 180 ns, respectively in the voltage windows of 0.5–0.9 V for reset and 1.9–4.8 V for set switching processes, obtained from quasi-static measurements. The reset switching time decreased exponentially with increasing amplitude of applied reset voltage pulse, while the set switching time remained insensitive to the amplitude of the set voltage pulse. A fast reset process with a switching time of ~400 ns was achieved by applying a reset voltage of ~1.8 V, higher than that of the quasi-static reset voltage window but below the set voltage window. The sluggish reset process in TiO2 thin film and the dependence of the reset switching time on the amplitude of the applied voltage pulse was understood on the basis of a self-accelerated thermal dissolution model of conducting filaments (CFs), where a higher temperature of the CFs owing to enhanced Joule heating at a higher applied voltage imposes faster diffusion of oxygen vacancies, resulting in a shorter reset switching time. Our results clearly indicate that fast resistive switching with switching times in hundreds of nanoseconds can be achieved in ALD-grown TiO2 thin films. This may find applications in fast non-volatile unipolar resistive switching memories.

Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: Formulation, proof of concept, and a pilot implementation

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

Mao, Yuezhi; Horn, Paul R.; Mardirossian, Narbe

2016-07-28

Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF (PC) approach with the same large target basis set producesmore » <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF (PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.« less

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

Simple and efficient LCAO basis sets for the diffuse states in carbon nanostructures.

PubMed

Papior, Nick R; Calogero, Gaetano; Brandbyge, Mads

2018-06-27

We present a simple way to describe the lowest unoccupied diffuse states in carbon nanostructures in density functional theory calculations using a minimal LCAO (linear combination of atomic orbitals) basis set. By comparing plane wave basis calculations, we show how these states can be captured by adding long-range orbitals to the standard LCAO basis sets for the extreme cases of planar sp 2 (graphene) and curved carbon (C 60 ). In particular, using Bessel functions with a long range as additional basis functions retain a minimal basis size. This provides a smaller and simpler atom-centered basis set compared to the standard pseudo-atomic orbitals (PAOs) with multiple polarization orbitals or by adding non-atom-centered states to the basis.

Simple and efficient LCAO basis sets for the diffuse states in carbon nanostructures

NASA Astrophysics Data System (ADS)

Papior, Nick R.; Calogero, Gaetano; Brandbyge, Mads

2018-06-01

We present a simple way to describe the lowest unoccupied diffuse states in carbon nanostructures in density functional theory calculations using a minimal LCAO (linear combination of atomic orbitals) basis set. By comparing plane wave basis calculations, we show how these states can be captured by adding long-range orbitals to the standard LCAO basis sets for the extreme cases of planar sp 2 (graphene) and curved carbon (C60). In particular, using Bessel functions with a long range as additional basis functions retain a minimal basis size. This provides a smaller and simpler atom-centered basis set compared to the standard pseudo-atomic orbitals (PAOs) with multiple polarization orbitals or by adding non-atom-centered states to the basis.

Lunar volatiles: balancing science and resource development

NASA Astrophysics Data System (ADS)

Crider, Dana

In the context of human exploration of the moon, the volatiles postulated to exist at the lunar poles have value as resources as well as scientific significance. Once sustained human operations commence on the moon, society will move from a paradigm in which examination of planetary materials has been unconstrained to one where use of those materials will support habitability and further exploration. A framework for the scientific investigation of lunar volatiles that allows for eventual economic exploitation can guide both activities and resolve the conflicts that will inevitably develop if the postulated lunar volatiles prove to be both extant and accessible. Scientific constraints on the framework include characterization at both poles of the isotopes, elements, and molecules in the volatiles, their relative and absolute abundances, and their horizontal and vertical distribution. A subset of this data is necessary in order to assess, develop, and initiate resource exploitation. In addition, the scientific record of volatiles in the cold traps can be contaminated by the cold-trapping of migrating volatiles released from operations elsewhere on the moon even if the indigenous, cold-trapped volatiles are not utilized. Possible decision points defining the transition from science-dominated to exploitation-dominated use include technology limits in the 70K environment, evolving science priorities (funding), and the resolution of major science issues. Inputs to policy development include any North vs. South Pole differences in volatile characteristics and the suitability of the volatiles to enable further scientific exploration of the moon. In the absence of national sovereignty on the moon, enforcement of any framework is an open question, particularly if science and commercial interests are in competition. The framework, processes, and precedent set by how we as a society choose to handle the scientific bounty and resource promise of lunar volatiles may eventually apply to Mars and near-earth asteroids. We believe there are useful lessons to be learned from the terrestrial experience with protected areas such as national parks, wilderness areas, and archeological sites. International agreements such as the Antarctic Treaty (in force since 1961), the Outer Space Treaty (1967), and the Moon Treaty (1979) carry relevant lessons as well.

Popping rocks from the Mid-Atlantic Ridge: Insights into mantle volatile concentrations and degassing dynamics

NASA Astrophysics Data System (ADS)

Jones, M.; Soule, S. A.; Kurz, M. D.; Wanless, V. D.; Le Roux, V.; Klein, F.; Mittelstaedt, E. L.; Curtice, J.

2016-12-01

During a 1985 cruise, the Mid-Atlantic Ridge (MAR) near 14°N yielded an unusually vesicular mid-ocean ridge (MOR) basalt that popped upon recovery from the seafloor due to the release of trapped volatiles. This `popping rock' has been inferred to be representative of primitive, undegassed magmas from the upper mantle due to its high volatile concentrations. Thus, the sample has been used to constrain CO2 flux from the MOR system, upper mantle volatile concentrations, and magma degassing dynamics. However, the lack of geologic context for the original popping rock raises questions about whether it truly reflects the volatile content of its mantle source. Here, we present results from a 2016 cruise to the MAR aimed at characterizing the geologic context of popping rocks and understanding their origins. The newly recovered samples display differences in volatile concentrations and vesicularities between popping and non-popping rocks. These differences may be related to geologic setting and eruption dynamics with potential implications for mantle volatile concentrations. Volatile concentrations in the outer quenched margin of new samples were measured by ion microprobe to elucidate degassing systematics, brine/magma interactions, and popping rock formation. The large variability in dissolved H2O (0.05-0.77 wt%) can be attributed to spatially variable brine contamination. Dissolved CO2 concentrations (153-356 ppm) are likely controlled by initial volatile concentrations and variable degrees of degassing. The subset of popping samples display low dissolved CO2 concentrations (161-178 ppm) and moderate dissolved H2O concentrations (.44-.50 wt%) and are at equilibrium with their eruption depth based on solubility calculations. X-ray microtomography reveals vesicularity in newly collected popping rocks exceeding 19%, making these samples the most highly vesicular recovered from the MAR. The total gas contents in the basaltic glasses are inferred from dissolved volatile concentrations and vesicularity. These calculations are aided by analysis of gas contents in vesicles by confocal Raman spectroscopy and vacuum crushing experiments. The preliminary results and seafloor observations allow an evaluation of the origins of popping rocks and their implications for mantle volatile concentrations.

Modeling and forecasting the volatility of Islamic unit trust in Malaysia using GARCH model

NASA Astrophysics Data System (ADS)

Ismail, Nuraini; Ismail, Mohd Tahir; Karim, Samsul Ariffin Abdul; Hamzah, Firdaus Mohamad

2015-10-01

Due to the tremendous growth of Islamic unit trust in Malaysia since it was first introduced on 12th of January 1993 through the fund named Tabung Ittikal managed by Arab-Malaysian Securities, vast studies have been done to evaluate the performance of Islamic unit trust offered in Malaysia's capital market. Most of the studies found that one of the factors that affect the performance of the fund is the volatility level. Higher volatility produces better performance of the fund. Thus, we believe that a strategy must be set up by the fund managers in order for the fund to perform better. By using a series of net asset value (NAV) data of three different types of fund namely CIMB-IDEGF, CIMB-IBGF and CIMB-ISF from a fund management company named CIMB Principal Asset Management Berhad over a six years period from 1st January 2008 until 31st December 2013, we model and forecast the volatility of these Islamic unit trusts. The study found that the best fitting models for CIMB-IDEGF, CIMB-IBGF and CIMB-ISF are ARCH(4), GARCH(3,3) and GARCH(3,1) respectively. Meanwhile, the fund that is expected to be the least volatile is CIMB-IDEGF and the fund that is expected to be the most volatile is CIMB-IBGF.

Simultaneous alloy-silicate fractionation of carbon, nitrogen, and sulfur at high pressures and temperatures: Implications for establishing the volatile budget of the Earth

NASA Astrophysics Data System (ADS)

Grewal, D. S.; Dasgupta, R.; Sun, C.; Tsuno, K.

2017-12-01

Constraining the origin, distribution and evolution of volatiles such as carbon (C), nitrogen (N) and sulfur (S) in terrestrial planets is essential to understand planetary differentiation, habitability and comparative planetology [1]. C/N ratio of Bulk Silicate Earth (BSE) is superchondritic (40 ± 8), while C/S ratio is nearly chondritic (0.49 ± 0.14) [2]. Accretion, core formation, and magma ocean (MO) crystallization are the key processes that could have set the relative budgets of C, N and S in different planetary reservoirs [3]. However, experiments using either C-N or C-S-bearing systems have shown that C is more siderophile than N and S, consequently core formation would have left behind subchondritic C/N and C/S ratios in BSE [4-6]. Accretion of extremely C-rich bodies during core formation or/and as a late veneer along with an early atmospheric blow-off are amongst the scenarios that have been suggested to explain C/N ratio while the addition of a differentiated body with a C-rich mantle has been suggested to explain C/S ratio in BSE [4-6]. However, no internally consistent explanations exist on the origin of all the volatile elements. We performed piston cylinder and multi-anvil experiments, using Fe-Ni-N-C±S alloy with variable amounts of S and mafic-ultramafic silicate mixtures in graphite saturated conditions at 1-7 GPa, 1600-1800 °C, and fO2 ranging from ΔIW of -1.1 to -0.3. EPMA and SIMS were used to determine major elements and volatile abundances in the coexisting alloy and silicate melt phases, while the speciation of the volatiles was determined using Raman spectroscopy. Our experimental data reveals that C becomes less siderophile in the presence of N and S during core-mantle differentiation involving an S-rich alloy. Using a set of inverse Monte-Carlo simulations, we propose that a disequilibrium merger of a Mars-sized planetary embryo with a C-saturated, S-rich core to a volatile-depleted proto-Earth during the main stage of accretion could have simultaneously satisfied C-N-S abundances and ratios in BSE along with setting up the stage of for the presence of NH3 and HCN in the Earth's early atmosphere via MO degassing. [1] Zahnle et al. (2007) Space Sci. Rev. [2] Marty (2012) EPSL. [3] Dasgupta et al. (2013) GCA. [4] Hirschmann (2016) AM. [5] Dalou et al. (2017) EPSL. [6] Li et al. (2016) Nat. Geosci.

Characteristics of Milk Fermented by Streptococcus thermophilus MGA45-4 and the Profiles of Associated Volatile Compounds during Fermentation and Storage.

PubMed

Dan, Tong; Jin, Rulin; Ren, Weiyi; Li, Ting; Chen, Haiyan; Sun, Tiansong

2018-04-11

The lactic acid bacterium Streptococcus thermophilus is a major starter culture for the production of dairy products. In this study, the physiochemical characteristics of milk fermented by the MGA45-4 isolate of S. thermophilus were analyzed. Our data indicate that milk fermented using S. thermophilus MGA45-4 maintained a high viable cell count (8.86 log10 colony-forming units/mL), and a relatively high pH (4.4), viscosity (834.33 mPa·s), and water holding capacity (40.85%) during 14 days of storage. By analyzing the volatile compound profile using solid-phase microextraction and gas chromatography/mass spectrometry, we identified 73 volatile compounds in the fermented milk product, including five carboxylic acids, 21 aldehydes, 13 ketones, 16 alcohols, five esters, and 13 aromatic carbohydrates. According to the odor activity values, 11 of these volatile compounds were found to play a key role in producing the characteristic flavor of fermented milk, particularly octanal, nonanal, hexanal, 2,3-butanedione, and 1-octen-3-ol, which had the highest odor activity values among all compounds analyzed. These findings thus provide more insights in the chemical/molecular characteristics of milk fermented using S. thermophilus , which may provide a basis for improving dairy product flavor/odor during the process of fermentation and storage.

Treatability of volatile chlorinated hydrocarbon-contaminated soils of different textures along a vertical profile by mechanical soil aeration: A laboratory test.

PubMed

Ma, Yan; Shi, Yi; Hou, Deyi; Zhang, Xi; Chen, Jiaqi; Wang, Zhifen; Xu, Zhu; Li, Fasheng; Du, Xiaoming

2017-04-01

Mechanical soil aeration is a simple, effective, and low-cost soil remediation technology that is suitable for sites contaminated with volatile chlorinated hydrocarbons (VCHs). Conventionally, this technique is used to treat the mixed soil of a site without considering the diversity and treatability of different soils within the site. A laboratory test was conducted to evaluate the effectiveness of mechanical soil aeration for remediating soils of different textures (silty, clayey, and sandy soils) along a vertical profile at an abandoned chloro-alkali chemical site in China. The collected soils were artificially contaminated with chloroform (TCM) and trichloroethylene (TCE). Mechanical soil aeration was effective for remediating VCHs (removal efficiency >98%). The volatilization process was described by an exponential kinetic function. In the early stage of treatment (0-7hr), rapid contaminant volatilization followed a pseudo-first order kinetic model. VCH concentrations decreased to low levels and showed a tailing phenomenon with very slow contaminant release after 8hr. Compared with silty and sandy soils, clayey soil has high organic-matter content, a large specific surface area, a high clay fraction, and a complex pore structure. These characteristics substantially influenced the removal process, making it less efficient, more time consuming, and consequently more expensive. Our findings provide a potential basis for optimizing soil remediation strategy in a cost-effective manner. Copyright © 2016. Published by Elsevier B.V.

Fatty Acid Composition and Volatile Constituents of Protaetia brevitarsis Larvae.

PubMed

Yeo, Hyelim; Youn, Kumju; Kim, Minji; Yun, Eun-Young; Hwang, Jae-Sam; Jeong, Woo-Sik; Jun, Mira

2013-06-01

A total of 48 different volatile oils were identified form P. brevitarsis larvae by gas chromatography/mass spectrometry (GC/MS). Acids (48.67%) were detected as the major group in P. brevitarsis larvae comprising the largest proportion of the volatile compounds, followed by esters (19.84%), hydrocarbons (18.90%), alcohols (8.37%), miscellaneous (1.71%), aldehydes (1.35%) and terpenes (1.16%). The major volatile constituents were 9-hexadecenoic acid (16.75%), 6-octadecenoic acid (14.88%) and n-hexadecanoic acid (11.06%). The composition of fatty acid was also determined by GC analysis and 16 fatty acids were identified. The predominant fatty acids were oleic acid (C18:1, 64.24%) followed by palmitic acid (C16:0, 15.89%), palmitoleic acid (C16:1, 10.43%) and linoleic acid (C18:2, 4.69%) constituting more than 95% of total fatty acids. The distinguished characteristic of the fatty acid profile of P. brevitarsis larvae was the high proportion of unsaturated fatty acid (80.54% of total fatty acids) versus saturated fatty acids (19.46% of total fatty acids). Furthermore, small but significant amounts of linoleic, linolenic and γ-linolenic acids bestow P. brevitarsis larvae with considerable nutritional value. The novel findings of the present study provide a scientific basis for the comprehensive utilization of the insect as a nutritionally promising food source and a possibility for more effective utilization.

Fatty Acid Composition and Volatile Constituents of Protaetia brevitarsis Larvae

PubMed Central

Yeo, Hyelim; Youn, Kumju; Kim, Minji; Yun, Eun-Young; Hwang, Jae-Sam; Jeong, Woo-Sik; Jun, Mira

2013-01-01

A total of 48 different volatile oils were identified form P. brevitarsis larvae by gas chromatography/mass spectrometry (GC/MS). Acids (48.67%) were detected as the major group in P. brevitarsis larvae comprising the largest proportion of the volatile compounds, followed by esters (19.84%), hydrocarbons (18.90%), alcohols (8.37%), miscellaneous (1.71%), aldehydes (1.35%) and terpenes (1.16%). The major volatile constituents were 9-hexadecenoic acid (16.75%), 6-octadecenoic acid (14.88%) and n-hexadecanoic acid (11.06%). The composition of fatty acid was also determined by GC analysis and 16 fatty acids were identified. The predominant fatty acids were oleic acid (C18:1, 64.24%) followed by palmitic acid (C16:0, 15.89%), palmitoleic acid (C16:1, 10.43%) and linoleic acid (C18:2, 4.69%) constituting more than 95% of total fatty acids. The distinguished characteristic of the fatty acid profile of P. brevitarsis larvae was the high proportion of unsaturated fatty acid (80.54% of total fatty acids) versus saturated fatty acids (19.46% of total fatty acids). Furthermore, small but significant amounts of linoleic, linolenic and γ-linolenic acids bestow P. brevitarsis larvae with considerable nutritional value. The novel findings of the present study provide a scientific basis for the comprehensive utilization of the insect as a nutritionally promising food source and a possibility for more effective utilization. PMID:24471125

Degradation Kinetics of VX

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

Gary S. Groenewold

2010-12-01

O-ethyl S-(2-diisopropylaminoethyl)phosphonothiolate (VX) is the most toxic of the conventional chemical warfare agents. It is a persistent compound, an attribute derived from its relative involatility and slow rates of hydrolysis. These properties suggest that VX can linger in an exposed environment for extended periods of time long after the air has cleared. Concern over prolonged risk from VX exposure is exacerbated by the fact that it poses a dermal contact hazard. Hence a detailed understanding of volatilization rates, and degradation pathways and rates occurring in various environments is needed. Historically, volatilization has not been considered to be an important mechanismmore » for VX depletion, but recent studies have shown that a significant fraction of VX may volatilize, depending on the matrix. A significant body of research has been conducted over the years to unravel VX degradation reaction pathways and to quantify the rates at which they proceed. Rigorous measurement of degradation rates is frequently difficult, and thus in many cases the degradation of VX has been described in terms of half lives, while in fewer instances rate constants have been measured. This variable approach to describing degradation kinetics reflects uncertainty regarding the exact nature of the degradation mechanisms. In this review, rates of VX degradation are compared on the basis of pseudo-first order rate constants, in order to provide a basis for assessing likelihood of VX persistence in a given environment. An issue of specific concern is that one VX degradation pathway produces S-2-(diisopropylaminoethyl) methylphosphonothioic acid (known as EA2192), which is a degradation product that retains much of the original toxicity of VX. Consequently degradation pathways and rates for EA2192 are also discussed.« less

Derivation of a formula for the resonance integral for a nonorthogonal basis set

PubMed Central

Yim, Yung-Chang; Eyring, Henry

1981-01-01

In a self-consistent field calculation, a formula for the off-diagonal matrix elements of the core Hamiltonian is derived for a nonorthogonal basis set by a polyatomic approach. A set of parameters is then introduced for the repulsion integral formula of Mataga-Nishimoto to fit the experimental data. The matrix elements computed for the nonorthogonal basis set in the π-electron approximation are transformed to those for an orthogonal basis set by the Löwdin symmetrical orthogonalization. PMID:16593009

[Analysis and toxicological evaluation of hazardous gases in sealed cabin].

PubMed

He, Z; Shi, J; Yu, B; Liang, H; Yu, F

1998-10-01

82 volatile organic compounds (VOCs) of eight organic sorts and 3 target inorganic compounds in a sealed cabin that simulating the flying spaceship were identified and quantified for 5 d, the law of hazardous gas concentration variation was discussed, and the atmosphere toxicology was evaluated preliminarily. It provides a basis for detecting gas compounds and evaluating the atmosphere toxicology in the spaceship.

Meteoritics, Number 19

DTIC Science & Technology

1964-06-01

of the Migeya meteorite, which contains volatile organic compounds (a feature which proves the absence of overheating during its life), is 4.3...pattern in their discovery of gallium and germanium in iron meteorites as small ad- mixtures. Iron meteorites are divided into four groups by their content...as a basis for the classification of meteorites by their composition that we have suggested- By comparing the data they obtained on gallium and

76 FR 37868 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing of...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-28

... every trading day since that time.\\5\\ \\5\\ CBOE maintains a micro-site for VXSLV: http://www.cboe.com/micro/VIXETF/VXSLV/ . VXSLV is an up-to-the-minute market estimate of the expected volatility of SLV... underlying option series on a real-time basis throughout each trading day, from 8:30 a.m. until 3 p.m. (CT...

Changes in Volatile Compounds of Chinese Luzhou-Flavor Liquor during the Fermentation and Distillation Process.

PubMed

Ding, Xiaofei; Wu, Chongde; Huang, Jun; Zhou, Rongqing

2015-11-01

The aim of this study was to investigate the dynamic of volatile compounds in the Zaopei during the fermentation and distillation process by headspace solid-phase microextraction-gas chromatography mass spectrometry (HS-SPME-GCMS). Physicochemical properties analysis of Zaopei (fermented grains [FG], fermented grains mixed with sorghum [FGS], streamed grains [SG], and streamed grains mixed with Daqu [SGD]) showed distinct changes. A total number of 66 volatile compounds in the Zaopei were identified, in which butanoic acid, hexanoic acid, ethyl hexanoate, ethyl lactate, ethyl octanoate, hexyl hexanoate, ethyl hydrocinnamate, ethyl oleate, ethyl hexadecanoate, and ethyl linoleate were considered to be the dominant compounds due to their high concentrations. FG had the highest volatile compounds (112.43 mg/kg), which significantly decreased by 17.05% in the FGS, 67.12% in the SG, and 73.75% in the SGD. Furthermore, about 61.49% of volatile compounds of FGS were evaporated into raw liquor, whereas head, heart, and tail liquor accounted for 29.84%, 39.49%, and 30.67%, respectively. Each volatile class generally presented a decreasing trend, except for furans. Especially, the percentage of esters was 55.51% to 67.41% in the Zaopei, and reached 92.60% to 97.67% in the raw liquor. Principal component analysis based ordination of volatile compounds data segregated FGS and SGD samples. In addition, radar diagrams of the odor activity values suggested that intense flavor of fruit was weakened most from FG to SGD. The dynamic of volatile compounds in the Zaopei during the fermentation and distillation process was tested by SPME-GCMS. The result of this study demonstrated that both volatile compounds of Zaopei and thermal reaction during distillation simply determined the unique feature of raw liquor. This study was conducted based on the real products from liquor manufactory, so it is practicable that the method can be used in an industry setting. © 2015 Institute of Food Technologists®

US EPA'S SUPERSITES PROGRAM

EPA Science Inventory

Dermal exposure to volatile organic compounds (VOCs) in water results from environmental contamination of surface, ground-, and drinking waters. This exposure occurs both in occupational and residential settings. Compartmental models incorporating body burden measurements have ...

Volatiles and Isotopes and the Exploration of Ancient and Modern Martian Habitability with the Curiosity Rover

NASA Technical Reports Server (NTRS)

Mhaffy, P. R.

2015-01-01

The Mars Science Laboratory Mission was designed to pave the way for the study of life beyond Earth through a search for a habitable environment in a carefully selected landing site on Mars. Its ongoing exploration of Gale Crater with the Curiosity Rover has provided a rich data set that revealed such an environment in an ancient lakebed [1]. Volatile and isotope measurements of both the atmosphere and solids contribute to our growing understanding of both modern and ancient environments.

Optical detection of explosives: spectral signatures for the explosive bouquet

NASA Astrophysics Data System (ADS)

Osborn, Tabetha; Kaimal, Sindhu; Causey, Jason; Burns, William; Reeve, Scott

2009-05-01

Research with canines suggests that sniffer dogs alert not on the odor from a pure explosive, but rather on a set of far more volatile species present in an explosive as impurities. Following the explosive trained canine example, we have begun examining the vapor signatures for many of these volatile impurities utilizing high resolution spectroscopic techniques in several molecular fingerprint regions. Here we will describe some of these high resolution measurements and discuss strategies for selecting useful spectral signature regions for individual molecular markers of interest.

Approximations to complete basis set-extrapolated, highly correlated non-covalent interaction energies.

PubMed

Mackie, Iain D; DiLabio, Gino A

2011-10-07

The first-principles calculation of non-covalent (particularly dispersion) interactions between molecules is a considerable challenge. In this work we studied the binding energies for ten small non-covalently bonded dimers with several combinations of correlation methods (MP2, coupled-cluster single double, coupled-cluster single double (triple) (CCSD(T))), correlation-consistent basis sets (aug-cc-pVXZ, X = D, T, Q), two-point complete basis set energy extrapolations, and counterpoise corrections. For this work, complete basis set results were estimated from averaged counterpoise and non-counterpoise-corrected CCSD(T) binding energies obtained from extrapolations with aug-cc-pVQZ and aug-cc-pVTZ basis sets. It is demonstrated that, in almost all cases, binding energies converge more rapidly to the basis set limit by averaging the counterpoise and non-counterpoise corrected values than by using either counterpoise or non-counterpoise methods alone. Examination of the effect of basis set size and electron correlation shows that the triples contribution to the CCSD(T) binding energies is fairly constant with the basis set size, with a slight underestimation with CCSD(T)∕aug-cc-pVDZ compared to the value at the (estimated) complete basis set limit, and that contributions to the binding energies obtained by MP2 generally overestimate the analogous CCSD(T) contributions. Taking these factors together, we conclude that the binding energies for non-covalently bonded systems can be accurately determined using a composite method that combines CCSD(T)∕aug-cc-pVDZ with energy corrections obtained using basis set extrapolated MP2 (utilizing aug-cc-pVQZ and aug-cc-pVTZ basis sets), if all of the components are obtained by averaging the counterpoise and non-counterpoise energies. With such an approach, binding energies for the set of ten dimers are predicted with a mean absolute deviation of 0.02 kcal/mol, a maximum absolute deviation of 0.05 kcal/mol, and a mean percent absolute deviation of only 1.7%, relative to the (estimated) complete basis set CCSD(T) results. Use of this composite approach to an additional set of eight dimers gave binding energies to within 1% of previously published high-level data. It is also shown that binding within parallel and parallel-crossed conformations of naphthalene dimer is predicted by the composite approach to be 9% greater than that previously reported in the literature. The ability of some recently developed dispersion-corrected density-functional theory methods to predict the binding energies of the set of ten small dimers was also examined. © 2011 American Institute of Physics

Assessment of the GECKO-A Modeling Tool and Simplified 3D Model Parameterizations for SOA Formation

NASA Astrophysics Data System (ADS)

Aumont, B.; Hodzic, A.; La, S.; Camredon, M.; Lannuque, V.; Lee-Taylor, J. M.; Madronich, S.

2014-12-01

Explicit chemical mechanisms aim to embody the current knowledge of the transformations occurring in the atmosphere during the oxidation of organic matter. These explicit mechanisms are therefore useful tools to explore the fate of organic matter during its tropospheric oxidation and examine how these chemical processes shape the composition and properties of the gaseous and the condensed phases. Furthermore, explicit mechanisms provide powerful benchmarks to design and assess simplified parameterizations to be included 3D model. Nevertheless, the explicit mechanism describing the oxidation of hydrocarbons with backbones larger than few carbon atoms involves millions of secondary organic compounds, far exceeding the size of chemical mechanisms that can be written manually. Data processing tools can however be designed to overcome these difficulties and automatically generate consistent and comprehensive chemical mechanisms on a systematic basis. The Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) has been developed for the automatic writing of explicit chemical schemes of organic species and their partitioning between the gas and condensed phases. GECKO-A can be viewed as an expert system that mimics the steps by which chemists might develop chemical schemes. GECKO-A generates chemical schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In its current version, GECKO-A can generate the full atmospheric oxidation scheme for most linear, branched and cyclic precursors, including alkanes and alkenes up to C25. Assessments of the GECKO-A modeling tool based on chamber SOA observations will be presented. GECKO-A was recently used to design a parameterization for SOA formation based on a Volatility Basis Set (VBS) approach. First results will be presented.

Communication: A novel implementation to compute MP2 correlation energies without basis set superposition errors and complete basis set extrapolation.

PubMed

Dixit, Anant; Claudot, Julien; Lebègue, Sébastien; Rocca, Dario

2017-06-07

By using a formulation based on the dynamical polarizability, we propose a novel implementation of second-order Møller-Plesset perturbation (MP2) theory within a plane wave (PW) basis set. Because of the intrinsic properties of PWs, this method is not affected by basis set superposition errors. Additionally, results are converged without relying on complete basis set extrapolation techniques; this is achieved by using the eigenvectors of the static polarizability as an auxiliary basis set to compactly and accurately represent the response functions involved in the MP2 equations. Summations over the large number of virtual states are avoided by using a formalism inspired by density functional perturbation theory, and the Lanczos algorithm is used to include dynamical effects. To demonstrate this method, applications to three weakly interacting dimers are presented.

Diel variation in fig volatiles across syconium development: making sense of scents.

PubMed

Borges, Renee M; Bessière, Jean-Marie; Ranganathan, Yuvaraj

2013-05-01

Plants produce volatile organic compounds (VOCs) in a variety of contexts that include response to abiotic and biotic stresses, attraction of pollinators and parasitoids, and repulsion of herbivores. Some of these VOCs may also exhibit diel variation in emission. In Ficus racemosa, we examined variation in VOCs released by fig syconia throughout syconium development and between day and night. Syconia are globular enclosed inflorescences that serve as developing nurseries for pollinating and parasitic fig wasps. Syconia are attacked by gallers early in their development, serviced by pollinators in mid phase, and are attractive to parasitoids in response to the development of gallers at later stages. VOC bouquets of the different development phases of the syconium were distinctive, as were their day and night VOC profiles. VOCs such as α-muurolene were characteristic of the pollen-receptive diurnal phase, and may serve to attract the diurnally-active pollinating wasps. Diel patterns of release of volatiles could not be correlated with their predicted volatility as determined by Henry's law constants at ambient temperatures. Therefore, factors other than Henry's law constant such as stomatal conductance or VOC synthesis must explain diel variation in VOC emission. A novel use of weighted gene co-expression network analysis (WGCNA) on the volatilome resulted in seven distinct modules of co-emitted VOCs that could be interpreted on the basis of syconium ecology. Some modules were characterized by the response of fig syconia to early galling by parasitic wasps and consisted largely of green leaf volatiles (GLVs). Other modules, that could be characterized by a combination of syconia response to oviposition and tissue feeding by larvae of herbivorous galler pollinators as well as of parasitized wasps, consisted largely of putative herbivore-induced plant volatiles (HIPVs). We demonstrated the usefulness of WGCNA analysis of the volatilome in making sense of the scents produced by the syconia at different stages and diel phases of their development.

Atomic Oxygen Interactions With Silicone Contamination on Spacecraft in Low Earth Orbit Studied

NASA Technical Reports Server (NTRS)

Banks, Bruce A.

2001-01-01

Silicones have been widely used on spacecraft as potting compounds, adhesives, seals, gaskets, hydrophobic surfaces, and atomic oxygen protective coatings. Contamination of optical and thermal control surfaces on spacecraft in low Earth orbit (LEO) has been an ever-present problem as a result of the interaction of atomic oxygen with volatile species from silicones and hydrocarbons onboard spacecraft. These interactions can deposit a contaminant that is a risk to spacecraft performance because it can form an optically absorbing film on the surfaces of Sun sensors, star trackers, or optical components or can increase the solar absorptance of thermal control surfaces. The transmittance, absorptance, and reflectance of such contaminant films seem to vary widely from very transparent SiOx films to much more absorbing SiOx-based films that contain hydrocarbons. At the NASA Glenn Research Center, silicone contamination that was oxidized by atomic oxygen has been examined from LEO spacecraft (including the Long Duration Exposure Facility and the Mir space station solar arrays) and from ground laboratory LEO simulations. The findings resulted in the development of predictive models that may help explain the underlying issues and effects. Atomic oxygen interactions with silicone volatiles and mixtures of silicone and hydrocarbon volatiles produce glassy SiOx-based contaminant coatings. The addition of hydrocarbon volatiles in the presence of silicone volatiles appears to cause much more absorbing (and consequently less transmitting) contaminant films than when no hydrocarbon volatiles are present. On the basis of the LDEF and Mir results, conditions of high atomic oxygen flux relative to low contaminant flux appear to result in more transparent contaminant films than do conditions of low atomic oxygen flux with high contaminant flux. Modeling predictions indicate that the deposition of contaminant films early in a LEO flight should depend much more on atomic oxygen flux than it does later in a mission.

Correlation consistent valence basis sets for use with the Stuttgart-Dresden-Bonn relativistic effective core potentials: The atoms Ga-Kr and In-Xe

NASA Astrophysics Data System (ADS)

Martin, Jan M. L.; Sundermann, Andreas

2001-02-01

We propose large-core correlation-consistent (cc) pseudopotential basis sets for the heavy p-block elements Ga-Kr and In-Xe. The basis sets are of cc-pVTZ and cc-pVQZ quality, and have been optimized for use with the large-core (valence-electrons only) Stuttgart-Dresden-Bonn (SDB) relativistic pseudopotentials. Validation calculations on a variety of third-row and fourth-row diatomics suggest them to be comparable in quality to the all-electron cc-pVTZ and cc-pVQZ basis sets for lighter elements. Especially the SDB-cc-pVQZ basis set in conjunction with a core polarization potential (CPP) yields excellent agreement with experiment for compounds of the later heavy p-block elements. For accurate calculations on Ga (and, to a lesser extent, Ge) compounds, explicit treatment of 13 valence electrons appears to be desirable, while it seems inevitable for In compounds. For Ga and Ge, we propose correlation consistent basis sets extended for (3d) correlation. For accurate calculations on organometallic complexes of interest to homogenous catalysis, we recommend a combination of the standard cc-pVTZ basis set for first- and second-row elements, the presently derived SDB-cc-pVTZ basis set for heavier p-block elements, and for transition metals, the small-core [6s5p3d] Stuttgart-Dresden basis set-relativistic effective core potential combination supplemented by (2f1g) functions with exponents given in the Appendix to the present paper.

Filter-based chemical sensors for hazardous materials

NASA Astrophysics Data System (ADS)

Major, Kevin J.; Ewing, Kenneth J.; Poutous, Menelaos K.; Sanghera, Jasbinder S.; Aggarwal, Ishwar D.

2014-05-01

The development of new techniques for the detection of homemade explosive devices is an area of intense research for the defense community. Such sensors must exhibit high selectivity to detect explosives and/or explosives related materials in a complex environment. Spectroscopic techniques such as FTIR are capable of discriminating between the volatile components of explosives; however, there is a need for less expensive systems for wide-range use in the field. To tackle this challenge we are investigating the use of multiple, overlapping, broad-band infrared (IR) filters to enable discrimination of volatile chemicals associated with an explosive device from potential background interferants with similar chemical signatures. We present an optical approach for the detection of fuel oil (the volatile component in ammonium nitrate-fuel oil explosives) that relies on IR absorption spectroscopy in a laboratory environment. Our proposed system utilizes a three filter set to separate the IR signals from fuel oil and various background interferants in the sample headspace. Filter responses for the chemical spectra are calculated using a Gaussian filter set. We demonstrate that using a specifically chosen filter set enables discrimination of pure fuel oil, hexanes, and acetone, as well as various mixtures of these components. We examine the effects of varying carrier gasses and humidity on the collected spectra and corresponding filter response. We study the filter response on these mixtures over time as well as present a variety of methods for observing the filter response functions to determine the response of this approach to detecting fuel oil in various environments.

Probability of Elevated Volatile Organic Compound (VOC) Concentrations in Groundwater in the Eagle River Watershed Valley-Fill Aquifer, Eagle County, North-Central Colorado, 2006-2007

USGS Publications Warehouse

Rupert, Michael G.; Plummer, Niel

2009-01-01

This raster data set delineates the predicted probability of elevated volatile organic compound (VOC) concentrations in groundwater in the Eagle River watershed valley-fill aquifer, Eagle County, North-Central Colorado, 2006-2007. This data set was developed by a cooperative project between the U.S. Geological Survey, Eagle County, the Eagle River Water and Sanitation District, the Town of Eagle, the Town of Gypsum, and the Upper Eagle Regional Water Authority. This project was designed to evaluate potential land-development effects on groundwater and surface-water resources so that informed land-use and water management decisions can be made. This groundwater probability map and its associated probability maps was developed as follows: (1) A point data set of wells with groundwater quality and groundwater age data was overlaid with thematic layers of anthropogenic (related to human activities) and hydrogeologic data by using a geographic information system to assign each well values for depth to groundwater, distance to major streams and canals, distance to gypsum beds, precipitation, soils, and well depth. These data then were downloaded to a statistical software package for analysis by logistic regression. (2) Statistical models predicting the probability of elevated nitrate concentrations, the probability of unmixed young water (using chlorofluorocarbon-11 concentrations and tritium activities), and the probability of elevated volatile organic compound concentrations were developed using logistic regression techniques. (3) The statistical models were entered into a GIS and the probability map was constructed.

Hybrid Grid and Basis Set Approach to Quantum Chemistry DMRG

NASA Astrophysics Data System (ADS)

Stoudenmire, Edwin Miles; White, Steven

We present a new approach for using DMRG for quantum chemistry that combines the advantages of a basis set with that of a grid approximation. Because DMRG scales linearly for quasi-one-dimensional systems, it is feasible to approximate the continuum with a fine grid in one direction while using a standard basis set approach for the transverse directions. Compared to standard basis set methods, we reach larger systems and achieve better scaling when approaching the basis set limit. The flexibility and reduced costs of our approach even make it feasible to incoporate advanced DMRG techniques such as simulating real-time dynamics. Supported by the Simons Collaboration on the Many-Electron Problem.

Dynamics of Metabolite Induction in Fungal Co-cultures by Metabolomics at Both Volatile and Non-volatile Levels

PubMed Central

Azzollini, Antonio; Boggia, Lorenzo; Boccard, Julien; Sgorbini, Barbara; Lecoultre, Nicole; Allard, Pierre-Marie; Rubiolo, Patrizia; Rudaz, Serge; Gindro, Katia; Bicchi, Carlo; Wolfender, Jean-Luc

2018-01-01

Fungal co-cultivation has emerged as a promising way for activating cryptic biosynthetic pathways and discovering novel antimicrobial metabolites. For the success of such studies, a key element remains the development of standardized co-cultivation methods compatible with high-throughput analytical procedures. To efficiently highlight induction processes, it is crucial to acquire a holistic view of intermicrobial communication at the molecular level. To tackle this issue, a strategy was developed based on the miniaturization of fungal cultures that allows for a concomitant survey of induction phenomena in volatile and non-volatile metabolomes. Fungi were directly grown in vials, and each sample was profiled by head space solid phase microextraction gas chromatography mass spectrometry (HS-SPME-GC-MS), while the corresponding solid culture medium was analyzed by liquid chromatography high resolution mass spectrometry (LC-HRMS) after solvent extraction. This strategy was implemented for the screening of volatile and non-volatile metabolite inductions in an ecologically relevant fungal co-culture of Eutypa lata (Pers.) Tul. & C. Tul. (Diatrypaceae) and Botryosphaeria obtusa (Schwein.) Shoemaker (Botryosphaeriaceae), two wood-decaying fungi interacting in the context of esca disease of grapevine. For a comprehensive evaluation of the results, a multivariate data analysis combining Analysis of Variance and Partial Least Squares approaches, namely AMOPLS, was used to explore the complex LC-HRMS and GC-MS datasets and highlight dynamically induced compounds. A time-series study was carried out over 9 days, showing characteristic metabolite induction patterns in both volatile and non-volatile dimensions. Relevant links between the dynamics of expression of specific metabolite production were observed. In addition, the antifungal activity of 2-nonanone, a metabolite incrementally produced over time in the volatile fraction, was assessed against Eutypa lata and Botryosphaeria obtusa in an adapted bioassay set for volatile compounds. This compound has shown antifungal activity on both fungi and was found to be co-expressed with a known antifungal compound, O-methylmellein, induced in solid media. This strategy could help elucidate microbial inter- and intra-species cross-talk at various levels. Moreover, it supports the study of concerted defense/communication mechanisms for efficiently identifying original antimicrobials. PMID:29459851

Possible climates on terrestrial exoplanets.

PubMed

Forget, F; Leconte, J

2014-04-28

What kind of environment may exist on terrestrial planets around other stars? In spite of the lack of direct observations, it may not be premature to speculate on exoplanetary climates, for instance, to optimize future telescopic observations or to assess the probability of habitable worlds. To begin with, climate primarily depends on (i) the atmospheric composition and the volatile inventory; (ii) the incident stellar flux; and (iii) the tidal evolution of the planetary spin, which can notably lock a planet with a permanent night side. The atmospheric composition and mass depends on complex processes, which are difficult to model: origins of volatiles, atmospheric escape, geochemistry, photochemistry, etc. We discuss physical constraints, which can help us to speculate on the possible type of atmosphere, depending on the planet size, its final distance for its star and the star type. Assuming that the atmosphere is known, the possible climates can be explored using global climate models analogous to the ones developed to simulate the Earth as well as the other telluric atmospheres in the solar system. Our experience with Mars, Titan and Venus suggests that realistic climate simulators can be developed by combining components, such as a 'dynamical core', a radiative transfer solver, a parametrization of subgrid-scale turbulence and convection, a thermal ground model and a volatile phase change code. On this basis, we can aspire to build reliable climate predictors for exoplanets. However, whatever the accuracy of the models, predicting the actual climate regime on a specific planet will remain challenging because climate systems are affected by strong positive feedbacks. They can drive planets with very similar forcing and volatile inventory to completely different states. For instance, the coupling among temperature, volatile phase changes and radiative properties results in instabilities, such as runaway glaciations and runaway greenhouse effect.

Transient Receptor Potential Channels Encode Volatile Chemicals Sensed by Rat Trigeminal Ganglion Neurons

PubMed Central

Schöbel, Nicole; Beltrán, Leopoldo; Wetzel, Christian Horst; Hatt, Hanns

2013-01-01

Primary sensory afferents of the dorsal root and trigeminal ganglia constantly transmit sensory information depicting the individual’s physical and chemical environment to higher brain regions. Beyond the typical trigeminal stimuli (e.g. irritants), environmental stimuli comprise a plethora of volatile chemicals with olfactory components (odorants). In spite of a complete loss of their sense of smell, anosmic patients may retain the ability to roughly discriminate between different volatile compounds. While the detailed mechanisms remain elusive, sensory structures belonging to the trigeminal system seem to be responsible for this phenomenon. In order to gain a better understanding of the mechanisms underlying the activation of the trigeminal system by volatile chemicals, we investigated odorant-induced membrane potential changes in cultured rat trigeminal neurons induced by the odorants vanillin, heliotropyl acetone, helional, and geraniol. We observed the dose-dependent depolarization of trigeminal neurons upon application of these substances occurring in a stimulus-specific manner and could show that distinct neuronal populations respond to different odorants. Using specific antagonists, we found evidence that TRPA1, TRPM8, and/or TRPV1 contribute to the activation. In order to further test this hypothesis, we used recombinantly expressed rat and human variants of these channels to investigate whether they are indeed activated by the odorants tested. We additionally found that the odorants dose-dependently inhibit two-pore potassium channels TASK1 and TASK3 heterologously expressed In Xenopus laevis oocytes. We suggest that the capability of various odorants to activate different TRP channels and to inhibit potassium channels causes neuronal depolarization and activation of distinct subpopulations of trigeminal sensory neurons, forming the basis for a specific representation of volatile chemicals in the trigeminal ganglia. PMID:24205061

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

NASA Technical Reports Server (NTRS)

Ishiwatari, R.; Ishiwatari, M.; Rohrback, B. G.; Kaplan, I. R.

1977-01-01

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5-116 hr) and temperatures (150-410 C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid less than 1%. The volatiles produced by heating the lipid and humic acid fractions were largely CO2 and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C2-C4 hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.

Density functional theory calculations of the lowest energy quintet and triplet states of model hemes: role of functional, basis set, and zero-point energy corrections.

PubMed

Khvostichenko, Daria; Choi, Andrew; Boulatov, Roman

2008-04-24

We investigated the effect of several computational variables, including the choice of the basis set, application of symmetry constraints, and zero-point energy (ZPE) corrections, on the structural parameters and predicted ground electronic state of model 5-coordinate hemes (iron(II) porphines axially coordinated by a single imidazole or 2-methylimidazole). We studied the performance of B3LYP and B3PW91 with eight Pople-style basis sets (up to 6-311+G*) and B97-1, OLYP, and TPSS functionals with 6-31G and 6-31G* basis sets. Only hybrid functionals B3LYP, B3PW91, and B97-1 reproduced the quintet ground state of the model hemes. With a given functional, the choice of the basis set caused up to 2.7 kcal/mol variation of the quintet-triplet electronic energy gap (DeltaEel), in several cases, resulting in the inversion of the sign of DeltaEel. Single-point energy calculations with triple-zeta basis sets of the Pople (up to 6-311G++(2d,2p)), Ahlrichs (TZVP and TZVPP), and Dunning (cc-pVTZ) families showed the same trend. The zero-point energy of the quintet state was approximately 1 kcal/mol lower than that of the triplet, and accounting for ZPE corrections was crucial for establishing the ground state if the electronic energy of the triplet state was approximately 1 kcal/mol less than that of the quintet. Within a given model chemistry, effects of symmetry constraints and of a "tense" structure of the iron porphine fragment coordinated to 2-methylimidazole on DeltaEel were limited to 0.3 kcal/mol. For both model hemes the best agreement with crystallographic structural data was achieved with small 6-31G and 6-31G* basis sets. Deviation of the computed frequency of the Fe-Im stretching mode from the experimental value with the basis set decreased in the order: nonaugmented basis sets, basis sets with polarization functions, and basis sets with polarization and diffuse functions. Contraction of Pople-style basis sets (double-zeta or triple-zeta) affected the results insignificantly for iron(II) porphyrin coordinated with imidazole. Poor performance of a "locally dense" basis set with a large number of basis functions on the Fe center was observed in calculation of quintet-triplet gaps. Our results lead to a series of suggestions for density functional theory calculations of quintet-triplet energy gaps in ferrohemes with a single axial imidazole; these suggestions are potentially applicable for other transition-metal complexes.

Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

NASA Astrophysics Data System (ADS)

Yahya, Khairunnisa; Glotfelty, Timothy; Wang, Kai; Zhang, Yang; Nenes, Athanasios

2017-06-01

Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from -40.8 % to a range of -34.6 to -27.7 %), with large differences between CB05-CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes (2005) series reduces the large negative CDNC bias associated with the default Abdul Razzak and Ghan (2000) parameterization from -35.4 % to a range of -0.8 to 7.1 %. However, it increases the errors due to overpredictions of CDNC, mainly over the northeastern US. This work indicates a need to improve other aerosol-cloud-radiation processes in the model, such as the spatial distribution of aerosol optical depth and cloud condensation nuclei, in order to further improve CDNC predictions.

Carbon and sulfur budget of the silicate Earth explained by accretion of differentiated planetary embryos

NASA Astrophysics Data System (ADS)

Li, Yuan; Dasgupta, Rajdeep; Tsuno, Kyusei; Monteleone, Brian; Shimizu, Nobumichi

2016-10-01

The abundances of volatile elements in the Earth's mantle have been attributed to the delivery of volatile-rich material after the main phase of accretion. However, no known meteorites could deliver the volatile elements, such as carbon, nitrogen, hydrogen and sulfur, at the relative abundances observed for the silicate Earth. Alternatively, Earth could have acquired its volatile inventory during accretion and differentiation, but the fate of volatile elements during core formation is known only for a limited set of conditions. Here we present constraints from laboratory experiments on the partitioning of carbon and sulfur between metallic cores and silicate mantles under conditions relevant for rocky planetary bodies. We find that carbon remains more siderophile than sulfur over a range of oxygen fugacities; however, our experiments suggest that in reduced or sulfur-rich bodies, carbon is expelled from the segregating core. Combined with previous constraints, we propose that the ratio of carbon to sulfur in the silicate Earth could have been established by differentiation of a planetary embryo that was then accreted to the proto-Earth. We suggest that the accretion of a Mercury-like (reduced) or a sulfur-rich (oxidized) differentiated body--in which carbon has been preferentially partitioned into the mantle--may explain the Earth's carbon and sulfur budgets.

Stochastic model of financial markets reproducing scaling and memory in volatility return intervals

NASA Astrophysics Data System (ADS)

Gontis, V.; Havlin, S.; Kononovicius, A.; Podobnik, B.; Stanley, H. E.

2016-11-01

We investigate the volatility return intervals in the NYSE and FOREX markets. We explain previous empirical findings using a model based on the interacting agent hypothesis instead of the widely-used efficient market hypothesis. We derive macroscopic equations based on the microscopic herding interactions of agents and find that they are able to reproduce various stylized facts of different markets and different assets with the same set of model parameters. We show that the power-law properties and the scaling of return intervals and other financial variables have a similar origin and could be a result of a general class of non-linear stochastic differential equations derived from a master equation of an agent system that is coupled by herding interactions. Specifically, we find that this approach enables us to recover the volatility return interval statistics as well as volatility probability and spectral densities for the NYSE and FOREX markets, for different assets, and for different time-scales. We find also that the historical S&P500 monthly series exhibits the same volatility return interval properties recovered by our proposed model. Our statistical results suggest that human herding is so strong that it persists even when other evolving fluctuations perturbate the financial system.

The dose-response relationship between the patch test and ROAT and the potential use for regulatory purposes.

PubMed

Fischer, Louise Arup; Voelund, Aage; Andersen, Klaus Ejner; Menné, Torkil; Johansen, Jeanne Duus

2009-10-01

Allergic contact dermatitis is common and can be prevented. The relationship between thresholds for patch tests and the repeated open application test (ROAT) is unclear. It would be desirable if patch test and ROAT data from already sensitized individuals could be used in prevention. The aim was to develop an equation that could predict the response to an allergen in a ROAT based on the dose-response curve derived by patch testing. Results from two human experimental elicitation studies with non-volatile allergens, nickel and the preservative methyldibromo glutaronitrile (MDBGN), were analysed by logistic dose-response statistics. The relation for volatile compounds was investigated using the results from experiments with the fragrance chemicals hydroxyisohexyl 3-cyclohexene carboxaldehyde and isoeugenol. For non-volatile compounds, the outcome of a ROAT can be estimated from the patch test by: ED(xx)(ROAT) = 0.0296 ED(xx)(patch test). For volatile compounds, the equation predicts that the response in the ROAT is more severe than the patch test response, but it overestimates the response. This equation may be used for non-volatile compounds other than nickel and MDBGN, after further validation. The relationship between the patch test and the ROAT can be used for prevention, to set safe levels of allergen exposure based on patch test data.

Spin-coated thin films of different metal phthalocyanines and porphyrin-phthalocyanine blend for optochemical sensors of volatile organic compounds

NASA Astrophysics Data System (ADS)

Rella, Roberto; Capone, Simona; Siciliano, Pietro; Spadavecchia, J.; Ciccarella, G.

2004-06-01

Spin-coated layers of ZnPc and CuP have been used as chemically interacting materials for the detection of alcohols, amines, ketones, alkanes and pyridine for applications in food quality control. The UV-VIS variations obtained by the exposure of the sensing layers to the mentioned analytes in controlled atmosphere have been analyzed and compared with those deriving by a single thin film obtained by mixing the two metal complexes in an appropriate ratio. A multichannel monitoring of the main bands of the sensing layer due to the interaction with the analyte vapors became the basis to construct a set of independent sensors located on a single sensing element. The effects in the variation of the absorption bands of the blend system are compared with the variations in absorbance observed with the two sensing layers fabricated separately with each single compound. The interaction between the VOCs species and the heterogeneous sensing layer shows a different behavior in the responses respect to the results obtained with each single compound.

Effects of Flavor and Texture on the Sensory Perception of Gouda-Type Cheese Varieties during Ripening Using Multivariate Analysis.

PubMed

Shiota, Makoto; Iwasawa, Ai; Suzuki-Iwashima, Ai; Iida, Fumiko

2015-12-01

The impact of flavor composition, texture, and other factors on desirability of different commercial sources of Gouda-type cheese using multivariate analyses on the basis of sensory and instrumental analyses were investigated. Volatile aroma compounds were measured using headspace solid-phase microextraction gas chromatography/mass spectrometry (GC/MS) and steam distillation extraction (SDE)-GC/MS, and fatty acid composition, low-molecular-weight compounds, including amino acids, and organic acids, as well pH, texture, and color were measured to determine their relationship with sensory perception. Orthogonal partial least squares-discriminant analysis (OPLS-DA) was performed to discriminate between 2 different ripening periods in 7 sample sets, revealing that ethanol, ethyl acetate, hexanoic acid, and octanoic acid increased with increasing sensory attribute scores for sweetness, fruity, and sulfurous. A partial least squares (PLS) regression model was constructed to predict the desirability of cheese using these parameters. We showed that texture and buttery flavors are important factors affecting the desirability of Gouda-type cheeses for Japanese consumers using these multivariate analyses. © 2015 Institute of Food Technologists®

Validation and Application of Pharmacokinetic Models for Interspecies Extrapolations in Toxicity Risk Assessments of Volatile Organics

DTIC Science & Technology

1988-08-30

Ai _.. ;:: -- I. OVERALL OBJECTIVE AND STATEMENT OF WORK The overall objective of the proposed project is to investigate the scientific basis...development and inter-species correlations with toxicity. A second series of tissue disposition experiments will be conducted to determine what ...elimination of halocarbons is hepatic metabolism. If metabolism plays a significant role in the disposition and subsequent neurobehavioral effects of

A Comprehensive Program for Measurement of Military Aircraft Emissions

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

Cheng, Mengdawn

2009-11-01

Emissions of gases and particulate matter by military aircraft were characterized inplume by 'extractive' and 'optical remote-sensing (ORS)' technologies. Non-volatile particle size distribution, number and mass concentrations were measured with good precision and reproducibly. Time-integrated particulate filter samples were collected and analyzed for smoke number, elemental composition, carbon contents, and sulfate. Observed at EEP the geometric mean diameter (as measured by the mobility diameter) generally increased as the engine power setting increased, which is consistent with downstream observations. The modal diameters at the downstream locations are larger than that at EEP at the same engine power level. The results indicatemore » that engine particles were processed by condensation, for example, leading to particle growth in-plume. Elemental analysis indicated little metals were present in the exhaust, while most of the exhaust materials in the particulate phase were carbon and sulfate (in the JP-8 fuel). CO, CO{sub 2}, NO, NO{sub 2}, SO{sub 2}, HCHO, ethylene, acetylene, propylene, and alkanes were measured. The last five species were most noticeable under engine idle condition. The levels of hydrocarbons emitted at high engine power level were generally below the detection limits. ORS techniques yielded real-time gaseous measurement, but the same techniques could not be extended directly to ultrafine particles found in all engine exhausts. The results validated sampling methodology and measurement techniques used for non-volatile particulate aircraft emissions, which also highlighted the needs for further research on sampling and measurement for volatile particulate matter and semi-volatile species in the engine exhaust especially at the low engine power setting.« less

Vortex-ultrasound-assisted dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the analysis of volatile bioactive components and comparative pharmacokinetic study of the herb-herb interactions in Guanxin Shutong Capsule.

PubMed

Mu, Jingqing; Gao, Xun; Li, Qing; Yang, Xiaomei; Yang, Wenling; Sun, Xu; Bi, Kaishun; Zhang, Huifen

2017-08-01

Guanxin Shutong Capsule, an effective traditional Chinese medicine, is widely used for coronary heart disease clinically. Volatile components are one of its important bioactive constituents. To better understand the material basis for the therapeutic effects, the components of Guanxin Shutong Capsule absorbed into the blood and their metabolites were identified based on gas chromatography with mass spectrometry coupled with vortex-ultrasound-assisted dispersive liquid-liquid microextraction. As a result, three prototypes and 15 metabolites were identified or tentatively characterized in rat plasma. Subsequently, a pharmacokinetic study was carried out to monitor the concentrations of the main bioactive constituents and metabolites (isoborneol, borneol, eugenol, and camphor) by gas chromatography with mass spectrometry in rat plasma following oral administration of single herb extract and different combinations of herbs in this prescription. Compared to other groups, a statistically significant difference of the pharmacokinetic properties was obtained when the total complex prescription was administered, indicating possible drug-drug interactions among the complex ingredients of Guanxin Shutong Capsule. These findings provided an experimental basis concerning the clinical application and medicinal efficacy of Guanxin Shutong Capsule in the treatment of coronary heart disease. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbon source potential and maturation in eocene New Zealand vitrinite-rich coals: Insights from traditional coal analyses, and Rock-Eval and biomarker studies

USGS Publications Warehouse

Newman, J.; Price, L.C.; Johnston, J.H.

1997-01-01

The results of traditional methods of coal characterisation (proximate, specific energy, and ultimate analyses) for 28 Eocene coal samples from the West Coast of New Zealand correspond well with biomarker ratios and Rock-Eval analyses. Isorank variations in vitrinite fluorescence and reflectance recorded for these samples are closely related to their volatile-matter content, and therefore indicate that the original vitrinite chemistry is a key controlling factor. By contrast, the mineral-matter content and the proportion of coal macerals present appear to have had only a minor influence on the coal samples' properties. Our analyses indicate that a number of triterpane biomarker ratios show peak maturities by high volatile bituminous A rank; apparent maturities are then reversed and decline at the higher medium volatile bituminous rank. The Rock-Eval S1 +S2 yield also maximizes by high volatile bituminous A rank, and then declines; however, this decline is retarded in samples with the most hydrogen-rich (perhydrous) vitrinites. These Rock-Eval and biomarker trends, as well as trends in traditional coal analyses, are used to define the rank at which expulsion of gas and oil occurs from the majority of the coals. This expulsion commences at high volatile A bituminous rank, and persists up to the threshold of medium volatile bituminous rank (c. 1.1% Ro ran. or 1.2% Ro max in this sample set), where marked hydrocarbon expulsion from perhydrous vitrinites begins to take place.

Social attraction mediated by fruit flies' microbiome.

PubMed

Venu, Isvarya; Durisko, Zachary; Xu, Jianping; Dukas, Reuven

2014-04-15

Larval and adult fruit flies are attracted to volatiles emanating from food substrates that have been occupied by larvae. We tested whether such volatiles are emitted by the larval gut bacteria by conducting tests under bacteria-free (axenic) conditions. We also tested attraction to two bacteria species, Lactobacillus brevis, which we cultured from larvae in our lab, and L. plantarum, a common constituent of fruit flies' microbiome in other laboratory populations and in wild fruit flies. Neither larvae nor adults showed attraction to axenic food that had been occupied by axenic larvae, but both showed the previously reported attraction to standard food that had been occupied by larvae with an intact microbiome. Larvae also showed significant attraction to volatiles from axenic food and larvae to which we added only either L. brevis or L. plantarum, and volatiles from L. brevis reared on its optimal growth medium. Controlled learning experiments indicated that larvae experienced with both standard and axenic used food do not perceive either as superior, while focal larvae experienced with simulated used food, which contains burrows, perceive it as superior to unused food. Our results suggest that flies rely on microbiome-derived volatiles for long-distance attraction to suitable food patches. Under natural settings, fruits often contain harmful fungi and bacteria, and both L. brevis and L. plantarum produce compounds that suppress the growth of some antagonistic fungi and bacteria. The larval microbiome volatiles may therefore lead prospective fruit flies towards substrates with a hospitable microbial environment.

Pluto's Global Surface Composition Through Pixel-by-Pixel Hapke Modeling of New Horizons Ralph LEISA Data

NASA Technical Reports Server (NTRS)

Protopapa, S.; Grundy, W. M.; Reuter, D. C.; Hamilton, D. P.; Dalle Ore, C. M.; Cook, J. C.; Cruikshank, D. P.; Schmitt, B.; Philippe, S.; Quirico, E.;

Pluto's global surface composition through pixel-by-pixel Hapke modeling of New Horizons Ralph/LEISA data

NASA Astrophysics Data System (ADS)

Protopapa, S.; Grundy, W. M.; Reuter, D. C.; Hamilton, D. P.; Dalle Ore, C. M.; Cook, J. C.; Cruikshank, D. P.; Schmitt, B.; Philippe, S.; Quirico, E.; Binzel, R. P.; Earle, A. M.; Ennico, K.; Howett, C. J. A.; Lunsford, A. W.; Olkin, C. B.; Parker, A.; Singer, K. N.; Stern, A.; Verbiscer, A. J.; Weaver, H. A.; Young, L. A.; New Horizons Science Team

2017-05-01

On July 14th 2015, NASA's New Horizons mission gave us an unprecedented detailed view of the Pluto system. The complex compositional diversity of Pluto's encounter hemisphere was revealed by the Ralph/LEISA infrared spectrometer on board of New Horizons. We present compositional maps of Pluto defining the spatial distribution of the abundance and textural properties of the volatiles methane and nitrogen ices and non-volatiles water ice and tholin. These results are obtained by applying a pixel-by-pixel Hapke radiative transfer model to the LEISA scans. Our analysis focuses mainly on the large scale latitudinal variations of methane and nitrogen ices and aims at setting observational constraints to volatile transport models. Specifically, we find three latitudinal bands: the first, enriched in methane, extends from the pole to 55°N, the second dominated by nitrogen, continues south to 35°N, and the third, composed again mainly of methane, reaches 20°N. We demonstrate that the distribution of volatiles across these surface units can be explained by differences in insolation over the past few decades. The latitudinal pattern is broken by Sputnik Planitia, a large reservoir of volatiles, with nitrogen playing the most important role. The physical properties of methane and nitrogen in this region are suggestive of the presence of a cold trap or possible volatile stratification. Furthermore our modeling results point to a possible sublimation transport of nitrogen from the northwest edge of Sputnik Planitia toward the south.

Gender, Emotion Work, and Relationship Quality: A Daily Diary Study

PubMed Central

Curran, Melissa A.; McDaniel, Brandon T.; Pollitt, Amanda M.; Totenhagen, Casey J.

2015-01-01

We use the gender relations perspective from feminist theorizing to investigate how gender and daily emotion work predict daily relationship quality in 74 couples (148 individuals in dating, cohabiting, or married relationships) primarily from the southwest U.S. Emotion work is characterized by activities that enhance others’ emotional well-being. We examined emotion work two ways: trait (individuals’ average levels) and state (individuals’ daily fluctuations). We examined actor and partner effects of emotion work and tested for gender differences. As outcome variables, we included six types of daily relationship quality: love, commitment, satisfaction, closeness, ambivalence, and conflict. This approach allowed us to predict three aspects of relationship quality: average levels, daily fluctuations, and volatility (overall daily variability across a week). Three patterns emerged. First, emotion work predicted relationship quality in this diverse set of couples. Second, gender differences were minimal for fixed effects: Trait and state emotion work predicted higher average scores on, and positive daily increases in, individuals’ own positive relationship quality and lower average ambivalence. Third, gender differences were more robust for volatility: For partner effects, having a partner who reported higher average emotion work predicted lower volatility in love, satisfaction, and closeness for women versus greater volatility in love and commitment for men. Neither gender nor emotion work predicted average levels, daily fluctuations, or volatility in conflict. We discuss implications and future directions pertaining to the unique role of gender in understanding the associations between daily emotion work and volatility in daily relationship quality for relational partners. PMID:26508808

Idiosyncratic risk in the Dow Jones Eurostoxx50 Index

NASA Astrophysics Data System (ADS)

Daly, Kevin; Vo, Vinh

2008-07-01

Recent evidence by Campbell et al. [J.Y. Campbell, M. Lettau B.G. Malkiel, Y. Xu, Have individual stocks become more volatile? An empirical exploration of idiosyncratic risk, The Journal of Finance (February) (2001)] shows an increase in firm-level volatility and a decline of the correlation among stock returns in the US. In relation to the Euro-Area stock markets, we find that both aggregate firm-level volatility and average stock market correlation have trended upwards. We estimate a linear model of the market risk-return relationship nested in an EGARCH(1, 1)-M model for conditional second moments. We then show that traditional estimates of the conditional risk-return relationship, that use ex-post excess-returns as the conditioning information set, lead to joint tests of the theoretical model (usually the ICAPM) and of the Efficient Market Hypothesis in its strong form. To overcome this problem we propose alternative measures of expected market risk based on implied volatility extracted from traded option prices and we discuss the conditions under which implied volatility depends solely on expected risk. We then regress market excess-returns on lagged market implied variance computed from implied market volatility to estimate the relationship between expected market excess-returns and expected market risk.We investigate whether, as predicted by the ICAPM, the expected market risk is the main factor in explaining the market risk premium and the latter is independent of aggregate idiosyncratic risk.

Gender, Emotion Work, and Relationship Quality: A Daily Diary Study.

PubMed

Curran, Melissa A; McDaniel, Brandon T; Pollitt, Amanda M; Totenhagen, Casey J

2015-08-01

We use the gender relations perspective from feminist theorizing to investigate how gender and daily emotion work predict daily relationship quality in 74 couples (148 individuals in dating, cohabiting, or married relationships) primarily from the southwest U.S. Emotion work is characterized by activities that enhance others' emotional well-being. We examined emotion work two ways: trait (individuals' average levels) and state (individuals' daily fluctuations). We examined actor and partner effects of emotion work and tested for gender differences. As outcome variables, we included six types of daily relationship quality: love, commitment, satisfaction, closeness, ambivalence, and conflict. This approach allowed us to predict three aspects of relationship quality: average levels, daily fluctuations, and volatility (overall daily variability across a week). Three patterns emerged. First, emotion work predicted relationship quality in this diverse set of couples. Second, gender differences were minimal for fixed effects: Trait and state emotion work predicted higher average scores on, and positive daily increases in, individuals' own positive relationship quality and lower average ambivalence. Third, gender differences were more robust for volatility: For partner effects, having a partner who reported higher average emotion work predicted lower volatility in love, satisfaction, and closeness for women versus greater volatility in love and commitment for men. Neither gender nor emotion work predicted average levels, daily fluctuations, or volatility in conflict. We discuss implications and future directions pertaining to the unique role of gender in understanding the associations between daily emotion work and volatility in daily relationship quality for relational partners.

Human skin volatiles: a review.

PubMed

Dormont, Laurent; Bessière, Jean-Marie; Cohuet, Anna

2013-05-01

Odors emitted by human skin are of great interest to biologists in many fields; applications range from forensic studies to diagnostic tools, the design of perfumes and deodorants, and the ecology of blood-sucking insect vectors of human disease. Numerous studies have investigated the chemical composition of skin odors, and various sampling methods have been used for this purpose. The literature shows that the chemical profile of skin volatiles varies greatly among studies, and the use of different sampling procedures is probably responsible for some of these variations. To our knowledge, this is the first review focused on human skin volatile compounds. We detail the different sampling techniques, each with its own set of advantages and disadvantages, which have been used for the collection of skin odors from different parts of the human body. We present the main skin volatile compounds found in these studies, with particular emphasis on the most frequently studied body regions, axillae, hands, and feet. We propose future directions for promising experimental studies on odors from human skin, particularly in relation to the chemical ecology of blood-sucking insects.

Characterization of Volatile Compounds with HS-SPME from Oxidized n-3 PUFA Rich Oils via Rancimat Tests.

PubMed

Yang, Kai-Min; Cheng, Ming-Ching; Chen, Chih-Wei; Tseng, Chin-Yin; Lin, Li-Yun; Chiang, Po-Yuan

2017-02-01

Algae oil and fish oil are n-3 PUFA mainstream commercial products. The various sources for the stability of n-3 PUFA oxidation are influenced by the fatty acid composition, extraction and refined processing. In this study, the oil stability index (OSI) occurs within 2.3 to 7.6 hours with three different n-3 PUFA rich oil. To set the OSI in the Rancimat test as the oil stability limit and observed various degrees of oxidation (0, 25, 50, 75, 100 and 125%). The volatile oxidation compounds were analyzed via headspace-solid phase microextraction (HS-SPME) and GC/MS. We detected 51 volatile compound variations during the oxidation, which were composed of aldehydes, hydrocarbons, cyclic compounds, alcohols, benzene compounds, ketones, furans, ester and pyrrolidine. The off-flavor characteristics can be strongly influenced by the synergy effects of volatile oxidation compounds. Chemometric analysis (PCA and AHC) was applied to identify the sensitive oxidation marker compounds, which included a (E,E)-2,4-heptadienal appropriate marker, via lipid oxidation in the n-3 PUFA rich oil.

Localized basis sets for unbound electrons in nanoelectronics.

PubMed

Soriano, D; Jacob, D; Palacios, J J

2008-02-21

It is shown how unbound electron wave functions can be expanded in a suitably chosen localized basis sets for any desired range of energies. In particular, we focus on the use of Gaussian basis sets, commonly used in first-principles codes. The possible usefulness of these basis sets in a first-principles description of field emission or scanning tunneling microscopy at large bias is illustrated by studying a simpler related phenomenon: The lifetime of an electron in a H atom subjected to a strong electric field.

Determination of volatile marker compounds of common coffee roast defects.

PubMed

Yang, Ni; Liu, Chujiao; Liu, Xingkun; Degn, Tina Kreuzfeldt; Munchow, Morten; Fisk, Ian

2016-11-15

Coffee beans from the same origin were roasted using six time-temperature profiles, in order to identify volatile aroma compounds associated with five common roast coffee defects (light, scorched, dark, baked and underdeveloped). Thirty-seven volatile aroma compounds were selected on the basis that they had previously been identified as potent odorants of coffee and were also identified in all coffee brew preparations; the relative abundance of these aroma compounds was then evaluated using gas chromatography mass spectrometry (GC-MS) with headspace solid phase micro extraction. Some of the 37 key aroma compounds were significantly changed in each coffee roast defect and changes in one marker compound was chosen for each defect type, that is, indole for light defect, 4-ethyl-2-methoxyphenol for scorched defect, phenol for dark defect, maltol for baked defect and 2,5-dimethylfuran for underdeveloped defect. The association of specific changes in aroma profiles for different roast defects has not been shown previously and could be incorporated into screening tools to enable the coffee industry quickly identify if roast defects occur during production. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Ammonia produced by bacterial colonies promotes growth of ampicillin-sensitive Serratia sp. by means of antibiotic inactivation.

PubMed

Cepl, Jaroslav; Blahůšková, Anna; Cvrčková, Fatima; Markoš, Anton

2014-05-01

Volatiles produced by bacterial cultures are known to induce regulatory and metabolic alterations in nearby con-specific or heterospecific bacteria, resulting in phenotypic changes including acquisition of antibiotic resistance. We observed unhindered growth of ampicillin-sensitive Serratia rubidaea and S. marcescens on ampicillin-containing media, when exposed to volatiles produced by dense bacterial growth. However, this phenomenon appeared to result from pH increase in the medium caused by bacterial volatiles rather than alterations in the properties of the bacterial cultures, as alkalization of ampicillin-containing culture media to pH 8.5 by ammonia or Tris exhibited the same effects, while pretreatment of bacterial cultures under the same conditions prior to antibiotic exposure did not increase ampicillin resistance. Ampicillin was readily inactivated at pH 8.5, suggesting that observed bacterial growth results from metabolic alteration of the medium, rather than an active change in the target bacterial population (i.e. induction of resistance or tolerance). However, even such seemingly simple mechanism may provide a biologically meaningful basis for protection against antibiotics in microbial communities growing on semi-solid media. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

BOREAS TGB-10 Volatile Organic Carbon Data over the SSA

NASA Technical Reports Server (NTRS)

Westberg, Hal; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor); Hall, Brad; Jackson, Andrea V.

2000-01-01

The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of biogenic hydrocarbon emissions with respect to boreal forest carbon cycles. This data set contains measured VOC concentrations. These data were obtained at the SSA-OJP site from May to September 1994. The data are stored in tabular ASCII files.

Near Hartree-Fock quality GTO basis sets for the second-row atoms

NASA Technical Reports Server (NTRS)

Partridge, Harry

1987-01-01

Energy optimized, near Hartree-Fock quality Gaussian basis sets ranging in size from (17s12p) to (20s15p) are presented for the ground states of the second-row atoms for Na(2P), Na(+), Na(-), Mg(3P), P(-), S(-), and Cl(-). In addition, optimized supplementary functions are given for the ground state basis sets to describe the negative ions, and the excited Na(2P) and Mg(3P) atomic states. The ratios of successive orbital exponents describing the inner part of the 1s and 2p orbitals are found to be nearly independent of both nuclear charge and basis set size. This provides a method of obtaining good starting estimates for other basis set optimizations.

Neutron Spectrometer Prospecting During the Mojave Volatiles Project Analog Field Test

NASA Technical Reports Server (NTRS)

Elphic, R. C.; Heldmann, J. L.; Colaprete, A.; Hunt, D. R.; Deans, M C.; Lim, D. S.; Foil, G.; Fong, T.

2015-01-01

We know there are volatiles sequestered at the poles of the Moon. While we have evidence of water ice and a number of other compounds based on remote sensing, the detailed distribution, and physical and chemical form are largely unknown. Additional orbital studies of lunar polar volatiles may yield further insights, but the most important next step is to use landed assets to fully characterize the volatile composition and distribution at scales of tens to hundreds of meters. To achieve this range of scales, mobility is needed. Because of the proximity of the Moon, near real-time operation of the surface assets is possible, with an associated reduction in risk and cost. This concept of operations is very different from that of rovers on Mars, and new operational approaches are required to carry out such real-time robotic exploration. The Mojave Volatiles Project (MVP) is a Moon- Mars Analog Mission Activities (MMAMA) program effort aimed at (1) determining effective approaches to operating a real-time but short-duration lunar surface robotic mission, and (2) performing prospecting science in a natural setting, as a test of these approaches. We know there are volatiles sequestered at the poles of the Moon. While we have evidence of water ice and a number of other compounds based on remote sensing, the detailed distribution, and physical and chemical form are largely unknown. Additional orbital studies of lunar polar volatiles may yield further insights, but the most important next step is to use landed assets to fully characterize the volatile composition and distribution at scales of tens to hundreds of meters. To achieve this range of scales, mobility is needed. Because of the proximity of the Moon, near real-time operation of the surface assets is possible, with an associated reduction in risk and cost. This concept of operations is very different from that of rovers on Mars, and new operational approaches are required to carry out such robotic exploration. The Mojave Volatiles Project (MVP) is a Moon- Mars Analog Mission Activities (MMAMA) program effort aimed at (1) determining effective approaches to operating a real-time but short-duration lunar surface robotic mission, and (2) performing prospecting science in a natural setting, as a test of these approaches. Here we describe some results from the first such test, carried out in the Mojave Desert between 16 and 24 October, 2014. The test site was an alluvial fan just E of the Soda Mountains, SW of Baker, California. This site contains desert pavements, ranging from the late Pleistocene to early-Holocene in age. These pavements are undergoing dissection by the ongoing development of washes. A principal objective was to determine the hydration state of different types of desert pavement and bare ground features. The mobility element of the test was provided by the KREX-2 rover, designed and operated by the Intelligent Robotics Group at NASA Ames Research Center.

Uncertainty quantification metrics for whole product life cycle cost estimates in aerospace innovation

NASA Astrophysics Data System (ADS)

Schwabe, O.; Shehab, E.; Erkoyuncu, J.

2015-08-01

The lack of defensible methods for quantifying cost estimate uncertainty over the whole product life cycle of aerospace innovations such as propulsion systems or airframes poses a significant challenge to the creation of accurate and defensible cost estimates. Based on the axiomatic definition of uncertainty as the actual prediction error of the cost estimate, this paper provides a comprehensive overview of metrics used for the uncertainty quantification of cost estimates based on a literature review, an evaluation of publicly funded projects such as part of the CORDIS or Horizon 2020 programs, and an analysis of established approaches used by organizations such NASA, the U.S. Department of Defence, the ESA, and various commercial companies. The metrics are categorized based on their foundational character (foundations), their use in practice (state-of-practice), their availability for practice (state-of-art) and those suggested for future exploration (state-of-future). Insights gained were that a variety of uncertainty quantification metrics exist whose suitability depends on the volatility of available relevant information, as defined by technical and cost readiness level, and the number of whole product life cycle phases the estimate is intended to be valid for. Information volatility and number of whole product life cycle phases can hereby be considered as defining multi-dimensional probability fields admitting various uncertainty quantification metric families with identifiable thresholds for transitioning between them. The key research gaps identified were the lacking guidance grounded in theory for the selection of uncertainty quantification metrics and lacking practical alternatives to metrics based on the Central Limit Theorem. An innovative uncertainty quantification framework consisting of; a set-theory based typology, a data library, a classification system, and a corresponding input-output model are put forward to address this research gap as the basis for future work in this field.

Relativistic Prolapse-Free Gaussian Basis Sets of Quadruple-ζ Quality: (aug-)RPF-4Z. III. The f-Block Elements.

PubMed

Teodoro, Tiago Quevedo; Visscher, Lucas; da Silva, Albérico Borges Ferreira; Haiduke, Roberto Luiz Andrade

2017-03-14

The f-block elements are addressed in this third part of a series of prolapse-free basis sets of quadruple-ζ quality (RPF-4Z). Relativistic adapted Gaussian basis sets (RAGBSs) are used as primitive sets of functions while correlating/polarization (C/P) functions are chosen by analyzing energy lowerings upon basis set increments in Dirac-Coulomb multireference configuration interaction calculations with single and double excitations of the valence spinors. These function exponents are obtained by applying the RAGBS parameters in a polynomial expression. Moreover, through the choice of C/P characteristic exponents from functions of lower angular momentum spaces, a reduction in the computational demand is attained in relativistic calculations based on the kinetic balance condition. The present study thus complements the RPF-4Z sets for the whole periodic table (Z ≤ 118). The sets are available as Supporting Information and can also be found at http://basis-sets.iqsc.usp.br .

Combination of large and small basis sets in electronic structure calculations on large systems

NASA Astrophysics Data System (ADS)

Røeggen, Inge; Gao, Bin

2018-04-01

Two basis sets—a large and a small one—are associated with each nucleus of the system. Each atom has its own separate one-electron basis comprising the large basis set of the atom in question and the small basis sets for the partner atoms in the complex. The perturbed atoms in molecules and solids model is at core of the approach since it allows for the definition of perturbed atoms in a system. It is argued that this basis set approach should be particularly useful for periodic systems. Test calculations are performed on one-dimensional arrays of H and Li atoms. The ground-state energy per atom in the linear H array is determined versus bond length.

Emission of biocides from treated materials: test procedures for water and air.

PubMed

Schoknecht, Ute; Wegner, Robby; Horn, Wolfgang; Jann, Oliver

2003-01-01

Methods for the determination of biocide emissions from treated materials into water and air were developed and tested in order to support a comparative ecological assessment of biocidal products. Leaching tests, experiments with simulated rain, extraction cleaning of carpets and emission chamber tests were performed with a series of treated materials. The experiments focused on the effect of changes in the procedure as well as characteristics of the specimens and demonstrate the suitability of the proposed methods for biocides of different product types. It was demonstrated that emissions of biocides into water can be compared on the basis of leaching tests in which the emission kinetics of the active ingredients are recorded. However, the water volume per surface area and the timetable for water changes have to be defined in such tests. Functions of flux rates related to time can be well described for inorganic compounds, whereas modelling of the data is more complicated for organic substances. Emission chamber tests using 20-litre and 23-litre glass exsiccators, originally developed to study volatile organic compounds, were successfully adapted for the investigation of the emission of biocides from treated materials which are usually semi volatile organic compounds. However test parameters and the method of analysis have to be adapted to the substances to be determined. Generally, it was found that the emission curves for the semi volatile organic compounds investigated differ from those of volatile organic compounds.

Impact of crema on the aroma release and the in-mouth sensory perception of espresso coffee.

PubMed

Barron, D; Pineau, N; Matthey-Doret, W; Ali, S; Sudre, J; Germain, J C; Kolodziejczyk, E; Pollien, P; Labbe, D; Jarisch, C; Dugas, V; Hartmann, C; Folmer, B

2012-09-01

A set of six espresso coffees with different foam characteristics and similar above cup and in-mouth flavour sensory profiles was produced by combination of two varying parameters, the extraction pressure and the filtration of the coffee beverage. The coffees were subsequently evaluated in a comparative manner by a set of analytical (headspace, nose-space) and sensory (Temporal Dominance of Sensations) techniques. The presence of espresso crema in its standard quantity was demonstrated to be associated with the optimum release of pleasant high volatiles, both in the above cup headspace and in-mouth. On the other hand, the TDS study demonstrated that increasing amount of crema was associated with increasing roasted dominance along coffee consumption. Furthermore, a parallel was established between the roasted sensory dominance and the dominant release of 2-methylfuran in the nose-space. This was, however, an indirect link as 2-methylfuran was indeed a chemical marker of roasting but does not contribute to the roasted aroma. Lowering the standard amount of crema by filtration clearly decreased the release of pleasant high volatiles and the in-mouth roasted sensory dominance. On the other hand, increasing the usual crema volume by increasing the extraction pressure did not bring any added value concerning the above cup and in-mouth release of pleasant high volatiles.

[Determination of methyl nonyl ketone in volatile oil from herbs of Houttuynia cordata by GC-MS].

PubMed

Yang, Lixin; Zhang, Yongxin; Yi, Hong; Yang, Hua; Zhang, Qiwei

2010-08-01

To develop a GC-MS method for the determination of methyl nonyl ketone in the volatile oil from the herbs of Houttuynia cordata. The sample was split in the 240 degrees C injection port, with 20:1 split ratio, and separated on a DB-5 (30 m x 0.25 mm, 0.25 microm film thickness) fused silica column with helium as the carrier gas. The temperature program was as follows: 100 degrees C for 2 min, the 5 degrees C x min(-1) to 150 degrees C, then 15 degrees C x min(-1) to 200 degrees C, and kept for 10 min. The MS transfer line temperature was set to 250 degrees C, the MS source temperature was set to 200 degrees C. The ionization mode was electron ionization (EI) and the selective ion monitor mode was used. A good linear relationship was constructed over the injection amount range of 5.5-110 ng of methyl nonyl ketone. The average recovery was 98.9%, and RSD was 2. 2%. The developed method was sensitive, accurate, and can be used for the determination of methyl nonyl ketone in the volatile oil and for the quality control of H. cordata.

Structure-activity relationships to estimate the effective Henry's law coefficients of organics of atmospheric interest

NASA Astrophysics Data System (ADS)

Raventos-Duran, Teresa; Valorso, Richard; Aumont, Bernard; Camredon, Marie

2010-05-01

The oxidation of volatile organic compounds emitted in the atmosphere involves complex reaction mechanisms which leads to the formation of oxygenated organic intermediates, usually denoted as secondary organics. The fate of these secondary organics remains poorly quantified due to a lack of information about their speciation, distribution and evolution in the gas and condensed phases. A significant fraction of secondary organics may dissolve into the tropospheric aqueous phase owing to the presence of polar moieties generated during the oxidation processes. The partitioning of organics between the gas and the aqueous atmospheric phases is usually described in the basis of Henry's law. Atmospheric models require a knowledge of the Henry's law coefficient (H) for every water soluble organic species described in the chemical mechanism. Methods that can predict reliable H values for the vast number of organic compounds are therefore required. We have compiled a data set of experimental Henry's law constants for compounds bearing functional groups of atmospheric relevance. This data set was then used to develop GROMHE, a structure activity relationship to predict H values based on a group contribution approach. We assessed its performance with two other available estimation methods. The results show that for all these methods the reliability of the estimates decreases with increasing solubility. We discuss differences between methods and found that GROMHE had greater prediction ability.

Mantle to surface degassing of carbon- and sulphur-rich alkaline magma at El Hierro, Canary Islands

NASA Astrophysics Data System (ADS)

Longpré, Marc-Antoine; Stix, John; Klügel, Andreas; Shimizu, Nobumichi

2017-02-01

Basaltic volcanoes transfer volatiles from the mantle to the surface of the Earth. The quantification of deep volatile fluxes relies heavily on estimates of the volatile content of primitive magmas, the best archive of which is provided by melt inclusions. Available data from volcanoes producing mafic alkaline lavas in a range of tectonic settings suggest high volatile fluxes, but information remains sparse, particularly for intraplate ocean islands. Here we present measurements of volatile and trace element concentrations, as well as sulphur speciation, in olivine-hosted melt inclusions and matrix glasses from quenched basanite lava balloon samples from the 2011-2012 submarine eruption at El Hierro, Canary Islands. The results reveal remarkably high concentrations of dissolved volatiles and incompatible trace elements in this magma, with ∼80 ppm Nb and up to 3420 ppm CO2, 3.0 wt.% H2O and 5080 ppm S. Reconstructed primitive CO2 contents, considering CO2/Nb systematics and possible CO2 sequestration in shrinkage bubbles, reach weight percent levels, indicating that carbon is a major constituent of Canary Island magmas at depth and that exsolution of a CO2-rich fluid begins in the mantle at pressures in excess of 1 GPa. Correlations between sulphur concentration, sulphur speciation and water content suggest strong reduction of an initially oxidised mantle magma, likely controlled by coupled H2O and S degassing. This late-stage redox change may have triggered sulphide saturation, recorded by globular sulphide inclusions in clinopyroxene and ulvöspinel. The El Hierro basanite thus had a particularly high volatile-carrying capacity and released a minimum of 1.3-2.1 Tg CO2 and 1.8-2.9 Tg S to the environment, causing substantial stress on the local submarine ecosystem. These results highlight the important contribution of alkaline ocean island volcanoes, such as the Canary Islands, to volatile fluxes from the mantle.

Volatile fingerprinting of pseudomonas aeruginosa and respiratory syncytial virus infection in an in vitro cystic fibrosis co-infection model.

PubMed

Purcaro, Giorgia; Rees, Christiaan; Melvin, Jeffrey A; Bomberg, Jennifer M; Hill, Jane E

2018-05-08

Volatile molecules in exhaled breath represent potential biomarkers in the setting of infectious diseases, particularly those affecting the respiratory tract. In particular, Pseudomonas aeruginosa is a critically-important respiratory pathogen in specific subsets of the population, such as those with cystic fibrosis. Infections caused by P. aeruginosa can be particularly problematic when co-infection with respiratory syncytial virus (RSV) occurs, as this is correlated with the establishment of chronic P. aeruginosa infection. In the present study, we evaluate the volatile metabolites produced by P. Aeruginosa (PAO1)-infected, RSV-infected, co-infected, or uninfected cystic fibrosis bronchial epithelial (CFBE) cells, in vitro. We identified a volatile metabolic signature that could discriminate between P. aeruginosa-infected and non-P. aeruginosa-infected CFBE with an area under the receiver operating characteristic curve (AUROC) of 0.850, using the machine learning algorithm Random Forest (RF). Although we could not discriminate between RSV-infected and non-RSV-infected CFBE (AUROC = 0.431), we note that sample classification probabilities for RSV-infected cell, generated using RF, were between those of uninfected CFBE and P. aeruginosa-infected CFBE, suggesting that RSV infection may result in a volatile metabolic profile that shares attributes with both of these groups. To more precisely elucidate the biological origins of the volatile metabolites that were discriminatory between P. aeruginosa-infected and non-P. aeruginosa-infected CFBE, we measured the volatile metabolites produced by P. aeruginosa grown in the absence of CFBE. Our findings suggest that the discriminatory metabolites produced likely result from the interaction of P. aeruginosa with the CFBE cells, rather than the metabolism of media components by the bacterium. Taken together, our findings support the notion that P. aeruginosa interacting with CFBE yields a particular volatile metabolic signature. Such a signature may have clinical utility in the monitoring of individuals with cystic fibrosis. © 2018 IOP Publishing Ltd.

OZONE GENERATORS IN INDOOR AIR SETTINGS

EPA Science Inventory

The report gives information on home/office ozone generators. It discusses their current uses as amelioratives for environmental tobacco smoke, biocontaminants, volatile organic compounds, and odors and details the advantages and disadvantages of each. Ozone appears to work well ...

[Study on quality standards of decoction pieces of salt Alpinia].

PubMed

Li, Wenbing; Hu, Changjiang; Long, Lanyan; Huang, Qinwan; Xie, Xiuqiong

2010-12-01

To establish the quality criteria for decoction pieces of salt Alpinia. Decoction pieces of salt Alpinia were measured with moisture, total ash, acid-insoluble ash, water-extract and volatile oils according to the procedures recorded in the Chinese Pharmacopoeia 2010. The content of Nootkatone was determined by HPLC, and NaCl, by chloridion electrode method. We obtained results of total ash, acid-insoluble ash, water-extract and volatile oils of 10 batches of decoction pieces of salt Alpinia moisture; Meanwhile we set the HPLC and chloridion electrode method. This research established a fine quality standard for decoction pieces of salt Alpinia.

Modelling winter organic aerosol at the European scale with CAMx: evaluation and source apportionment with a VBS parameterization based on novel wood burning smog chamber experiments

NASA Astrophysics Data System (ADS)

Ciarelli, Giancarlo; Aksoyoglu, Sebnem; El Haddad, Imad; Bruns, Emily A.; Crippa, Monica; Poulain, Laurent; Äijälä, Mikko; Carbone, Samara; Freney, Evelyn; O'Dowd, Colin; Baltensperger, Urs; Prévôt, André S. H.

2017-06-01

We evaluated a modified VBS (volatility basis set) scheme to treat biomass-burning-like organic aerosol (BBOA) implemented in CAMx (Comprehensive Air Quality Model with extensions). The updated scheme was parameterized with novel wood combustion smog chamber experiments using a hybrid VBS framework which accounts for a mixture of wood burning organic aerosol precursors and their further functionalization and fragmentation in the atmosphere. The new scheme was evaluated for one of the winter EMEP intensive campaigns (February-March 2009) against aerosol mass spectrometer (AMS) measurements performed at 11 sites in Europe. We found a considerable improvement for the modelled organic aerosol (OA) mass compared to our previous model application with the mean fractional bias (MFB) reduced from -61 to -29 %. We performed model-based source apportionment studies and compared results against positive matrix factorization (PMF) analysis performed on OA AMS data. Both model and observations suggest that OA was mainly of secondary origin at almost all sites. Modelled secondary organic aerosol (SOA) contributions to total OA varied from 32 to 88 % (with an average contribution of 62 %) and absolute concentrations were generally under-predicted. Modelled primary hydrocarbon-like organic aerosol (HOA) and primary biomass-burning-like aerosol (BBPOA) fractions contributed to a lesser extent (HOA from 3 to 30 %, and BBPOA from 1 to 39 %) with average contributions of 13 and 25 %, respectively. Modelled BBPOA fractions were found to represent 12 to 64 % of the total residential-heating-related OA, with increasing contributions at stations located in the northern part of the domain. Source apportionment studies were performed to assess the contribution of residential and non-residential combustion precursors to the total SOA. Non-residential combustion and road transportation sector contributed about 30-40 % to SOA formation (with increasing contributions at urban and near industrialized sites), whereas residential combustion (mainly related to wood burning) contributed to a larger extent, around 60-70 %. Contributions to OA from residential combustion precursors in different volatility ranges were also assessed: our results indicate that residential combustion gas-phase precursors in the semivolatile range (SVOC) contributed from 6 to 30 %, with higher contributions predicted at stations located in the southern part of the domain. On the other hand, the oxidation products of higher-volatility precursors (the sum of intermediate-volatility compounds (IVOCs) and volatile organic compounds (VOCs)) contribute from 15 to 38 % with no specific gradient among the stations. Although the new parameterization leads to a better agreement between model results and observations, it still under-predicts the SOA fraction, suggesting that uncertainties in the new scheme and other sources and/or formation mechanisms remain to be elucidated. Moreover, a more detailed characterization of the semivolatile components of the emissions is needed.

Dynamical basis sets for algebraic variational calculations in quantum-mechanical scattering theory

NASA Technical Reports Server (NTRS)

Sun, Yan; Kouri, Donald J.; Truhlar, Donald G.; Schwenke, David W.

1990-01-01

New basis sets are proposed for linear algebraic variational calculations of transition amplitudes in quantum-mechanical scattering problems. These basis sets are hybrids of those that yield the Kohn variational principle (KVP) and those that yield the generalized Newton variational principle (GNVP) when substituted in Schlessinger's stationary expression for the T operator. Trial calculations show that efficiencies almost as great as that of the GNVP and much greater than the KVP can be obtained, even for basis sets with the majority of the members independent of energy.

On basis set superposition error corrected stabilization energies for large n-body clusters.

PubMed

Walczak, Katarzyna; Friedrich, Joachim; Dolg, Michael

2011-10-07

In this contribution, we propose an approximate basis set superposition error (BSSE) correction scheme for the site-site function counterpoise and for the Valiron-Mayer function counterpoise correction of second order to account for the basis set superposition error in clusters with a large number of subunits. The accuracy of the proposed scheme has been investigated for a water cluster series at the CCSD(T), CCSD, MP2, and self-consistent field levels of theory using Dunning's correlation consistent basis sets. The BSSE corrected stabilization energies for a series of water clusters are presented. A study regarding the possible savings with respect to computational resources has been carried out as well as a monitoring of the basis set dependence of the approximate BSSE corrections. © 2011 American Institute of Physics

Single-carbon discrimination by selected peptides for individual detection of volatile organic compounds

NASA Astrophysics Data System (ADS)

Ju, Soomi; Lee, Ki-Young; Min, Sun-Joon; Yoo, Yong Kyoung; Hwang, Kyo Seon; Kim, Sang Kyung; Yi, Hyunjung

2015-03-01

Although volatile organic compounds (VOCs) are becoming increasingly recognized as harmful agents and potential biomarkers, selective detection of the organic targets remains a tremendous challenge. Among the materials being investigated for target recognition, peptides are attractive candidates because of their chemical robustness, divergence, and their homology to natural olfactory receptors. Using a combinatorial peptide library and either a graphitic surface or phenyl-terminated self-assembled monolayer as relevant target surfaces, we successfully selected three interesting peptides that differentiate a single carbon deviation among benzene and its analogues. The heterogeneity of the designed target surfaces provided peptides with varying affinity toward targeted molecules and generated a set of selective peptides that complemented each other. Microcantilever sensors conjugated with each peptide quantitated benzene, toluene and xylene to sub-ppm levels in real time. The selection of specific receptors for a group of volatile molecules will provide a strong foundation for general approach to individually monitoring VOCs.

High quality Gaussian basis sets for fourth-row atoms

NASA Technical Reports Server (NTRS)

Partridge, Harry; Faegri, Knut, Jr.

1992-01-01

Energy optimized Gaussian basis sets of triple-zeta quality for the atoms Rb-Xe have been derived. Two series of basis sets are developed: (24s 16p 10d) and (26s 16p 10d) sets which were expanded to 13d and 19p functions as the 4d and 5p shells become occupied. For the atoms lighter than Cd, the (24s 16p 10d) sets with triple-zeta valence distributions are higher in energy than the corresponding double-zeta distribution. To ensure a triple-zeta distribution and a global energy minimum, the (26s 16p 10d) sets were derived. Total atomic energies from the largest basis sets are between 198 and 284 (mu)E(sub H) above the numerical Hartree-Fock energies.

Storage temperature and time influences sensory quality of mandarin oranges by altering soluble solids, acidity and aroma volatile composition

USDA-ARS?s Scientific Manuscript database

Mandarin oranges are very prone to losing flavor quality during storage and, as a result, often have a short shelf life. To better understand the basis of this flavor loss, two mandarin varieties (‘W. Murcott’ and ‘Owari’) were stored for 0, 3 and 6 weeks at either 0 °C, 4 °C, or 8 °C plus 1 week at...

Scientific need for a cometary mission

NASA Technical Reports Server (NTRS)

Whipple, F. L.

1979-01-01

Known facts about comets are reviewed including their organic and inorganic content. Photographs are used to show the differences in the physical appearances of the three types of comets. Space missions will provide the opportunity to determine the sequence of events that led to their formation and that of the solar system; how volatiles arrived on earth; and the basis for the existence of life on earth; and the source of the outer planetary system.

Relativistic well-tempered Gaussian basis sets for helium through mercury

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

Okada, S.; Matsuoka, O.

1989-10-01

Exponent parameters of the nonrelativistically optimized well-tempered Gaussian basis sets of Huzinaga and Klobukowski have been employed for Dirac--Fock--Roothaan calculations without their reoptimization. For light atoms He (atomic number {ital Z}=2)--Rh ({ital Z}=45), the number of exponent parameters used has been the same as the nonrelativistic basis sets and for heavier atoms Pd ({ital Z}=46)--Hg({ital Z}=80), two 2{ital p} (and three 3{ital d}) Gaussian basis functions have been augmented. The scheme of kinetic energy balance and the uniformly charged sphere model of atomic nuclei have been adopted. The qualities of the calculated basis sets are close to the Dirac--Fock limit.

Characterization of aroma compounds in apple cider using solvent-assisted flavor evaporation and headspace solid-phase microextraction.

PubMed

Xu, Yan; Fan, Wenlai; Qian, Michael C

2007-04-18

The aroma-active compounds in two apple ciders were identified using gas chromatography-olfactometry (GC-O) and GC-mass spectrometry (MS) techniques. The volatile compounds were extracted using solvent-assisted flavor evaporation (SAFE) and headspace solid-phase microextraction (HS-SPME). On the basis of odor intensity, the most important aroma compounds in the two apple cider samples were 2-phenylethanol, butanoic acid, octanoic acid, 2-methylbutanoic acid, 2-phenylethyl acetate, ethyl 2-methylbutanoate, ethyl butanoate, ethyl hexanoate, 4-ethylguaiacol, eugenol, and 4-vinylphenol. Sulfur-containing compounds, terpene derivatives, and lactones were also detected in ciders. Although most of the aroma compounds were common in both ciders, the aroma intensities were different. Comparison of extraction techniques showed that the SAFE technique had a higher recovery for acids and hydroxy-containing compounds, whereas the HS-SPME technique had a higher recovery for esters and highly volatile compounds.

Volatility of bitumen prices and implications for the industry

USGS Publications Warehouse

Attanasi, E.D.

2008-01-01

Sustained crude oil price increases have led to increased investment in and production of Canadian bitumen to supplement North American oil supplies. For new projects, the evaluation of profitability is based on a prediction of the future price path of bitumen and ultimately light/medium crude oil. This article examines the relationship between the bitumen and light crude oil prices in the context of a simple error-correction economic-adjustment model. The analysis shows bitumen prices to be significantly more volatile than light crude prices. Also, the dominant effect of an oil price shock on bitumen prices is immediate and is amplified, both in absolute terms and percentage price changes. It is argued that the bitumen industry response to such market risks will likely be a realignment toward vertical integration via new downstream construction, mergers, or on a de facto basis by the establishment of alliances. ?? 2008 International Association for Mathematical Geology.

On the attempts to measure water (and other volatiles) directly at the surface of a comet

PubMed Central

Sheridan, S.; Morgan, G. H.; Barber, S. J.; Morse, A. D.

2017-01-01

The Ptolemy instrument on the Philae lander (of the Rosetta space mission) was able to make measurements of the major volatiles, water, carbon monoxide and carbon dioxide, directly at the surface of comet 67P/Churyumov–Gerasimenko. We give some background to the mission and highlight those instruments that have already given insights into the notion of water in comets, and which will continue to do so as more results are either acquired or more fully interpreted. On the basis of our results, we show how comets may in fact be heterogeneous over their surface, and how surface measurements can be used in a quest to comprehend the daily cycles of processes that affect the evolution of comets. This article is part of the themed issue ‘The origin, history and role of water in the evolution of the inner Solar System’. PMID:28416724

Natural Products: An Alternative to Conventional Therapy for Dermatophytosis?

PubMed

Lopes, Graciliana; Pinto, Eugénia; Salgueiro, Lígia

2017-02-01

The increased incidence of fungal infections, associated with the widespread use of antifungal drugs, has resulted in the development of resistance, making it necessary to discover new therapeutic alternatives. Among fungal infections, dermatophytoses constitute a serious public health problem, affecting 20-25 % of the world population. Medicinal plants represent an endless source of bioactive molecules, and their volatile and non-volatile extracts are clearly recognized for being the historical basis of therapeutic health care. Because of this, the research on natural products with antifungal activity against dermatophytes has considerably increased in recent years. However, despite the recognized anti-dermatophytic potential of natural products, often advantageous face to commercial drugs, there is still a long way to go until their use in therapeutics. This review attempts to summarize the current status of anti-dermatophytic natural products, focusing on their mechanism of action, the developed pharmaceutical formulations and their effectiveness in human and animal models of infection.

On the attempts to measure water (and other volatiles) directly at the surface of a comet

NASA Astrophysics Data System (ADS)

Wright, I. P.; Sheridan, S.; Morgan, G. H.; Barber, S. J.; Morse, A. D.

2017-04-01

The Ptolemy instrument on the Philae lander (of the Rosetta space mission) was able to make measurements of the major volatiles, water, carbon monoxide and carbon dioxide, directly at the surface of comet 67P/Churyumov-Gerasimenko. We give some background to the mission and highlight those instruments that have already given insights into the notion of water in comets, and which will continue to do so as more results are either acquired or more fully interpreted. On the basis of our results, we show how comets may in fact be heterogeneous over their surface, and how surface measurements can be used in a quest to comprehend the daily cycles of processes that affect the evolution of comets. This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

Electrical reliability, multilevel data storage and mechanical stability of MoS2-PMMA nanocomposite-based non-volatile memory device

NASA Astrophysics Data System (ADS)

Bhattacharjee, Snigdha; Sarkar, Pranab Kumar; Prajapat, Manoj; Roy, Asim

2017-07-01

Molybdenum disulfide (MoS2) is of great interest for its applicability in various optoelectronic devices. Here we report the resistive switching properties of polymethylmethacrylate embedding MoS2 nano-crystals. The devices are developed on an ITO-coated PET substrate with copper as the top electrode. Systematic evaluation of resistive switching parameters, on the basis of MoS2 content, suggests non-volatile memory characteristics. A decent ON/OFF ratio, high retention time and long endurance of 3  ×  103, 105 s and 105 cycles are respectively recorded in a device with 1 weight percent (wt%) of MoS2. The bending cyclic measurements confirm the flexibility of the memory devices with good electrical reliability as well as mechanical stability. In addition, multilevel storage has been demonstrated by controlling the current compliance and span of voltage sweeping in the memory device.

Changes in chemical composition of frozen coated fish products during deep-frying.

PubMed

Pérez-Palacios, Trinidad; Petisca, Catarina; Casal, Susana; Ferreira, Isabel M P L V O

2014-03-01

This work evaluates the influence of deep-frying coated fish products on total fat, fatty acid (FA) and amino acid profile, and on the formation of volatile compounds, with special attention on furan and its derivatives due to their potential harmful characteristics. As expected, deep-frying in sunflower oil increased linoleic acid content, but total fat amount increased only by 2% on a dry basis. Eicosapentanoic and docosahexanoic acids were preserved while γ- and α-linoleic acids were oxidised. Deep-frying also induces proteolysis, releasing free AA, and the formation of volatile compounds, particularly aldehydes and ketones arising from polyunsaturated FA. In addition, high quantities of furanic compounds, particularly furan and furfuryl alcohol, are generated during deep-frying coated fish. The breaded crust formed could contribute simultaneously for the low uptake of fat, preservation of long chain n-3 FA, and for the high amounts of furanic compounds formed during the deep-frying process.

Performance assessment of density functional methods with Gaussian and Slater basis sets using 7σ orbital momentum distributions of N2O

NASA Astrophysics Data System (ADS)

Wang, Feng; Pang, Wenning; Duffy, Patrick

2012-12-01

Performance of a number of commonly used density functional methods in chemistry (B3LYP, Bhandh, BP86, PW91, VWN, LB94, PBe0, SAOP and X3LYP and the Hartree-Fock (HF) method) has been assessed using orbital momentum distributions of the 7σ orbital of nitrous oxide (NNO), which models electron behaviour in a chemically significant region. The density functional methods are combined with a number of Gaussian basis sets (Pople's 6-31G*, 6-311G**, DGauss TZVP and Dunning's aug-cc-pVTZ as well as even-tempered Slater basis sets, namely, et-DZPp, et-QZ3P, et-QZ+5P and et-pVQZ). Orbital momentum distributions of the 7σ orbital in the ground electronic state of NNO, which are obtained from a Fourier transform into momentum space from single point electronic calculations employing the above models, are compared with experimental measurement of the same orbital from electron momentum spectroscopy (EMS). The present study reveals information on performance of (a) the density functional methods, (b) Gaussian and Slater basis sets, (c) combinations of the density functional methods and basis sets, that is, the models, (d) orbital momentum distributions, rather than a group of specific molecular properties and (e) the entire region of chemical significance of the orbital. It is found that discrepancies of this orbital between the measured and the calculated occur in the small momentum region (i.e. large r region). In general, Slater basis sets achieve better overall performance than the Gaussian basis sets. Performance of the Gaussian basis sets varies noticeably when combining with different Vxc functionals, but Dunning's augcc-pVTZ basis set achieves the best performance for the momentum distributions of this orbital. The overall performance of the B3LYP and BP86 models is similar to newer models such as X3LYP and SAOP. The present study also demonstrates that the combinations of the density functional methods and the basis sets indeed make a difference in the quality of the calculated orbitals.

A Comparison of the Behavior of Functional/Basis Set Combinations for Hydrogen-Bonding in the Water Dimer with Emphasis on Basis Set Superposition Error

PubMed Central

Plumley, Joshua A.; Dannenberg, J. J.

2011-01-01

We evaluate the performance of nine functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-DFT molecular orbital calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise corrected PES. The calculated ΔE's with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, due to error compensation, the smaller basis sets gave the best results (in comparison to experimental and high level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. Since many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: 1) D95(d,p) with B3LYP, B97D, M06 or MPWB1k; 2) 6-311G(d,p) with B3LYP; 3) D95++(d,p) with B3LYP, B97D or MPWB1K; 4)6-311++G(d,p) with B3LYP or B97D; and 5) aug-cc-pVDZ with M05-2X, M06-2X or X3LYP. PMID:21328398

A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.

PubMed

Plumley, Joshua A; Dannenberg, J J

2011-06-01

We evaluate the performance of ten functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-density functional theory (non-DFT) molecular orbital (MO) calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise (CP) corrected PES. The calculated interaction energies (ΔEs) with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, because of error compensation, the smaller basis sets gave the best results (in comparison to experimental and high-level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. As many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: (1) D95(d,p) with B3LYP, B97D, M06, or MPWB1k; (2) 6-311G(d,p) with B3LYP; (3) D95++(d,p) with B3LYP, B97D, or MPWB1K; (4) 6-311++G(d,p) with B3LYP or B97D; and (5) aug-cc-pVDZ with M05-2X, M06-2X, or X3LYP. Copyright © 2011 Wiley Periodicals, Inc.

On the validity of the basis set superposition error and complete basis set limit extrapolations for the binding energy of the formic acid dimer

NASA Astrophysics Data System (ADS)

Miliordos, Evangelos; Xantheas, Sotiris S.

2015-03-01

We report the variation of the binding energy of the Formic Acid Dimer with the size of the basis set at the Coupled Cluster with iterative Singles, Doubles and perturbatively connected Triple replacements [CCSD(T)] level of theory, estimate the Complete Basis Set (CBS) limit, and examine the validity of the Basis Set Superposition Error (BSSE)-correction for this quantity that was previously challenged by Kalescky, Kraka, and Cremer (KKC) [J. Chem. Phys. 140, 084315 (2014)]. Our results indicate that the BSSE correction, including terms that account for the substantial geometry change of the monomers due to the formation of two strong hydrogen bonds in the dimer, is indeed valid for obtaining accurate estimates for the binding energy of this system as it exhibits the expected decrease with increasing basis set size. We attribute the discrepancy between our current results and those of KKC to their use of a valence basis set in conjunction with the correlation of all electrons (i.e., including the 1s of C and O). We further show that the use of a core-valence set in conjunction with all electron correlation converges faster to the CBS limit as the BSSE correction is less than half than the valence electron/valence basis set case. The uncorrected and BSSE-corrected binding energies were found to produce the same (within 0.1 kcal/mol) CBS limits. We obtain CCSD(T)/CBS best estimates for De = - 16.1 ± 0.1 kcal/mol and for D0 = - 14.3 ± 0.1 kcal/mol, the later in excellent agreement with the experimental value of -14.22 ± 0.12 kcal/mol.

Characterizing and Understanding the Remarkably Slow Basis Set Convergence of Several Minnesota Density Functionals for Intermolecular Interaction Energies

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

Mardirossian, Narbe; Head-Gordon, Martin

2013-08-22

For a set of eight equilibrium intermolecular complexes, it is discovered in this paper that the basis set limit (BSL) cannot be reached by aug-cc-pV5Z for three of the Minnesota density functionals: M06-L, M06-HF, and M11-L. In addition, the M06 and M11 functionals exhibit substantial, but less severe, difficulties in reaching the BSL. By using successively finer grids, it is demonstrated that this issue is not related to the numerical integration of the exchange-correlation functional. In addition, it is shown that the difficulty in reaching the BSL is not a direct consequence of the structure of the augmented functions inmore » Dunning’s basis sets, since modified augmentation yields similar results. By using a very large custom basis set, the BSL appears to be reached for the HF dimer for all of the functionals. As a result, it is concluded that the difficulties faced by several of the Minnesota density functionals are related to an interplay between the form of these functionals and the structure of standard basis sets. It is speculated that the difficulty in reaching the basis set limit is related to the magnitude of the inhomogeneity correction factor (ICF) of the exchange functional. A simple modification of the M06-L exchange functional that systematically reduces the basis set superposition error (BSSE) for the HF dimer in the aug-cc-pVQZ basis set is presented, further supporting the speculation that the difficulty in reaching the BSL is caused by the magnitude of the exchange functional ICF. In conclusion, the BSSE is plotted with respect to the internuclear distance of the neon dimer for two of the examined functionals.« less

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

Holland, Troy Michael; Kress, Joel David; Bhat, Kabekode Ghanasham

Year 1 Objectives (August 2016 – December 2016) – The original Independence model is a sequentially regressed set of parameters from numerous data sets in the Aspen Plus modeling framework. The immediate goal with the basic data model is to collect and evaluate those data sets relevant to the thermodynamic submodels (pure substance heat capacity, solvent mixture heat capacity, loaded solvent heat capacities, and volatility data). These data are informative for the thermodynamic parameters involved in both vapor-liquid equilibrium, and in the chemical equilibrium of the liquid phase.

BREATH MEASUREMENT AND MODELS TO ASSESS VOC DERMAL ABSORPTION IN WATER

EPA Science Inventory

Dermal exposure to volatile organic compounds (VOCs) in water results from environmental contamination of surface, ground-, and drinking waters. This exposure occurs both in occupational and residential settings. Compartmental models incorporating body burden measurements have ...

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

Miliordos, Evangelos; Aprà, Edoardo; Xantheas, Sotiris S.

We establish a new estimate for the binding energy between two benzene molecules in the parallel-displaced (PD) conformation by systematically converging (i) the intra- and intermolecular geometry at the minimum, (ii) the expansion of the orbital basis set, and (iii) the level of electron correlation. The calculations were performed at the second-order Møller–Plesset perturbation (MP2) and the coupled cluster including singles, doubles, and a perturbative estimate of triples replacement [CCSD(T)] levels of electronic structure theory. At both levels of theory, by including results corrected for basis set superposition error (BSSE), we have estimated the complete basis set (CBS) limit bymore » employing the family of Dunning’s correlation-consistent polarized valence basis sets. The largest MP2 calculation was performed with the cc-pV6Z basis set (2772 basis functions), whereas the largest CCSD(T) calculation was with the cc-pV5Z basis set (1752 basis functions). The cluster geometries were optimized with basis sets up to quadruple-ζ quality, observing that both its intra- and intermolecular parts have practically converged with the triple-ζ quality sets. The use of converged geometries was found to play an important role for obtaining accurate estimates for the CBS limits. Our results demonstrate that the binding energies with the families of the plain (cc-pVnZ) and augmented (aug-cc-pVnZ) sets converge [within <0.01 kcal/mol for MP2 and <0.15 kcal/mol for CCSD(T)] to the same CBS limit. In addition, the average of the uncorrected and BSSE-corrected binding energies was found to converge to the same CBS limit much faster than either of the two constituents (uncorrected or BSSE-corrected binding energies). Due to the fact that the family of augmented basis sets (especially for the larger sets) causes serious linear dependency problems, the plain basis sets (for which no linear dependencies were found) are deemed as a more efficient and straightforward path for obtaining an accurate CBS limit. We considered extrapolations of the uncorrected (ΔE) and BSSE-corrected (ΔE cp) binding energies, their average value (ΔE ave), as well as the average of the latter over the plain and augmented sets (Δ~E ave) with the cardinal number of the basis set n. Our best estimate of the CCSD(T)/CBS limit for the π–π binding energy in the PD benzene dimer is D e = -2.65 ± 0.02 kcal/mol. The best CCSD(T)/cc-pV5Z calculated value is -2.62 kcal/mol, just 0.03 kcal/mol away from the CBS limit. For comparison, the MP2/CBS limit estimate is -5.00 ± 0.01 kcal/mol, demonstrating a 90% overbinding with respect to CCSD(T). Finally, the spin-component-scaled (SCS) MP2 variant was found to closely reproduce the CCSD(T) results for each basis set, while scaled opposite spin (SOS) MP2 yielded results that are too low when compared to CCSD(T).« less

Application of Sensory Evaluation, HS-SPME GC-MS, E-Nose, and E-Tongue for Quality Detection in Citrus Fruits.

PubMed

Qiu, Shanshan; Wang, Jun

2015-10-01

In this study, electronic tongue (E-tongue), headspace solid-phase microextraction gas chromatography-mass spectrometer (GC-MS), electronic nose (E-nose), and quantitative describe analysis (QDA) were applied to describe the 2 types of citrus fruits (Satsuma mandarins [Citrus unshiu Marc.] and sweet oranges [Citrus sinensis {L.} Osbeck]) and their mixing juices systematically and comprehensively. As some aroma components or some flavor molecules interacted with the whole juice matrix, the changes of most components in the fruit juice were not in proportion to the mixing ratio of the 2 citrus fruits. The potential correlations among the signals of E-tongue and E-nose, volatile components, and sensory attributes were analyzed by using analysis of variance partial least squares regression. The result showed that the variables from the sensor signals (E-tongue system and E-nose system) had significant and positive (or negative) correlations to the most variables of volatile components (GC-MS) and sensory attributes (QDA). The simultaneous utilization of E-tongue and E-nose obtained a perfect classification result with 100% accuracy rate based on linear discriminant analysis and also attained a satisfying prediction with high coefficient association for the sensory attributes (R(2) > 0.994 for training sets and R(2) > 0.983 for testing sets) and for the volatile components (R(2) > 0.992 for training sets and R(2) > 0.990 for testing sets) based on random forest. Being easy-to-use, cost-effective, robust, and capable of providing a fast analysis procedure, E-nose and E-tongue could be used as an alternative detection system to traditional analysis methods, such as GC-MS and sensory evaluation by human panel in the fruit industry. Being easy-to-use, cost-effective, robust, and capable of providing a fast analysis procedure, E-nose and E-tongue could be used as an alternative detection system to traditional analysis methods for characterizing food flavors. Based on those results, one can draw a conclusion that the fusion system composed of E-tongue and E-nose could guarantee a satisfying result in the prediction of sensory attributes and volatile components for fruit quality profile. © 2015 Institute of Food Technologists®

Characterization of the volatile profile of Antarctic bacteria by using solid-phase microextraction-gas chromatography-mass spectrometry.

PubMed

Romoli, Riccardo; Papaleo, Maria Cristiana; de Pascale, Donatella; Tutino, Maria Luisa; Michaud, Luigi; LoGiudice, Angelina; Fani, Renato; Bartolucci, Gianluca

2011-10-01

Bacteria belonging to the Burkholderia cepacia complex (Bcc) are significant pathogens in Cystic Fibrosis (CF) patients and are resistant to a plethora of antibiotics. In this context, microorganisms from Antarctica are interesting because they produce antimicrobial compounds inhibiting the growth of other bacteria. This is particularly true for bacteria isolated from Antarctic sponges. The aim of this work was to characterize a set of Antarctic bacteria for their ability to produce new natural drugs that could be exploited in the control of infections in CF patients by Bcc bacteria. Hence, 11 bacterial strains allocated to different genera (e.g., Pseudoalteromonas, Arthrobacter and Psychrobacter) were tested for their ability to inhibit the growth of 21 Bcc strains and some other human pathogens. All these bacteria completely inhibited the growth of most, if not all, Bcc strains, suggesting a highly specific activity toward Bcc strains. Experimental evidences showed that the antimicrobial compounds are small volatile organic compounds, and are constitutively produced via an unknown pathway. The microbial volatile profile was obtained by SPME-GC-MS within the m/z interval of 40-450. Solid phase micro extraction technique affords the possibility to extract the volatile compounds in head space with a minimal sample perturbation. Principal component analysis and successive cluster discriminant analysis was applied to evaluate the relationships among the volatile organic compounds with the aim of classifying the microorganisms by their volatile profile. These data highlight the potentiality of Antarctic bacteria as novel sources of antibacterial substances to face Bcc infections in CF patients. Copyright © 2011 John Wiley & Sons, Ltd.

Circadian clock gene LATE ELONGATED HYPOCOTYL directly regulates the timing of floral scent emission in Petunia

PubMed Central

Fenske, Myles P.; Hewett Hazelton, Kristen D.; Hempton, Andrew K.; Shim, Jae Sung; Yamamoto, Breanne M.; Riffell, Jeffrey A.; Imaizumi, Takato

2015-01-01

Flowers present a complex display of signals to attract pollinators, including the emission of floral volatiles. Volatile emission is highly regulated, and many species restrict emissions to specific times of the day. This rhythmic emission of scent is regulated by the circadian clock; however, the mechanisms have remained unknown. In Petunia hybrida, volatile emissions are dominated by products of the floral volatile benzenoid/phenylpropanoid (FVBP) metabolic pathway. Here we demonstrate that the circadian clock gene P. hybrida LATE ELONGATED HYPOCOTYL (LHY; PhLHY) regulates the daily expression patterns of the FVBP pathway genes and floral volatile production. PhLHY expression peaks in the morning, antiphasic to the expression of P. hybrida GIGANTEA (PhGI), the master scent regulator ODORANT1 (ODO1), and many other evening-expressed FVBP genes. Overexpression phenotypes of PhLHY in Arabidopsis caused an arrhythmic clock phenotype, which resembles those of LHY overexpressors. In Petunia, constitutive expression of PhLHY depressed the expression levels of PhGI, ODO1, evening-expressed FVBP pathway genes, and FVBP emission in flowers. Additionally, in the Petunia lines in which PhLHY expression was reduced, the timing of peak expression of PhGI, ODO1, and the FVBP pathway genes advanced to the morning. Moreover, PhLHY protein binds to cis-regulatory elements called evening elements that exist in promoters of ODO1 and other FVBP genes. Thus, our results imply that PhLHY directly sets the timing of floral volatile emission by restricting the expression of ODO1 and other FVBP genes to the evening in Petunia. PMID:26124104

Circadian clock gene LATE ELONGATED HYPOCOTYL directly regulates the timing of floral scent emission in Petunia.

PubMed

Fenske, Myles P; Hewett Hazelton, Kristen D; Hempton, Andrew K; Shim, Jae Sung; Yamamoto, Breanne M; Riffell, Jeffrey A; Imaizumi, Takato

2015-08-04

Flowers present a complex display of signals to attract pollinators, including the emission of floral volatiles. Volatile emission is highly regulated, and many species restrict emissions to specific times of the day. This rhythmic emission of scent is regulated by the circadian clock; however, the mechanisms have remained unknown. In Petunia hybrida, volatile emissions are dominated by products of the floral volatile benzenoid/phenylpropanoid (FVBP) metabolic pathway. Here we demonstrate that the circadian clock gene P. hybrida LATE ELONGATED HYPOCOTYL (LHY; PhLHY) regulates the daily expression patterns of the FVBP pathway genes and floral volatile production. PhLHY expression peaks in the morning, antiphasic to the expression of P. hybrida GIGANTEA (PhGI), the master scent regulator ODORANT1 (ODO1), and many other evening-expressed FVBP genes. Overexpression phenotypes of PhLHY in Arabidopsis caused an arrhythmic clock phenotype, which resembles those of LHY overexpressors. In Petunia, constitutive expression of PhLHY depressed the expression levels of PhGI, ODO1, evening-expressed FVBP pathway genes, and FVBP emission in flowers. Additionally, in the Petunia lines in which PhLHY expression was reduced, the timing of peak expression of PhGI, ODO1, and the FVBP pathway genes advanced to the morning. Moreover, PhLHY protein binds to cis-regulatory elements called evening elements that exist in promoters of ODO1 and other FVBP genes. Thus, our results imply that PhLHY directly sets the timing of floral volatile emission by restricting the expression of ODO1 and other FVBP genes to the evening in Petunia.

Alcohol acyl transferase 1 links two distinct volatile pathways that produce esters and phenylpropenes in apple fruit.

PubMed

Yauk, Yar-Khing; Souleyre, Edwige J F; Matich, Adam J; Chen, Xiuyin; Wang, Mindy Y; Plunkett, Blue; Dare, Andrew P; Espley, Richard V; Tomes, Sumathi; Chagné, David; Atkinson, Ross G

2017-07-01

Fruit accumulate a diverse set of volatiles including esters and phenylpropenes. Volatile esters are synthesised via fatty acid degradation or from amino acid precursors, with the final step being catalysed by alcohol acyl transferases (AATs). Phenylpropenes are produced as a side branch of the general phenylpropanoid pathway. Major quantitative trait loci (QTLs) on apple (Malus × domestica) linkage group (LG)2 for production of the phenylpropene estragole and volatile esters (including 2-methylbutyl acetate and hexyl acetate) both co-located with the MdAAT1 gene. MdAAT1 has previously been shown to be required for volatile ester production in apple (Plant J., 2014, https://doi.org/10.1111/tpj.12518), and here we show it is also required to produce p-hydroxycinnamyl acetates that serve as substrates for a bifunctional chavicol/eugenol synthase (MdoPhR5) in ripe apple fruit. Fruit from transgenic 'Royal Gala' MdAAT1 knockdown lines produced significantly reduced phenylpropene levels, whilst manipulation of the phenylpropanoid pathway using MdCHS (chalcone synthase) knockout and MdMYB10 over-expression lines increased phenylpropene production. Transient expression of MdAAT1, MdoPhR5 and MdoOMT1 (O-methyltransferase) genes reconstituted the apple pathway to estragole production in tobacco. AATs from ripe strawberry (SAAT1) and tomato (SlAAT1) fruit can also utilise p-coumaryl and coniferyl alcohols, indicating that ripening-related AATs are likely to link volatile ester and phenylpropene production in many different fruit. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

A wind tunnel for measuring selenium volatilization under field-like conditions

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

Dungan, R.S.; Stork, A.; Frankenberger, W.T. Jr.

2000-04-01

A wind tunnel was developed to measure the loss of volatile selenium (Se) from soil under field-like conditions. The wind tunnel consisted of a volatilization chamber made of Plexiglas (2.4 m long x 0.8 m wide x 1.2 m high), which was set above a stainless steel lysimeter (0.5 m{sup 2} surface area x 0.8 m deep). High air exchange rates (avg. 700 air changes h{sup {minus}1}) were used to simulate field-like environmental conditions inside the wind tunnel. To monitor the fate and transport of the Se, radiolabeled {sup 75}Se as sodium selenite (Na{sub 2}{sup 75}SeO{sub 3}) was incorporated intomore » the top 5 cm of soil. Volatile Se was trapped on activated carbon filters and measured directly using gamma counting. A 135-d bare-soil experiment was carried out, during which 2.7% of the Se was released through volatilization without added C. The average flux rate of gaseous Se was 17 mg m{sup {minus}2} h{sup {minus}1}, with a high of 72 mg m{sup {minus}2} h{sup {minus}1} occurring on Day 6. After 135 d, 59 and 43% of the {sup 75}Se was located in the 0 to 5 and 5 to 10 cm soil layers, respectively. A total of 84.5% of all applied {sup 75}Se was recovered. The purpose of this study was to improve estimates on Se volatilization from seleniferous soils and help close the gap between previous laboratory and field experiments.« less

Atomization Energies of SO and SO2; Basis Set Extrapolation Revisted

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Ricca, Alessandra; Arnold, James (Technical Monitor)

1998-01-01

The addition of tight functions to sulphur and extrapolation to the complete basis set limit are required to obtain accurate atomization energies. Six different extrapolation procedures are tried. The best atomization energies come from the series of basis sets that yield the most consistent results for all extrapolation techniques. In the variable alpha approach, alpha values larger than 4.5 or smaller than 3, appear to suggest that the extrapolation may not be reliable. It does not appear possible to determine a reliable basis set series using only the triple and quadruple zeta based sets. The scalar relativistic effects reduce the atomization of SO and SO2 by 0.34 and 0.81 kcal/mol, respectively, and clearly must be accounted for if a highly accurate atomization energy is to be computed. The magnitude of the core-valence (CV) contribution to the atomization is affected by missing diffuse valence functions. The CV contribution is much more stable if basis set superposition errors are accounted for. A similar study of SF, SF(+), and SF6 shows that the best family of basis sets varies with the nature of the S bonding.

Calculating Interaction Energies Using First Principle Theories: Consideration of Basis Set Superposition Error and Fragment Relaxation

ERIC Educational Resources Information Center

Bowen, J. Philip; Sorensen, Jennifer B.; Kirschner, Karl N.

2007-01-01

The analysis explains the basis set superposition error (BSSE) and fragment relaxation involved in calculating the interaction energies using various first principle theories. Interacting the correlated fragment and increasing the size of the basis set can help in decreasing the BSSE to a great extent.

Hydrogeologic and chemical data for the O-Field area, Aberdeen Proving Ground, Maryland

USGS Publications Warehouse

Nemoff, P.R.; Vroblesky, D.A.

1989-01-01

O-Field, located at the Edgewood area of Aberdeen Proving Ground , Maryland, was periodically used for disposal of munitions, waste chemicals, and chemical-warfare agents from World War II through the 1950' s. This report includes various physical, geologic, chemical, and hydrologic data obtained from well-core, groundwater, surface water, and bottom-sediment sampling sites at and near the O-Field disposal area. The data are presented in tables and hydrographs. Three site-location maps are also included. Well-core data include lithologic logs for 11 well- cluster sites, grain-size distributions, various chemical characteristics, and confining unit characteristics. Groundwater data include groundwater chemistry, method blanks for volatile organic carbon, available data on volatile and base/neutral organics, and compilation of corresponding method blanks, chemical-warfare agents, explosive-related products, radionuclides, herbicides, and groundwater levels. Surface-water data include field-measured characteristics; concentrations of various inorganic constituents including arsenic; selected organic constituents with method blanks; detection limits of organics; and a compilation of information on corresponding acids, volatiles, and semivolatiles. Bottom- sediment data include inorganic properties and constituents; organic chemistry; detection limits for organic chemicals; a compilation of information on acids, volatiles, and semivolatiles; and method blanks corresponding to acids, volatiles, and semivolatiles. A set of 15 water- level hydrographs for the period March 1986 through September 1987 also is included in the report. (USGS)

Aroma characterization of tangerine hybrids by gas-chromatography-olfactometry and sensory evaluation.

PubMed

Miyazaki, Takayuki; Plotto, Anne; Baldwin, Elizabeth A; Reyes-De-Corcuera, José I; Gmitter, Fred G

2012-03-15

Tangerines have a distinct flavor among citrus fruit. However, information on tangerine volatiles remains limited. Volatile compounds from a breeding population of tangerines were earlier identified by gas chromatography-mass spectrometry. In this study, five hybrids with a distinct volatile profile were analyzed by gas-chromatography-olfactometry (GC-O) and descriptive sensory analysis. Forty-nine aroma active compounds were found in a consensus by GC-O. Aldehydes were the most important group with odor activity, as well as monoterpenes, esters, alcohols and ketones. 1,8-Cineole, β-myrcene, (E,E)-2,4-nonadienal, hexanal, ethyl-2-methylbutanoate, and linalool were perceived with high intensity in most samples. Two 'Clementine' × 'Minneola' and one 'Fortune' × 'Murcott' hybrids with tangerine, sulfury and woody/spicy flavors had aroma active compounds with terpeney, fatty/vegetable and metallic/rubber descriptors. A tangerine with 'Valencia' orange in its parentage had a characteristic orange flavor, which could be explained by esters and ketones, high in fruity and floral odor intensities. A hybrid of unknown origin had a distinct fruity-non-citrus and pumpkin/fatty flavor; that sample had the lowest amount of aroma-active volatiles, with the least compounds with terpeney odors. There was no one compound characteristic of tangerine flavor. Nevertheless, each sample sensory characteristic could be explained by a set of aroma-active volatile compounds.

Development of supercritical CO2 extraction of bioactive phytochemicals from black poplar (Populus nigra L.) buds followed by GC-MS and UHPLC-DAD-QqTOF-MS.

PubMed

Kuś, Piotr M; Okińczyc, Piotr; Jakovljević, Martina; Jokić, Stela; Jerković, Igor

2018-05-25

The supercritical CO 2 (SC-CO 2 ) extraction process of black poplar (Populus nigra L.) buds was optimized (pressure, temperature) based on the yields of major phytochemicals (volatiles and non-volatiles). The optimal settings were 30 MPa/60 °C. Major volatiles determined by GC-MS in the optimized SC-CO 2 extract (mg of benzyl salicylate equivalent (BSE) per 100 g of buds) were: pinostrobin chalcone (1574.2), β-eudesmol (640.8), α-eudesmol (581.9), 2-methyl-2-butenyl-p-coumarate (289.9), pentyl-p-coumarate (457.0), γ-eudesmol (294.4), and benzyl salicylate (289.2). Partial qualitative similarity was observed between SC-CO 2 extracts and corresponding hydrodistilled essential oil dominated by sesquiterpenes, but with lower yields. Major compounds (mg per 100 g of buds) identified by UHPLC-DAD-QqTOF-MS in the optimized SC-CO 2 extract were: pinostrobin (751.7), pinocembrin (485.6), 3-O-pinobanksin acetate and methyl-butenyl-p-coumarate (290.2; 144.9 of pinobanksin and p-coumaric acid equivalents, respectively). SC-CO 2 extraction was found useful for green, efficient and simultaneous extraction of both volatile/non-volatile, bioactive phytochemicals of poplar buds - precursors of poplar-type propolis. Copyright © 2018 Elsevier B.V. All rights reserved.

Italian and Spanish commercial tomato sauces for pasta dressing: study of sensory and head-space profiles by Flash Profiling and solid-phase microextraction-gas chomatography-mass spectrometry.

PubMed

Bendini, Alessandra; Vallverdú-Queralt, Anna; Valli, Enrico; Palagano, Rosa; Lamuela-Raventos, Rosa Maria; Toschi, Tullia Gallina

2017-08-01

The sensory and head-space profiles of Italian and Spanish commercial tomato sauces were investigated. The Flash Profiling method was used to evaluate sensory characteristics. Samples within each set were ranked according to selected descriptors. One hundred volatile compounds were identified by solid-phase microextraction-gas chomatography-mass spectrometry. For Italian samples, the sensory notes of basil/aromatic herbs, acid and cooked tomato were among those perceived most by the assessors, whereas, in Spanish samples, the sensory attributes of garlic/onion and onion/sweet pepper and, in Italian samples, cooked tomato were among those found most frequently. Data were elaborated using multivariate statistical approaches and interesting correlations were observed among the different sensory attributes and related volatile compounds. Spanish samples were characterized by the highest content of volatiles linked to the thermal treatment of tomatoes and to raw and sautéed garlic and onion, whereas the Italian samples were characterized by terpenic compounds typical of basil and volatile molecules derived from fresh tomato. These results confirm the influence of both formulation and production processes on the aromatic profile (sensory attributes and volatile compounds) of tomato products, which is probably related to the different eating habits and culinary traditions in Italy and Spain. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Effect of pH, temperature, and moisture on the formation of volatile compounds in glycine/glucose model systems.

PubMed

Ames, J M; Guy, R C; Kipping, G J

2001-09-01

Mixtures of glycine, glucose, and starch were extrusion cooked using sodium hydroxide at 0, 3, and 6 g/L of extruder water feed, 18% moisture, and 120, 150, and 180 degrees C target die temperatures, giving extrudates with pH values of 5.6, 6.8, and 7.4. Freeze-dried equimolar solutions of glucose and glycine were heated either dry or after equilibration to approximately 13% moisture at 180 degrees C in a reaction-tube system designed to mimic the heating profile in an extruder. Volatile compounds were isolated onto Tenax and analyzed by gas chromatography-mass spectrometry. For the extrudates, total yields of volatiles increased with decreasing pH at 180 degrees C, reached a maximum at pH 6.8 at 150 degrees C, and increased with increasing pH at 120 degrees C. Amounts increased with temperature at all pH values. Pyrazines were the most abundant class for all sets of conditions (54-79% of total volatiles). Pyrroles, ketones, furans, oxazoles, and pyridines were also identified. Yields of volatiles from the reaction-tube samples increased by >60% in the moist system. Levels of individual classes also increased in the presence of moisture, except pyrazines, which decreased approximately 3.5-fold. Twenty-one of the compounds were common to the reaction-tube samples and the extrudates.

Time course effects of fermentation on fatty acid and volatile compound profiles of Cheonggukjang using new soybean cultivars.

PubMed

Cho, Kye Man; Lim, Ho-Jeong; Kim, Mi-So; Kim, Da Som; Hwang, Chung Eun; Nam, Sang Hae; Joo, Ok Soo; Lee, Byong Won; Kim, Jae Kyeom; Shin, Eui-Cheol

2017-07-01

In this study, we investigated the effects of the potential probiotic Bacillus subtilis CSY191 on the fatty acid profiles of Cheonggukjang, a fermented soybean paste, prepared using new Korean brown soybean cultivars, protein-rich cultivar (Saedanbaek), and oil-rich cultivar (Neulchan). Twelve fatty acids were identified in the sample set-myristic, palmitic, palmitoleic, stearic, oleic, vaccenic, linoleic, α-linolenic, arachidic, gondoic, behenic, and lignoceric acids-yet, no specific changes driven by fermentation were noted in the fatty acid profiles. To further explore the effects of fermentation of B. subtilis CSY191, complete profiles of volatiles were monitored. In total, 121, 136, and 127 volatile compounds were detected in the Saedanbaek, Daewon (control cultivar), and Neulchan samples, respectively. Interestingly, the content of pyrazines-compounds responsible for pungent and unpleasant Cheonggukjang flavors-was significantly higher in Neulchan compared to that in Saedanbaek. Although the fermentation period was not a strong factor affecting the observed changes in fatty acid profiles, we noted that profiles of volatiles in Cheonggukjang changed significantly over time, and different cultivars represented specific volatile profiles. Thus, further sensory evaluation might be needed to determine if such differences influence consumers' preferences. Furthermore, additional studies to elucidate the associations between B. subtilis CSY191 fermentation and other nutritional components (e.g., amino acids) and their health-promoting potential are warranted. Copyright © 2016. Published by Elsevier B.V.

Volatile biomarkers of symptomatic and asymptomatic malaria infection in humans

PubMed Central

Wanjiku, Caroline; Stanczyk, Nina M.; Pulido, Hannier; Betz, Heike S.

2018-01-01

Malaria remains among the world’s deadliest diseases, and control efforts depend critically on the availability of effective diagnostic tools, particularly for the identification of asymptomatic infections, which play a key role in disease persistence and may account for most instances of transmission but often evade detection by current screening methods. Research on humans and in animal models has shown that infection by malaria parasites elicits changes in host odors that influence vector attraction, suggesting that such changes might yield robust biomarkers of infection status. Here we present findings based on extensive collections of skin volatiles from human populations with high rates of malaria infection in Kenya. We report broad and consistent effects of malaria infection on human volatile profiles, as well as significant divergence in the effects of symptomatic and asymptomatic infections. Furthermore, predictive models based on machine learning algorithms reliably determined infection status based on volatile biomarkers. Critically, our models identified asymptomatic infections with 100% sensitivity, even in the case of low-level infections not detectable by microscopy, far exceeding the performance of currently available rapid diagnostic tests in this regard. We also identified a set of individual compounds that emerged as consistently important predictors of infection status. These findings suggest that volatile biomarkers may have significant potential for the development of a robust, noninvasive screening method for detecting malaria infections under field conditions. PMID:29760095

Modeling volatility using state space models.

PubMed

Timmer, J; Weigend, A S

1997-08-01

In time series problems, noise can be divided into two categories: dynamic noise which drives the process, and observational noise which is added in the measurement process, but does not influence future values of the system. In this framework, we show that empirical volatilities (the squared relative returns of prices) exhibit a significant amount of observational noise. To model and predict their time evolution adequately, we estimate state space models that explicitly include observational noise. We obtain relaxation times for shocks in the logarithm of volatility ranging from three weeks (for foreign exchange) to three to five months (for stock indices). In most cases, a two-dimensional hidden state is required to yield residuals that are consistent with white noise. We compare these results with ordinary autoregressive models (without a hidden state) and find that autoregressive models underestimate the relaxation times by about two orders of magnitude since they do not distinguish between observational and dynamic noise. This new interpretation of the dynamics of volatility in terms of relaxators in a state space model carries over to stochastic volatility models and to GARCH models, and is useful for several problems in finance, including risk management and the pricing of derivative securities. Data sets used: Olsen & Associates high frequency DEM/USD foreign exchange rates (8 years). Nikkei 225 index (40 years). Dow Jones Industrial Average (25 years).

Characterisation of the volatile profile of coconut water from five varieties using an optimised HS-SPME-GC analysis.

PubMed

Prades, Alexia; Assa, Rebecca Rachel Ablan; Dornier, Manuel; Pain, Jean-Pierre; Boulanger, Renaud

2012-09-01

Coconut (Cocos nucifera L.) water is a refreshing tropical drink whose international market has recently been growing. However, little is yet known about its physicochemical composition, particularly its aroma. This study set out to characterise the volatile profile of water from five coconut varieties. Aroma compounds were characterised by headspace solid phase microextraction gas chromatography (HS-SPME-GC) analysis. An experimental design was established to optimise SPME conditions, leading to an equilibration time of 10 min followed by an extraction time of 60 min at 50 °C. Accordingly, immature coconut water from WAT (West African Tall), PB121 (MYD × WAT Hybrid), MYD (Malayan Yellow Dwarf), EGD (Equatorial Guinea Green Dwarf) and THD (Thailand Aromatic Green Dwarf) palms was analysed and described. Ketones were mainly present in the Tall and Hybrid varieties, whereas aldehydes were most abundant in the Dwarf palms. Tall coconut water was characterised by a high lactone content. THD exhibited a high ethyl octanoate level. The cluster analysis of the volatile fraction from the five coconut cultivars was found to be related to their genetic classification. The volatile compounds of immature coconut water from five varieties were characterised for the first time. Volatile profile analysis could be a useful tool for the selection of Dwarf coconut varieties, which are mainly consumed as a beverage. Copyright © 2012 Society of Chemical Industry.

A New Sulfur and Carbon Degassing Inventory for the Southern Central American Volcanic Arc: The Importance of Accurate Time-Series Data Sets and Possible Tectonic Processes Responsible for Temporal Variations in Arc-Scale Volatile Emissions

NASA Astrophysics Data System (ADS)

de Moor, J. M.; Kern, C.; Avard, G.; Muller, C.; Aiuppa, A.; Saballos, A.; Ibarra, M.; LaFemina, P.; Protti, M.; Fischer, T. P.

2017-12-01

This work presents a new database of SO2 and CO2 fluxes from the Southern Central American Volcanic Arc (SCAVA) for the period 2015-2016. We report ˜300 SO2 flux measurements from 10 volcanoes and gas ratios from 11 volcanoes in Costa Rica and Nicaragua representing the most extensive available assessment of this ˜500 km arc segment. The SO2 flux from SCAVA is estimated at 6,240 ± 1,150 T/d, about a factor of three higher than previous estimations (1972-2013). We attribute this increase in part to our more complete assessment of the arc. Another consideration in interpreting the difference is the context of increased volcanic activity, as there were more eruptions in 2015-2016 than in any period since ˜1980. A potential explanation for increased degassing and volcanic activity is a change in crustal stress regime (from compression to extension, opening volcanic conduits) following two large (Mw > 7) earthquakes in the region in 2012. The CO2 flux from the arc is estimated at 22,500 ± 4,900 T/d, which is equal to or greater than estimates of C input into the SCAVA subduction zone. Time-series data sets for arc degassing need to be improved in temporal and spatial coverage to robustly constrain volatile budgets and tectonic controls. Arc volatile budgets are strongly influenced by short-lived degassing events and arc systems likely display significant short-term variations in volatile output, calling for expansion of nascent geochemical monitoring networks to achieve spatial and temporal coverage similar to traditional geophysical networks.

An analysis of the financial crisis in the KOSPI market using Hurst exponents

NASA Astrophysics Data System (ADS)

Yim, Kyubin; Oh, Gabjin; Kim, Seunghwan

2014-09-01

Recently, the study of the financial crisis has progressed to include the concept of the complex system, thereby improving the understanding of this extreme event from a neoclassical economic perspective. To determine which variables are related to the financial event caused by the 2008 US subprime crisis using temporal correlations, we investigate the diverse variables that may explain the financial system. These variables include return, volatility, trading volume and inter-trade duration data sets within the TAQ data for 27 highly capitalized individual companies listed on the KOSPI stock market. During 2008 and 2009, the Hurst exponent for the return time series over the whole period was less than 0.5, and the Hurst exponents for other variables, such as the volatility, trading volume and inter-trade duration, were greater than 0.5. Additionally, we analyze the relationships between the variation of temporal correlation and market instability based on these Hurst exponents and the degree of multifractality. We find that for the data related to trading volume, the Hurst exponents do not allow us to detect changes in market status, such as changes from normal to abnormal status, whereas other variables, including the return, volatility and weekly inter-trade duration, indicate a significant change in market status after the Lehman Brothers' bankruptcy. In addition, the multifractality and the measurement defined by subtracting the Hurst exponent of the return time series from that of the volatility time series decrease sharply after the US subprime event and recover approximately 50 days after the Lehman Brothers' collapse. Our findings suggest that the temporal features of financial quantities in the TAQ data set and the market complexity perform very well at diagnosing financial market stability.

The effect of diffuse basis functions on valence bond structural weights

NASA Astrophysics Data System (ADS)

Galbraith, John Morrison; James, Andrew M.; Nemes, Coleen T.

2014-03-01

Structural weights and bond dissociation energies have been determined for H-F, H-X, and F-X molecules (-X = -OH, -NH2, and -CH3) at the valence bond self-consistent field (VBSCF) and breathing orbital valence bond (BOVB) levels of theory with the aug-cc-pVDZ and 6-31++G(d,p) basis sets. At the BOVB level, the aug-cc-pVDZ basis set yields a counterintuitive ordering of ionic structural weights when the initial heavy atom s-type basis functions are included. For H-F, H-OH, and F-X, the ordering follows chemical intuition when these basis functions are not included. These counterintuitive weights are shown to be a result of the diffuse polarisation function on one VB fragment being spatially located, in part, on the other VB fragment. Except in the case of F-CH3, this problem is corrected with the 6-31++G(d,p) basis set. The initial heavy atom s-type functions are shown to make an important contribution to the VB orbitals and bond dissociation energies and, therefore, should not be excluded. It is recommended to not use diffuse basis sets in valence bond calculations unless absolutely necessary. If diffuse basis sets are needed, the 6-31++G(d,p) basis set should be used with caution and the structural weights checked against VBSCF values which have been shown to follow the expected ordering in all cases.

Lunar Geoscience: Key Questions for Future Lunar Exploration

NASA Astrophysics Data System (ADS)

Head, James

2014-05-01

Lunar Geoscience: Key Questions for Future Lunar Exploration James W. Head, Department of Geological Sciences, Brown University, Providence, RI 02912 USA. (Invited paper/solicited talk for EGU 2014 PS2.3 Lunar session, Bernard H. Foing, Convener EGU PS2.3) The last several decades of intensive robotic exploration of the Moon has built on early Apollo and Luna exploration to provide fundamental knowledge of Earth's satellite and an excellent perspective on the most well-documented planetary body other than Earth. This new planetological perspective has raised substantial new questions about the nature of the origin of the Moon, its early differentiation and bombardment history, its internal thermal evolution, the production of its secondary crust as exemplified by the lunar maria, and tertiary crust as potentially seen in steep-sided domes and impact melt differentiates, the abundance of interior volatiles and their role in volcanic eruptions, and the abundance of surface volatiles and their concentration in polar regions. On the basis of this new information, a series of specific outstanding geoscience questions can be identified that can serve as guides for future human and robotic exploration. These include: 1) What is the nature and abundance of impact melt seas and what rock types do they produce upon differentiation and solidification? 2) Where are lunar mantle samples located on the lunar surface and what processes are responsible for placing them there? 3) What processes are responsible for producing the silica-rich viscous domes, such as those seen at Gruithuisen? 4) What are the volatile species involved in the emplacement of lunar pyroclastic deposits and what clues do they provide about deep magmatic volatiles and shallow volatile formation processes? 5) How do we account for the differing characteristics of regional dark mantling pyroclastic deposits? 6) When did mare basalt volcanism begin (earliest cryptmaria) and how and where is it manifested? 7) Was there extensive volcanism and resurfacing prior to mare basalt volcanism; if so, what is its origin and how is it manifested? 8) Are there other shallow magmatic intrusions besides floor-fractured craters, and if so, what is their origin? 9) What clues can we derive from the geology and gravity structure of floor-fractured craters concerning the modes of emplacement and magmatic evolution of shallow intrusions; does differentiation and volatile build-up take place? 10) What are the factors that explain the formation of complex craters, peak-ring basins and multi-ring basins? 11) What are the ages of key multi-ring basin impact melt sheets and how do they help to determine lunar impact chronology and flux? 12) How can lunar crustal density and thickness structure revealed by GRAIL be related to geological impact, magmatic and tectonic processes? 13) What is the origin, distribution and mode of emplacement of polar and circum-polar volatile deposits? 14) What is the origin of central peaks and their often unusual mineralogy and how do we account for the evidence for heterogeneous melt composition and structure? These and other major geoscience questions form the basis for robust and exciting future international robotic and human exploration and sample return missions. A series of candidate sites of interest are identified that can address these questions.

Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

DOE PAGES

Morgan, Trevor James; Turn, Scott Q.; George, Anthe

2015-08-26

A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.« less

Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

PubMed Central

Morgan, Trevor James; Turn, Scott Q.; George, Anthe

2015-01-01

A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis. PMID:26308860

Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

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

Morgan, Trevor James; Turn, Scott Q.; George, Anthe

A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.« less

Establishing an index arbitrage model by applying neural networks method--a case study of Nikkei 225 index.

PubMed

Chen, A P; Chianglin, C Y; Chung, H P

2001-10-01

This paper applies the neural network method to establish an index arbitrage model and compares the arbitrage performances to that from traditional cost of carry arbitrage model. From the empirical results of the Nikkei 225 stock index market, following conclusions can be stated: (1) The basis will get enlarged for a time period, more profitability may be obtained from the trend. (2) If the neural network is applied within the index arbitrage model, twofold of return would be obtained than traditional arbitrage model can do. (3) If the T_basis has volatile trend, the neural network arbitrage model will ignore the peak. Although arbitrageur would lose the chance to get profit, they may reduce the market impact risk.

On the effects of basis set truncation and electron correlation in conformers of 2-hydroxy-acetamide

NASA Astrophysics Data System (ADS)

Szarecka, A.; Day, G.; Grout, P. J.; Wilson, S.

Ab initio quantum chemical calculations have been used to study the differences in energy between two gas phase conformers of the 2-hydroxy-acetamide molecule that possess intramolecular hydrogen bonding. In particular, rotation around the central C-C bond has been considered as a factor determining the structure of the hydrogen bond and stabilization of the conformer. Energy calculations include full geometiy optimization using both the restricted matrix Hartree-Fock model and second-order many-body perturbation theory with a number of commonly used basis sets. The basis sets employed ranged from the minimal STO-3G set to [`]split-valence' sets up to 6-31 G. The effects of polarization functions were also studied. The results display a strong basis set dependence.

Applicability of canisters for sample storage in the determination of hazardous air pollutants

NASA Astrophysics Data System (ADS)

Kelly, Thomas J.; Holdren, Michael W.

This paper evaluates the applicability of canisters for storage of air samples containing volatile organic compounds listed among the 189 hazardous air pollutants (HAPs) in the 1990 U.S. Clean Air Act Amendments. Nearly 100 HAPs have sufficient vapor pressure to be considered volatile compounds. Of those volatile organic HAPs, 52 have been tested previously for stability during storage in canisters. The published HAP stability studies are reviewed, illustrating that for most of the 52 HAPs tested, canisters are an effective sample storage approach. However, the published stability studies used a variety of canister types and test procedures, and generally considered only a few compounds in a very small set of canisters. A comparison of chemical and physical properties of the HAPs has also been conducted, to evaluate the applicability of canister sampling for other HAPs, for which canister stability testing has never been conducted. Of 45 volatile HAPs never tested in canisters, this comparison identifies nine for which canisters should be effective, and 17 for which canisters are not likely to be effective. For the other 19 HAPs, no clear decision can be reached on the likely applicability of air sample storage in canisters.

Determination of the solubility of low volatility liquid organic compounds in water using volatile-tracer assisted headspace gas chromatography.

PubMed

Zhang, Shu-Xin; Chai, Xin-Sheng; Barnes, Donald G

2016-02-26

This study reports a new headspace gas chromatographic method (HS-GC) for the determination of water solubility of low volatility liquid organic compounds (LVLOs). The HS-GC analysis was performed on a set of aqueous solutions containing a range of concentrations of toluene-spiked (as a tracer) LVLOs, from under-saturation to over-saturation. A plot of the toluene tracer GC signal vs. the concentration of the LVLO results in two lines of different slopes that intersect at the concentration corresponding to the compound's solubility in water. The results showed that the HS-GC method has good precision (RSD <6.3%) and good accuracy, in which the relative deference between the data measured by the HS-GC method and the reference method were within 6.0%. The HS-GC method is simple and particularly suitable for measuring the solubility of LVLOs at elevated temperatures. This approach should be of special interest to those concerned about the impact of the presence of low-volatility organic liquids in waters of environmental and biological systems. Copyright © 2016 Elsevier B.V. All rights reserved.

Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO

NASA Astrophysics Data System (ADS)

Tsimpidi, A. P.; Karydis, V. A.; Zavala, M.; Lei, W.; Bei, N.; Molina, L.; Pandis, S. N.

2011-06-01

Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 includes the recently developed volatility basis-set framework in which both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico de Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites is encouraging. The average predicted PM1 organic aerosol (OA) concentration in T0, T1, and T2 is 18 μg m-3, 11.7 μg m-3, and 10.5 μg m-3 respectively, while the corresponding measured values are 17.2 μg m-3, 11 μg m-3, and 9 μg m-3. The average predicted locally-emitted primary OA concentrations, 4.4 μg m-3 at T0, 1.2 μg m-3 at T1 and 1.7 μg m-3 at PTP, are in reasonably good agreement with the corresponding PMF analysis estimates based on the Aerosol Mass Spectrometer (AMS) observations of 4.5, 1.3, and 2.9 μg m-3 respectively. The model reproduces reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m-3 predicted versus 7.5 μg m-3 measured), in T1 (6.3 μg m-3 predicted versus 4.6 μg m-3 measured) and in PTP (6.6 μg m-3 predicted versus 5.9 μg m-3 measured). The rest of the OA mass (6.1 μg m-3 and 4.2 μg m-3 in T0 and T1 respectively) is assumed to originate from biomass burning activities and is introduced to the model as part of the boundary conditions. Inside Mexico City (at T0), the locally-produced OA is predicted to be on average 60 % locally-emitted primary (POA), 6 % semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 34 % traditional SOA from the oxidation of VOCs (V-SOA). The average contributions of the OA components to the locally-produced OA for the entire modelling domain are predicted to be 32 % POA, 10 % S-SOA and I-SOA, and 58 % V-SOA. The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.

NHEXAS PHASE I REGION 5 STUDY--VOCS IN BLOOD ANALYTICAL RESULTS

EPA Science Inventory

This data set includes analytical results for measurements of VOCs (volatile organic compounds) in 145 blood samples. These samples were collected to examine the relationships between personal exposure measurements, environmental measurements, and body burden. Venous blood sample...

Next Generation Air Monitoring (NGAM) VOC Sensor Evaluation Report

EPA Science Inventory

This report summarizes the results of next generation air monitor (NGAM) volatile organic compound (VOC) evaluations performed using both laboratory as well as field scale settings. These evaluations focused on challenging lower cost (<$2500) NGAM technologies to either controlle...

Electroantennographic Bioassay as a Screening Tool for Host Plant Volatiles

PubMed Central

Beck, John J.; Light, Douglas M.; Gee, Wai S.

2012-01-01

Plant volatiles play an important role in plant-insect interactions. Herbivorous insects use plant volatiles, known as kairomones, to locate their host plant.1,2 When a host plant is an important agronomic commodity feeding damage by insect pests can inflict serious economic losses to growers. Accordingly, kairomones can be used as attractants to lure or confuse these insects and, thus, offer an environmentally friendly alternative to pesticides for insect control.3 Unfortunately, plants can emit a vast number volatiles with varying compositions and ratios of emissions dependent upon the phenology of the commodity or the time of day. This makes identification of biologically active components or blends of volatile components an arduous process. To help identify the bioactive components of host plant volatile emissions we employ the laboratory-based screening bioassay electroantennography (EAG). EAG is an effective tool to evaluate and record electrophysiologically the olfactory responses of an insect via their antennal receptors. The EAG screening process can help reduce the number of volatiles tested to identify promising bioactive components. However, EAG bioassays only provide information about activation of receptors. It does not provide information about the type of insect behavior the compound elicits; which could be as an attractant, repellent or other type of behavioral response. Volatiles eliciting a significant response by EAG, relative to an appropriate positive control, are typically taken on to further testing of behavioral responses of the insect pest. The experimental design presented will detail the methodology employed to screen almond-based host plant volatiles4,5 by measurement of the electrophysiological antennal responses of an adult insect pest navel orangeworm (Amyelois transitella) to single components and simple blends of components via EAG bioassay. The method utilizes two excised antennae placed across a "fork" electrode holder. The protocol demonstrated here presents a rapid, high-throughput standardized method for screening volatiles. Each volatile is at a set, constant amount as to standardize the stimulus level and thus allow antennal responses to be indicative of the relative chemoreceptivity. The negative control helps eliminate the electrophysiological response to both residual solvent and mechanical force of the puff. The positive control (in this instance acetophenone) is a single compound that has elicited a consistent response from male and female navel orangeworm (NOW) moth. An additional semiochemical standard that provides consistent response and is used for bioassay studies with the male NOW moth is (Z,Z)-11,13-hexdecadienal, an aldehyde component from the female-produced sex pheromone.6-8 PMID:22588282

On the optimization of Gaussian basis sets

NASA Astrophysics Data System (ADS)

Petersson, George A.; Zhong, Shijun; Montgomery, John A.; Frisch, Michael J.

2003-01-01

A new procedure for the optimization of the exponents, αj, of Gaussian basis functions, Ylm(ϑ,φ)rle-αjr2, is proposed and evaluated. The direct optimization of the exponents is hindered by the very strong coupling between these nonlinear variational parameters. However, expansion of the logarithms of the exponents in the orthonormal Legendre polynomials, Pk, of the index, j: ln αj=∑k=0kmaxAkPk((2j-2)/(Nprim-1)-1), yields a new set of well-conditioned parameters, Ak, and a complete sequence of well-conditioned exponent optimizations proceeding from the even-tempered basis set (kmax=1) to a fully optimized basis set (kmax=Nprim-1). The error relative to the exact numerical self-consistent field limit for a six-term expansion is consistently no more than 25% larger than the error for the completely optimized basis set. Thus, there is no need to optimize more than six well-conditioned variational parameters, even for the largest sets of Gaussian primitives.

Accurate and balanced anisotropic Gaussian type orbital basis sets for atoms in strong magnetic fields.

PubMed

Zhu, Wuming; Trickey, S B

2017-12-28

In high magnetic field calculations, anisotropic Gaussian type orbital (AGTO) basis functions are capable of reconciling the competing demands of the spherically symmetric Coulombic interaction and cylindrical magnetic (B field) confinement. However, the best available a priori procedure for composing highly accurate AGTO sets for atoms in a strong B field [W. Zhu et al., Phys. Rev. A 90, 022504 (2014)] yields very large basis sets. Their size is problematical for use in any calculation with unfavorable computational cost scaling. Here we provide an alternative constructive procedure. It is based upon analysis of the underlying physics of atoms in B fields that allow identification of several principles for the construction of AGTO basis sets. Aided by numerical optimization and parameter fitting, followed by fine tuning of fitting parameters, we devise formulae for generating accurate AGTO basis sets in an arbitrary B field. For the hydrogen iso-electronic sequence, a set depends on B field strength, nuclear charge, and orbital quantum numbers. For multi-electron systems, the basis set formulae also include adjustment to account for orbital occupations. Tests of the new basis sets for atoms H through C (1 ≤ Z ≤ 6) and ions Li + , Be + , and B + , in a wide B field range (0 ≤ B ≤ 2000 a.u.), show an accuracy better than a few μhartree for single-electron systems and a few hundredths to a few mHs for multi-electron atoms. The relative errors are similar for different atoms and ions in a large B field range, from a few to a couple of tens of millionths, thereby confirming rather uniform accuracy across the nuclear charge Z and B field strength values. Residual basis set errors are two to three orders of magnitude smaller than the electronic correlation energies in multi-electron atoms, a signal of the usefulness of the new AGTO basis sets in correlated wavefunction or density functional calculations for atomic and molecular systems in an external strong B field.

Accurate and balanced anisotropic Gaussian type orbital basis sets for atoms in strong magnetic fields

NASA Astrophysics Data System (ADS)

Zhu, Wuming; Trickey, S. B.

2017-12-01

In high magnetic field calculations, anisotropic Gaussian type orbital (AGTO) basis functions are capable of reconciling the competing demands of the spherically symmetric Coulombic interaction and cylindrical magnetic (B field) confinement. However, the best available a priori procedure for composing highly accurate AGTO sets for atoms in a strong B field [W. Zhu et al., Phys. Rev. A 90, 022504 (2014)] yields very large basis sets. Their size is problematical for use in any calculation with unfavorable computational cost scaling. Here we provide an alternative constructive procedure. It is based upon analysis of the underlying physics of atoms in B fields that allow identification of several principles for the construction of AGTO basis sets. Aided by numerical optimization and parameter fitting, followed by fine tuning of fitting parameters, we devise formulae for generating accurate AGTO basis sets in an arbitrary B field. For the hydrogen iso-electronic sequence, a set depends on B field strength, nuclear charge, and orbital quantum numbers. For multi-electron systems, the basis set formulae also include adjustment to account for orbital occupations. Tests of the new basis sets for atoms H through C (1 ≤ Z ≤ 6) and ions Li+, Be+, and B+, in a wide B field range (0 ≤ B ≤ 2000 a.u.), show an accuracy better than a few μhartree for single-electron systems and a few hundredths to a few mHs for multi-electron atoms. The relative errors are similar for different atoms and ions in a large B field range, from a few to a couple of tens of millionths, thereby confirming rather uniform accuracy across the nuclear charge Z and B field strength values. Residual basis set errors are two to three orders of magnitude smaller than the electronic correlation energies in multi-electron atoms, a signal of the usefulness of the new AGTO basis sets in correlated wavefunction or density functional calculations for atomic and molecular systems in an external strong B field.

The application of midbond basis sets in efficient and accurate ab initio calculations on electron-deficient systems

NASA Astrophysics Data System (ADS)

Choi, Chu Hwan

2002-09-01

Ab initio chemistry has shown great promise in reproducing experimental results and in its predictive power. The many complicated computational models and methods seem impenetrable to an inexperienced scientist, and the reliability of the results is not easily interpreted. The application of midbond orbitals is used to determine a general method for use in calculating weak intermolecular interactions, especially those involving electron-deficient systems. Using the criteria of consistency, flexibility, accuracy and efficiency we propose a supermolecular method of calculation using the full counterpoise (CP) method of Boys and Bernardi, coupled with Moller-Plesset (MP) perturbation theory as an efficient electron-correlative method. We also advocate the use of the highly efficient and reliable correlation-consistent polarized valence basis sets of Dunning. To these basis sets, we add a general set of midbond orbitals and demonstrate greatly enhanced efficiency in the calculation. The H2-H2 dimer is taken as a benchmark test case for our method, and details of the computation are elaborated. Our method reproduces with great accuracy the dissociation energies of other previous theoretical studies. The added efficiency of extending the basis sets with conventional means is compared with the performance of our midbond-extended basis sets. The improvement found with midbond functions is notably superior in every case tested. Finally, a novel application of midbond functions to the BH5 complex is presented. The system is an unusual van der Waals complex. The interaction potential curves are presented for several standard basis sets and midbond-enhanced basis sets, as well as for two popular, alternative correlation methods. We report that MP theory appears to be superior to coupled-cluster (CC) in speed, while it is more stable than B3LYP, a widely-used density functional theory (DFT). Application of our general method yields excellent results for the midbond basis sets. Again they prove superior to conventional extended basis sets. Based on these results, we recommend our general approach as a highly efficient, accurate method for calculating weakly interacting systems.

From source to surface: Tracking magmatic boron and chlorine input into the geothermal systems of the Taupo Volcanic Zone, New Zealand

NASA Astrophysics Data System (ADS)

Bégué, Florence; Deering, Chad D.; Gravley, Darren M.; Chambefort, Isabelle; Kennedy, Ben M.

2017-10-01

The magmatic contribution into geothermal fluids in the central Taupo Volcanic Zone (TVZ), New Zealand, has been attributed to either andesitic, 'arc-type' fluids, or rhyolitic, 'rift-type' fluids to explain the compositional diversity of discharge waters. However, this model relies on outdated assumptions related to geochemical trends associated with the magma at depth of typical arc to back-arc settings. Current tectonic models have shown that the TVZ is situated within a rifting arc and hosts magmatic systems dominated by distinct rhyolite types, that are likely to have evolved under different conditions than the subordinate andesites. Therefore, a new appraisal of the existing models is required to further understand the origin of the spatial compositional diversity observed in the geothermal fluids and its relationship to the structural setting. Here, we use volatile concentrations (i.e. H2O, Cl, B) from rhyolitic and andesitic mineral-hosted melt inclusions to evaluate the magmatic contribution to the TVZ geothermal systems. The andesite and two different types of rhyolites (R1 and R2) are each distinct in Cl/H2O and B/Cl, which will affect volatile solubility and phase separation (vapor vs. hydrosaline liquid) of the exsolved volatile phase. Ultimately, these key differences in the magmatic volatile constituents will play a significant role in governing the concentration of Cl discharged into geothermal systems. We estimate bulk fluid compositions (B and Cl) in equilibrium with the different melt types to show the potential contribution of 'parent' fluids to the geothermal systems throughout the TVZ. The results of this analysis show that the variability in fluid compositions partly reflects degassing from previously unaccounted for distinct magma source compositions. We suggest the geothermal systems that appear to have an 'arc-type' andesitic fluid contribution are actually derived from a rhyolite melt in equilibrium with a highly crystalline andesite magma. This model is in better agreement with the current understanding of magma petrogenesis in the central TVZ and its atypical rifted-arc tectonic setting, and show that the central TVZ records an arc, not back-arc, fluid signature.

Rapid Diagnosis of Tuberculosis from Analysis of Urine Volatile Organic Compounds

PubMed Central

Lim, Sung H.; Martino, Raymond; Anikst, Victoria; Xu, Zeyu; Mix, Samantha; Benjamin, Robert; Schub, Herbert; Eiden, Michael; Rhodes, Paul A.; Banaei, Niaz

2017-01-01

The World Health Organization has called for simple, sensitive, and non-sputum diagnostics for tuberculosis. We report development of a urine tuberculosis test using a colorimetric sensor array (CSA). The sensor comprised of 73 different indicators captures high-dimensional, spatiotemporal signatures of volatile chemicals emitted by human urine samples. The sensor responses to 63 urine samples collected from 22 tuberculosis cases and 41 symptomatic controls were measured under five different urine test conditions. Basified testing condition yielded the best accuracy with 85.5% sensitivity and 79.5% specificity. The CSA urine assay offers desired features needed for tuberculosis diagnosis in endemic settings. PMID:29057329

Basis set limit and systematic errors in local-orbital based all-electron DFT

NASA Astrophysics Data System (ADS)

Blum, Volker; Behler, Jörg; Gehrke, Ralf; Reuter, Karsten; Scheffler, Matthias

2006-03-01

With the advent of efficient integration schemes,^1,2 numeric atom-centered orbitals (NAO's) are an attractive basis choice in practical density functional theory (DFT) calculations of nanostructured systems (surfaces, clusters, molecules). Though all-electron, the efficiency of practical implementations promises to be on par with the best plane-wave pseudopotential codes, while having a noticeably higher accuracy if required: Minimal-sized effective tight-binding like calculations and chemically accurate all-electron calculations are both possible within the same framework; non-periodic and periodic systems can be treated on equal footing; and the localized nature of the basis allows in principle for O(N)-like scaling. However, converging an observable with respect to the basis set is less straightforward than with competing systematic basis choices (e.g., plane waves). We here investigate the basis set limit of optimized NAO basis sets in all-electron calculations, using as examples small molecules and clusters (N2, Cu2, Cu4, Cu10). meV-level total energy convergence is possible using <=50 basis functions per atom in all cases. We also find a clear correlation between the errors which arise from underconverged basis sets, and the system geometry (interatomic distance). ^1 B. Delley, J. Chem. Phys. 92, 508 (1990), ^2 J.M. Soler et al., J. Phys.: Condens. Matter 14, 2745 (2002).

Volatile composition and sensory profile of Cantharellus cibarius Fr. as affected by drying method.

PubMed

Politowicz, Joanna; Lech, Krzysztof; Sánchez-Rodríguez, Lucía; Szumny, Antoni; Carbonell-Barrachina, Ángel A

2017-12-01

In this work, the influence of different drying methods on the aroma composition and sensory quality of chanterelle mushrooms (Cantharellus cibarius Fr.) was evaluated. The drying methods tested were convective drying (CD), freeze drying (FD), vacuum microwave drying (VMD) and a combination of convective pre-drying and vacuum microwave finish drying (CPD-VMFD). Analyses of fresh and dried chanterelle samples by HS-SPME and GC/MS and GC-FID showed the presence of 39 volatile compounds at different concentrations. The most abundant compounds in fresh chanterelle were 1-hexanol (33.4 μg per 100 g dry basis (db)), 1-octen-3-ol (80.2 μg per 100 g db) and 2-octen-1-ol (19.3 μg per 100 g db). The results showed that fresh and dried chanterelle contained very low levels of aroma compounds; however, the highest contents of volatile compounds were found in samples after (i) CD at 80 °C (129 μg per 100 g db), (ii) CPD-VMFD at 70 °C-480/240 W (136 μg per 100 g db) and (iii) CPD-VMFD at 80 °C-480/240 W (136 μg per 100 g db). The best dehydration methods, which resulted in high contents of volatile compounds and appropriate sensory quality, according to descriptive sensory analysis and PCA tools, were CD at 70 and 80 °C. Besides, these methods led to spongy dried mushrooms with high intensities of fresh, mushroom ID, with proper color and without intense shrinkage. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Volatiles in raw and cooked meat from lambs fed olive cake and linseed.

PubMed

Gravador, R S; Serra, A; Luciano, G; Pennisi, P; Vasta, V; Mele, M; Pauselli, M; Priolo, A

2015-04-01

This study was conducted to determine the effects of feeding olive cake and linseed to lambs on the volatile organic compounds (VOCs) in raw and cooked meat. Four groups of eight male Appenninica lambs each were fed: conventional cereal-based concentrates (diet C), concentrates containing 20% on a dry matter (DM) basis of rolled linseed (diet L), concentrates containing 35% DM of stoned olive cake (diet OC), or concentrates containing both rolled linseed (10% DM) and stoned olive cake (17% DM; diet OCL). The longissimus dorsi muscle of each lamb was sampled at slaughter and was subjected to VOC profiling through the use of SPME-GC-MS. In the raw meat, the concentration of 3-methylpentanoic acid was higher in treatment C as compared with treatments L, OC and OCL (P<0.01). Moreover the level of nonanoic acid was greater in treatments C and OC than in treatment L (P<0.05). With respect to alcohols, in raw meat the amount of 2-phenoxyethanol in treatment OCL was lower than in treatments C (P<0.01) and OC (P<0.05), while in cooked meat the amount of 1-pentanol was higher in treatment C than in treatment OC (P<0.05). Apart from these compounds, none of the lipid oxidation-derived volatiles was significantly affected by the dietary treatment. Therefore, the results suggest that the replacement of cereal concentrates with linseed and/or olive cake did not cause appreciable changes in the production of volatile organic compounds in lamb meat.

[Study on effect of oil-bearing solution environment of Caryophylli Flos and other traditional Chinese medicines on system flux and oil recovery rate].

PubMed

Fan, Wen-Ling; Guo, Li-Wei; Lin, Ying; Shen, Jie; Cao, Gui-Ping; Zhu, Yun; Xu, Min; Yang, Lei

2013-10-01

The membrane enrichment process of traditional Chinese medicine volatile oil is environmental friendly and practical, with a good application prospect. In this article, oil-bearing solutions of eight traditional Chinese medicines, namely Caryophylli Flos, Schizonepetae Herba, Eupatorii Herb, Acori Talarinowii Rhizoma, Magnoliae Flos, Chrysanthemum indicum, Cyperi Rhizoma and Citri Reticulatae Pericarpium Viride, were taken as the experimental system. Under unified conditions (membrane: PVDF-14W, temperature: 40 degreeC, pressure: 0. 1 MPa, membrane surface speed: 150 r min- 1), trans-membrane was conducted for above eight oil-bearing solutions to explore the effect of their oil-bearing solution environment on system flux and oil recovery rate. The results showed that systems with smaller pH had a lower flux, without significant effect on oil recovery rate. Greater differences between the surface tension of solutions and that of pure water contributed to a lower oil recovery rate. The conductivity had no notable effect on membrane enrichment process. Systems with high turbidity had a lower flux, without remarkable effect on oil recovery rat. Heavy oils showed lower flux than light ones, but with a slightly higher oil recovery rat. Systems with higher viscosity had a lower flux than those with lower viscosity. Except for Magnoliae Flos volatile oil, all of the remaining volatile oils showed a much higher oil recovery rat than systems with high viscosity. The above results could provide data support and theoretical basis for the industrialization of membrane enrichment volatile oil technology.

Basis set construction for molecular electronic structure theory: natural orbital and Gauss-Slater basis for smooth pseudopotentials.

PubMed

Petruzielo, F R; Toulouse, Julien; Umrigar, C J

2011-02-14

A simple yet general method for constructing basis sets for molecular electronic structure calculations is presented. These basis sets consist of atomic natural orbitals from a multiconfigurational self-consistent field calculation supplemented with primitive functions, chosen such that the asymptotics are appropriate for the potential of the system. Primitives are optimized for the homonuclear diatomic molecule to produce a balanced basis set. Two general features that facilitate this basis construction are demonstrated. First, weak coupling exists between the optimal exponents of primitives with different angular momenta. Second, the optimal primitive exponents for a chosen system depend weakly on the particular level of theory employed for optimization. The explicit case considered here is a basis set appropriate for the Burkatzki-Filippi-Dolg pseudopotentials. Since these pseudopotentials are finite at nuclei and have a Coulomb tail, the recently proposed Gauss-Slater functions are the appropriate primitives. Double- and triple-zeta bases are developed for elements hydrogen through argon. These new bases offer significant gains over the corresponding Burkatzki-Filippi-Dolg bases at various levels of theory. Using a Gaussian expansion of the basis functions, these bases can be employed in any electronic structure method. Quantum Monte Carlo provides an added benefit: expansions are unnecessary since the integrals are evaluated numerically.

Automated, real-time fresh gas flow recommendations alter isoflurane consumption during the maintenance phase of anesthesia in a simulator-based study.

PubMed

Luria, Isaac; Lampotang, Samsun; Schwab, Wilhelm; Cooper, Lou Ann; Lizdas, David; Gravenstein, Nikolaus

2013-11-01

The Low Flow Wizard (LFW) provides real-time guidance for user optimization of fresh gas flow (FGF) settings during general inhaled anesthesia. The LFW can continuously inform users whether it determines their FGF to be too little, efficient, or too much, and its color-coded recommendations respond in real time to changes in FGF performed by users. Our study objective was to determine whether the LFW feature, as implemented in the Dräger Apollo workstation, alters FGF selection and thereby volatile anesthetic consumption without affecting patient care. To reduce potentially confounding variables, we used a human patient simulator that consumes and exhales volatile anesthetics. Standard monitoring was provided for the patient initially with invasive arterial blood pressure added after anesthetic induction. In this within-group study, each of 17 participants acted as his or her own control. Each participant was asked to anesthetize an identical simulated patient twice using a Dräger Apollo workstation, first with the LFW feature disabled and subsequently enabled. The volatile anesthetic was isoflurane. Both simulation runs were set up to have similar time durations for the different phases of anesthesia: induction, incision, and maintenance. Emergence was not simulated. The isoflurane vaporizer was weighed before and after each simulation run on a digital scale to verify total computed volatile liquid anesthetic consumption. In addition, the product of FGF (reported by the Apollo) times the isoflurane volumetric concentration (sampled by a multigas analyzer at the equivalent of the FGF hose for the Apollo) was integrated over time to obtain isoflurane consumption rate (on-the-fly anesthetic consumption rate measurement). The maintenance isoflurane consumption rate and FGF were significantly lower with the LFW display enabled than without (P = 0.005). The mean reduction in FGF was 53.6% (95% confidence interval, 39.2%-67.9%). There was no significant difference in alveolar isoflurane concentration (P = 0.13 for differences <0.1%). The isoflurane consumption measurement closely matched the consumption measured via the digital scale. Our data in a simulated anesthetic suggest that enabling the display of FGF efficiency data by the LFW results in a median percent reduction in volatile liquid anesthetic consumption rate of 53.2%. Since the lower limit of the 95% confidence interval for the median is 39.4%, this finding is likely to translate into cost savings and less waste anesthetic gas generated in the clinical setting and released into the atmosphere.

Auxiliary basis sets for density-fitting second-order Møller-Plesset perturbation theory: weighted core-valence correlation consistent basis sets for the 4d elements Y-Pd.

PubMed

Hill, J Grant

2013-09-30

Auxiliary basis sets (ABS) specifically matched to the cc-pwCVnZ-PP and aug-cc-pwCVnZ-PP orbital basis sets (OBS) have been developed and optimized for the 4d elements Y-Pd at the second-order Møller-Plesset perturbation theory level. Calculation of the core-valence electron correlation energies for small to medium sized transition metal complexes demonstrates that the error due to the use of these new sets in density fitting is three to four orders of magnitude smaller than that due to the OBS incompleteness, and hence is considered negligible. Utilizing the ABSs in the resolution-of-the-identity component of explicitly correlated calculations is also investigated, where it is shown that i-type functions are important to produce well-controlled errors in both integrals and correlation energy. Benchmarking at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations level indicates impressive convergence with respect to basis set size for the spectroscopic constants of 4d monofluorides; explicitly correlated double-ζ calculations produce results close to conventional quadruple-ζ, and triple-ζ is within chemical accuracy of the complete basis set limit. Copyright © 2013 Wiley Periodicals, Inc.

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

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

Zhang, Gaigong; Lin, Lin, E-mail: linlin@math.berkeley.edu; Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Since the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H{sub 2} and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

DOE PAGES

Zhang, Gaigong; Lin, Lin; Hu, Wei; ...

2017-01-27

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Sin ce the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H 2 and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

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

Zhang, Gaigong; Lin, Lin; Hu, Wei

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Sin ce the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H 2 and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn-Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

NASA Astrophysics Data System (ADS)

Zhang, Gaigong; Lin, Lin; Hu, Wei; Yang, Chao; Pask, John E.

2017-04-01

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn-Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann-Feynman forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Since the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann-Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H2 and liquid Al-Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.

The Venus flytrap attracts insects by the release of volatile organic compounds.

PubMed

Kreuzwieser, Jürgen; Scheerer, Ursel; Kruse, Jörg; Burzlaff, Tim; Honsel, Anne; Alfarraj, Saleh; Georgiev, Plamen; Schnitzler, Jörg-Peter; Ghirardo, Andrea; Kreuzer, Ines; Hedrich, Rainer; Rennenberg, Heinz

2014-02-01

Does Dionaea muscipula, the Venus flytrap, use a particular mechanism to attract animal prey? This question was raised by Charles Darwin 140 years ago, but it remains unanswered. This study tested the hypothesis that Dionaea releases volatile organic compounds (VOCs) to allure prey insects. For this purpose, olfactory choice bioassays were performed to elucidate if Dionaea attracts Drosophila melanogaster. The VOCs emitted by the plant were further analysed by GC-MS and proton transfer reaction-mass spectrometry (PTR-MS). The bioassays documented that Drosophila was strongly attracted by the carnivorous plant. Over 60 VOCs, including terpenes, benzenoids, and aliphatics, were emitted by Dionaea, predominantly in the light. This work further tested whether attraction of animal prey is affected by the nutritional status of the plant. For this purpose, Dionaea plants were fed with insect biomass to improve plant N status. However, although such feeding altered the VOC emission pattern by reducing terpene release, the attraction of Drosophila was not affected. From these results it is concluded that Dionaea attracts insects on the basis of food smell mimicry because the scent released has strong similarity to the bouquet of fruits and plant flowers. Such a volatile blend is emitted to attract insects searching for food to visit the deadly capture organ of the Venus flytrap.

Real-time measurement of sodium chloride in individual aerosol particles by mass spectrometry

NASA Technical Reports Server (NTRS)

Sinha, M. P.; Friedlander, S. K.

1985-01-01

The method of particle analysis by mass spectrometry has been applied to the quantitative measurement of sodium chloride in individual particles on a real-time basis. Particles of known masses are individually introduced, in the form of a beam, into a miniature Knudsen cell oven (1600 K). The oven is fabricated from rhenium metal sheet (0.018 mm thick) and is situated in the ion source of a quadrupole mass spectrometer. A particle once inside the oven is trapped and completely volatilized; this overcomes the problem of partial volatilization due to particles bouncing from the filament surface. Individual particles are thermally volatilized and ionized inside the rhenium oven, and produce discrete sodium ion pulses whose intensities are measured with the quadrupole mass spectrometer. An ion pulse width of several milliseconds (4-12 ms) is found for particles in the mass range 1.3 x 10 to the -13th to 5.4 x 10 to the -11th g. The sodium ion intensity is found to be proportional to the particle mass to the 0.86-power. The intensity distribution for monodisperse aerosol particles possesses a geometric standard deviation of 1.09, showing that the method can be used for the determination of the mass distribution function with good resolution in a polydisperse aerosol.

The Venus flytrap attracts insects by the release of volatile organic compounds

PubMed Central

Kreuzwieser, Jürgen; Honsel, Anne

2014-01-01

Does Dionaea muscipula, the Venus flytrap, use a particular mechanism to attract animal prey? This question was raised by Charles Darwin 140 years ago, but it remains unanswered. This study tested the hypothesis that Dionaea releases volatile organic compounds (VOCs) to allure prey insects. For this purpose, olfactory choice bioassays were performed to elucidate if Dionaea attracts Drosophila melanogaster. The VOCs emitted by the plant were further analysed by GC-MS and proton transfer reaction-mass spectrometry (PTR-MS). The bioassays documented that Drosophila was strongly attracted by the carnivorous plant. Over 60 VOCs, including terpenes, benzenoids, and aliphatics, were emitted by Dionaea, predominantly in the light. This work further tested whether attraction of animal prey is affected by the nutritional status of the plant. For this purpose, Dionaea plants were fed with insect biomass to improve plant N status. However, although such feeding altered the VOC emission pattern by reducing terpene release, the attraction of Drosophila was not affected. From these results it is concluded that Dionaea attracts insects on the basis of food smell mimicry because the scent released has strong similarity to the bouquet of fruits and plant flowers. Such a volatile blend is emitted to attract insects searching for food to visit the deadly capture organ of the Venus flytrap. PMID:24420576

Viscozyme L pretreatment on palm kernels improved the aroma of palm kernel oil after kernel roasting.

PubMed

Zhang, Wencan; Leong, Siew Mun; Zhao, Feifei; Zhao, Fangju; Yang, Tiankui; Liu, Shaoquan

2018-05-01

With an interest to enhance the aroma of palm kernel oil (PKO), Viscozyme L, an enzyme complex containing a wide range of carbohydrases, was applied to alter the carbohydrates in palm kernels (PK) to modulate the formation of volatiles upon kernel roasting. After Viscozyme treatment, the content of simple sugars and free amino acids in PK increased by 4.4-fold and 4.5-fold, respectively. After kernel roasting and oil extraction, significantly more 2,5-dimethylfuran, 2-[(methylthio)methyl]-furan, 1-(2-furanyl)-ethanone, 1-(2-furyl)-2-propanone, 5-methyl-2-furancarboxaldehyde and 2-acetyl-5-methylfuran but less 2-furanmethanol and 2-furanmethanol acetate were found in treated PKO; the correlation between their formation and simple sugar profile was estimated by using partial least square regression (PLS1). Obvious differences in pyrroles and Strecker aldehydes were also found between the control and treated PKOs. Principal component analysis (PCA) clearly discriminated the treated PKOs from that of control PKOs on the basis of all volatile compounds. Such changes in volatiles translated into distinct sensory attributes, whereby treated PKO was more caramelic and burnt after aqueous extraction and more nutty, roasty, caramelic and smoky after solvent extraction. Copyright © 2018 Elsevier Ltd. All rights reserved.

Benchmark of Ab Initio Bethe-Salpeter Equation Approach with Numeric Atom-Centered Orbitals

NASA Astrophysics Data System (ADS)

Liu, Chi; Kloppenburg, Jan; Kanai, Yosuke; Blum, Volker

The Bethe-Salpeter equation (BSE) approach based on the GW approximation has been shown to be successful for optical spectra prediction of solids and recently also for small molecules. We here present an all-electron implementation of the BSE using numeric atom-centered orbital (NAO) basis sets. In this work, we present benchmark of BSE implemented in FHI-aims for low-lying excitation energies for a set of small organic molecules, the well-known Thiel's set. The difference between our implementation (using an analytic continuation of the GW self-energy on the real axis) and the results generated by a fully frequency dependent GW treatment on the real axis is on the order of 0.07 eV for the benchmark molecular set. We study the convergence behavior to the complete basis set limit for excitation spectra, using a group of valence correlation consistent NAO basis sets (NAO-VCC-nZ), as well as for standard NAO basis sets for ground state DFT with extended augmentation functions (NAO+aug). The BSE results and convergence behavior are compared to linear-response time-dependent DFT, where excellent numerical convergence is shown for NAO+aug basis sets.

Kinetic balance and variational bounds failure in the solution of the Dirac equation in a finite Gaussian basis set

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Faegri, Knut, Jr.

1990-01-01

The paper investigates bounds failure in calculations using Gaussian basis sets for the solution of the one-electron Dirac equation for the 2p1/2 state of Hg(79+). It is shown that bounds failure indicates inadequacies in the basis set, both in terms of the exponent range and the number of functions. It is also shown that overrepresentation of the small component space may lead to unphysical results. It is concluded that it is important to use matched large and small component basis sets with an adequate size and exponent range.

Ab Initio and Analytic Intermolecular Potentials for Ar-CF₄

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

Vayner, Grigoriy; Alexeev, Yuri; Wang, Jiangping

2006-03-09

Ab initio calculations at the CCSD(T) level of theory are performed to characterize the Ar + CF ₄ intermolecular potential. Extensive calculations, with and without a correction for basis set superposition error (BSSE), are performed with the cc-pVTZ basis set. Additional calculations are performed with other correlation consistent (cc) basis sets to extrapolate the Ar---CF₄potential energy minimum to the complete basis set (CBS) limit. Both the size of the basis set and BSSE have substantial effects on the Ar + CF₄ potential. Calculations with the cc-pVTZ basis set and without a BSSE correction, appear to give a good representation ofmore » the potential at the CBS limit and with a BSSE correction. In addition, MP2 theory is found to give potential energies in very good agreement with those determined by the much higher level CCSD(T) theory. Two analytic potential energy functions were determined for Ar + CF₄by fitting the cc-pVTZ calculations both with and without a BSSE correction. These analytic functions were written as a sum of two body potentials and excellent fits to the ab initio potentials were obtained by representing each two body interaction as a Buckingham potential.« less

On the performance of large Gaussian basis sets for the computation of total atomization energies

NASA Technical Reports Server (NTRS)

Martin, J. M. L.

1992-01-01

The total atomization energies of a number of molecules have been computed using an augmented coupled-cluster method and (5s4p3d2f1g) and 4s3p2d1f) atomic natural orbital (ANO) basis sets, as well as the correlation consistent valence triple zeta plus polarization (cc-pVTZ) correlation consistent valence quadrupole zeta plus polarization (cc-pVQZ) basis sets. The performance of ANO and correlation consistent basis sets is comparable throughout, although the latter can result in significant CPU time savings. Whereas the inclusion of g functions has significant effects on the computed Sigma D(e) values, chemical accuracy is still not reached for molecules involving multiple bonds. A Gaussian-1 (G) type correction lowers the error, but not much beyond the accuracy of the G1 model itself. Using separate corrections for sigma bonds, pi bonds, and valence pairs brings down the mean absolute error to less than 1 kcal/mol for the spdf basis sets, and about 0.5 kcal/mol for the spdfg basis sets. Some conclusions on the success of the Gaussian-1 and Gaussian-2 models are drawn.

78 FR 63267 - Self-Regulatory Organizations; The Options Clearing Corporation; Notice of No Objection to...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-23

... the set of risk factors whose behavior is included in the econometric models underlying STANS, time series of proportional changes in implied volatilities for a range of tenors and in-the-money and out-of...

Styles and timing of volatile-driven activity in the eastern Hellas region of Mars

NASA Astrophysics Data System (ADS)

Crown, David A.; Bleamaster, Leslie F.; Mest, Scott C.

2005-12-01

Recent analyses of Mars Global Surveyor and Mars Odyssey data sets provide new insights into the geologic evolution of the eastern Hellas region of Mars, in particular, the role of volatiles. Here, we present results of our recent work and integrate these with previous studies by various investigators to provide a synthesis of the history of volatile-driven activity of the region. We utilize high-resolution images from the Mars Orbiter Camera and Thermal Emission Imaging System combined with Mars Orbiter Laser Altimeter digital elevation models and profiles to examine fluvial systems that dissect the circum-Hellas highlands, to characterize stages in the development of the Dao, Niger, Harmakhis, and Reull Valles canyon systems, and to evaluate evidence for ancient lakes in Hellas Planitia. The occurrence of valley networks, dissected highland crater rims, and crater interior deposits such as layered plateaus suggests widespread ancient degradation of the circum-Hellas highlands. Canyon development, which represents subsequent more localized activity, may have included an early fluvial phase followed by the collapse and sapping dominated stages that, along with recent wall erosion and floor resurfacing, produced the currently observed morphologies. The prominent role of collapse and sapping along the east rim of Hellas, along with the presence of numerous channels extending toward the basin and sequences of finely layered deposits along the basin rim, suggests a volatile-rich substrate across a broad depositional shelf. The east rim of the basin was an accumulation zone for atmospheric volatiles and/or the edge of volatile-rich deposits associated with the basin floor. This evidence combined with topographic data and cratered terrain preservation around the basin is consistent with a lacustrine period or periods in early Martian history. The style, magnitude, and spatial extent of volatile-driven activity in eastern Hellas have varied considerably with time, and these variations may represent a transition from a water- to an ice-dominated surface environment.

The effect of primary versus secondary processes on the volatile content of MORB glasses: An example from the equatorial Mid-Atlantic Ridge (5°N-3°S)

NASA Astrophysics Data System (ADS)

Le Voyer, Marion; Cottrell, Elizabeth; Kelley, Katherine A.; Brounce, Maryjo; Hauri, Erik H.

2015-01-01

We report microanalysis of volatile and trace element compositions, as well as Fe3+/ΣFe ratios, from 45 basaltic glasses from cruise RC2806 along the equatorial Mid-Atlantic Ridge. The along-strike variations in volatiles result from the complex geodynamical setting of the area, including numerous transform faults, variations in ridge depth, melting degree, and source composition. The strongest gradient is centered on 1.7°N and encompasses an increase of H2O, Cl, and F contents as well as high F/Zr ratio spatially coincident with radiogenic isotope anomalies. We interpret these variations as source enrichment due to the influence of the nearby high-μ-type Sierra Leone plume. South of the St. Paul fracture zone, H2O and F contents, as well as H2O/Ce and F/Zr ratios, decrease progressively. This gradient in volatiles is consistent with progressive dilution of an enriched component in a heterogeneous mantle due to the progressive increase in the degree of melting. These two large-scale gradients are interrupted by small-scale anomalies in volatile contents attributed to (1) low-degree melts preferentially sampling enriched heterogeneities near transform faults and (2) local assimilation of hydrothermal fluids in four samples from dredge 16D. Finally, 20 RC2806 samples described as "popping rocks" during collection do not show any difference in volatile content dissolved in the glass or in vesicularity when compared to the RC2806 "nonpopping" samples. Our observations lead us to question the interpretation of the CO2 content in the highly vesicular 2πD43 "popping rock" as being representative of the CO2 content of undegassed mid-ocean ridge basalt.

Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

NASA Astrophysics Data System (ADS)

Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

2016-05-01

In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

Estimation of the volatility distribution of organic aerosol combining thermodenuder and isothermal dilution measurements

NASA Astrophysics Data System (ADS)

Louvaris, Evangelos E.; Karnezi, Eleni; Kostenidou, Evangelia; Kaltsonoudis, Christos; Pandis, Spyros N.

2017-10-01

A method is developed following the work of Grieshop et al. (2009) for the determination of the organic aerosol (OA) volatility distribution combining thermodenuder (TD) and isothermal dilution measurements. The approach was tested in experiments that were conducted in a smog chamber using organic aerosol (OA) produced during meat charbroiling. A TD was operated at temperatures ranging from 25 to 250 °C with a 14 s centerline residence time coupled to a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a scanning mobility particle sizer (SMPS). In parallel, a dilution chamber filled with clean air was used to dilute isothermally the aerosol of the larger chamber by approximately a factor of 10. The OA mass fraction remaining was measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements were used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20 % of the OA evaporated within 15 min. Almost all the OA evaporated in the TD at approximately 200 °C. The resulting volatility distributions suggested that around 60-75 % of the cooking OA (COA) at concentrations around 500 µg m-3 consisted of low-volatility organic compounds (LVOCs), 20-30 % of semivolatile organic compounds (SVOCs), and around 10 % of intermediate-volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA was 100 ± 20 kJ mol-1 and the effective accommodation coefficient was 0.06-0.07. Addition of the dilution measurements to the TD data results in a lower uncertainty of the estimated vaporization enthalpy as well as the SVOC content of the OA.

The geologic classification of the meteorites

USGS Publications Warehouse

Elston, Donald Parker

1968-01-01

The meteorite classes of Prior and Mason are assigned to three proposed genetic groups on the basis of a combination of compositional, mineralogical, and elemental characteristics: l) the calcium-poor, volatile-rich carbonaceous chondrites and achondrites; 2) the calcium-poor, volatile-poor chondrites (enstatite, bronzite, hypersthene, and pigeonite), achondrites (enstatite, hypersthene, and pigeonite), stonyirons (pallasites, siderophyre), and irons; and, 3) the calcium-rich (basaltic) achondrites. Chondrites are correlated with calcium-poor achondrites and the silicate phase of the pallasitic meteorites on Fe contents of olivine and pyroxene; and with metal of the stony-irons and irons on the basis of trace elements (Ga and Ge). Transitions in structure and texture between the chondrites and achondrites are recognized. The Van Schmus-Wood chemical-petrologic classification of the chondrites has been modified and expanded to a mineralogic-petrologic classification of the chondrites and calcium-poor achondrites. Chondrites apparently are the first rocks of the solar system. Paragenetic and textural relations in the Murray carbonaceous chondrite shed new light on the manner of accretion, and on the character of dispersed solid materials ('dust', and chondrules and metal) that existed in the solar system before accretion. Two pre-accretionary mineral assemblages (components) are recognized in the carbonaceous chondrites and in the unequilibrated volatile-poor chondrites. They are: 1) a 'low temperature' water-, rare gas-, and carbon-bearing component; and, 2) a high temperature anhydrous silicate and metal component. Paragenetic relations indicate that component 2 materials predate chondrite formation. An accretionary assemblage (component 3) also is recognized in the carbonaceous chondrites and in the unequilibrated volatile-poor chondrites. Component 3 consists of very fine grains of olivine and pyroxene, which occur as pervasive disseminations, as small irregular aggregates of grains, and as large subround to round, finely granular accretional chondrules. Evidence in Murray indicates that component 3 silicates precipitated abruptly and at low pressures, possibly from a high temperature gas, in an environment that contained dispersed component 1 and 2 materials. All component 3 aggregates in Murray contain component 1 material, most commonly as flakes, and locally as tiny granules and larger spherules, some of which are hollow and some of which were broken prior to their mechanical incorporation in accretionary chondrules. Accretion may have occurred as ices associated with dispersed water-bearing component 1 materials temporarily melted during the precipitation of component 3 silicates, and then abruptly refroze to form an icy cementing material. Group 1 materials may be cometary, and group 2 materials may be asteroidal. Schematic models are proposed. Evidence is reviewed for the lunar origin of the pyroxeneplagioclase achondrites. On the basis of natural remanent magnetism, it is suggested that the very scarce diopside-olivine achondrites may be samples from Mars. A classification of the meteorite breccias, including the calcium-poor and calcium-rich mesosiderites, and irons that contain silicate fragments, is proposed. A fragmentation history of the meteorites is outlined on the basis of evidence in the polymict breccias, and from gas retention ages in stones and exposure ages in irons. Cometal impacts appear to have caused the initial fragmentation, stud possibly the perturbation of orbits, of two inferred asteroidal bodies (enstatite and bronzite), one and possibly both events occurring before 2000 m.y. ago. Several impacts apparently occurred on the inferred hypersthene body in the interval 1000 to 2000 m.y. ago. Major breakups of the three bodies apparently occurred as the result of interasteroidal collisions at about 900 m.y. ago, and 600 to 700 m.y. ago. The breakups were followed by a number of fr

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

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Polarized atomic orbitals for self-consistent field electronic structure calculations

NASA Astrophysics Data System (ADS)

Lee, Michael S.; Head-Gordon, Martin

1997-12-01

We present a new self-consistent field approach which, given a large "secondary" basis set of atomic orbitals, variationally optimizes molecular orbitals in terms of a small "primary" basis set of distorted atomic orbitals, which are simultaneously optimized. If the primary basis is taken as a minimal basis, the resulting functions are termed polarized atomic orbitals (PAO's) because they are valence (or core) atomic orbitals which have distorted or polarized in an optimal way for their molecular environment. The PAO's derive their flexibility from the fact that they are formed from atom-centered linear-combinations of the larger set of secondary atomic orbitals. The variational conditions satisfied by PAO's are defined, and an iterative method for performing a PAO-SCF calculation is introduced. We compare the PAO-SCF approach against full SCF calculations for the energies, dipoles, and molecular geometries of various molecules. The PAO's are potentially useful for studying large systems that are currently intractable with larger than minimal basis sets, as well as offering potential interpretative benefits relative to calculations in extended basis sets.

Identification and quantification of the major volatile constituents in antidepressant active fraction of xiaoyaosan by gas chromatography-mass spectrometry.

PubMed

Zhou, Yuzhi; Ren, Yanling; Ma, Zhijie; Jia, Guangcheng; Gao, Xiaoxia; Zhang, Lizeng; Qin, Xuemei

2012-05-07

Xiaoyaosan (XYS), a well-known formula for relieving depression, was originated from the book of "Taiping Huimin Heji Jufang" in Song Dynasty (960-1127 AD), composed of Radix Bupleuri, Radix Angelicae Sinensis, Radix Paeoniae Alba, Rhizoma Atractylodis Macrocephalae, Poria, Herba Menthae, Rhizoma Zingiberis Recens and Radix Glycyrrhizae with dose proportion of 6:6:6:6:6:3:2:2. It is commonly used for the treatment of depression-related syndromes in China. In the formula, Radix Bupleuri usually serves as the principal drug, Radix Angelicae Sinensis and Radix Paeoniae Alba serve as the ministerial drugs, Rhizoma Atractylodis Macrocephalae, Poria, Herba Menthae and Rhizoma Zingiberis Recens serve as adjunctive drugs, Radix Glycyrrhizae serves as messenger drug, they coordinate with each other and enhance the effect of the formula. In our previous experiments, the antidepressant effect of XYS was revealed. However, the antidepressant part (or component) of this prescription was still obscure. An experimental despair animal model: the mice tail suspension test (TST) was used to evaluate the antidepressant activity of XYS and its fractions. GC-MS method was developed to identify the volatile components and determine 4 major volatile components in active fraction. In the TST test, the effect of a low polar fraction (XY-EA) was superior to other fractions of XYS. 13 volatile compounds in the XY-EA were identified on the basis of standards, isolation and structural determination in our laboratory, NIST 05 database and literature data. The content of 4 major volatile compounds in XY-EA which is 6.703%. The petroleum ether fraction (XY-EA) appears to be the active fraction of XYS. 4 major components Z-ligustilide, palmitic acid, atractylenolide I, and atractylenolide II may be the antidepressant active compounds. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Gram-negative and -positive bacteria differentiation in blood culture samples by headspace volatile compound analysis.

PubMed

Dolch, Michael E; Janitza, Silke; Boulesteix, Anne-Laure; Graßmann-Lichtenauer, Carola; Praun, Siegfried; Denzer, Wolfgang; Schelling, Gustav; Schubert, Sören

2016-12-01

Identification of microorganisms in positive blood cultures still relies on standard techniques such as Gram staining followed by culturing with definite microorganism identification. Alternatively, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry or the analysis of headspace volatile compound (VC) composition produced by cultures can help to differentiate between microorganisms under experimental conditions. This study assessed the efficacy of volatile compound based microorganism differentiation into Gram-negatives and -positives in unselected positive blood culture samples from patients. Headspace gas samples of positive blood culture samples were transferred to sterilized, sealed, and evacuated 20 ml glass vials and stored at -30 °C until batch analysis. Headspace gas VC content analysis was carried out via an auto sampler connected to an ion-molecule reaction mass spectrometer (IMR-MS). Measurements covered a mass range from 16 to 135 u including CO2, H2, N2, and O2. Prediction rules for microorganism identification based on VC composition were derived using a training data set and evaluated using a validation data set within a random split validation procedure. One-hundred-fifty-two aerobic samples growing 27 Gram-negatives, 106 Gram-positives, and 19 fungi and 130 anaerobic samples growing 37 Gram-negatives, 91 Gram-positives, and two fungi were analysed. In anaerobic samples, ten discriminators were identified by the random forest method allowing for bacteria differentiation into Gram-negative and -positive (error rate: 16.7 % in validation data set). For aerobic samples the error rate was not better than random. In anaerobic blood culture samples of patients IMR-MS based headspace VC composition analysis facilitates bacteria differentiation into Gram-negative and -positive.

It's the little things that matter most: The role of volatiles in volcanoes and their magmatic roots

NASA Astrophysics Data System (ADS)

Keller, T.; Suckale, J.

2017-12-01

Many volcanic eruptions are driven by volatiles - mostly H2O and CO2 - that degas from magmas rising up beneath the volcano. Gas expands during ascent, thus frequently creating lavas with upward of 50% vesicularity. That is a particularly compelling observation considering that volatiles are only present at concentrations of order 100 ppm in the mantle source. Yet, even at these small concentrations, volatiles significantly lower the peridotite solidus. That leads to the production of reactive volatile-rich melts at depth, which has important consequences for melt transport in the asthenosphere. Thus, volatiles have a pivotal role both at the beginning and the end of the magmatic storyline. A growing amount of observational evidence provides various perspectives on these systems. Volcanic products are characterised increasingly well by geochemical and petrological data. And, volcano monitoring now often provides continuous records of degassing flux and composition. What is missing to better interpret these data are coupled fluid mechanic and thermodynamic models that link melt production and reactive transport in the mantle and crust with degassing-driven volcanic activity at the surface. Such models need to describe the deformation and segregation of multiple material phases (liquids, solids, gases) and track the reactive transport of diverse chemical components (major elements, trace elements, volatiles). I will present progress towards a generalization of existing two-phase model for melt transport in the mantle, extending them to three-phase flows appropriate for magma circulation and degassing in volcanoes. What sets the two environments apart is the presence of a compressible vapor in volcanoes. Also, volcanic degassing may occur by convecting suspensions as well as porous segregation. The model framework we are developing for these processes is based on mixture theory. Uncovering the underlying physics that connects these diverse expressions of magma transport will provide an opportunity to gain deeper insights into magmatic and volcanic phenomena as related rather than separate processes. In time we may thus come to more fully understand how it is that the little things that are mantle volatiles do matter most in volcanoes and their magmatic roots.

Addressing Inter-set Write-Variation for Improving Lifetime of Non-Volatile Caches

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

Mittal, Sparsh; Vetter, Jeffrey S

We propose a technique which minimizes inter-set write variation in NVM caches for improving its lifetime. Our technique uses cache coloring scheme to add a software-controlled mapping layer between groups of physical pages (called memory regions) and cache sets. Periodically, the number of writes to different colors of the cache is computed and based on this result, the mapping of a few colors is changed to channel the write traffic to least utilized cache colors. This change helps to achieve wear-leveling.

Computational fluid dynamics study of pulverized coal combustion in blast furnace raceway

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

Shen, Y.S.; Maldonado, D.; Guo, B.Y.

In this work, a numerical model is used to study the flow and coal combustion along the coal plume in a large-scale setting simulating the lance-blowpipe-tuyere-raceway region of a blast furnace. The model formulation is validated against the measurements in terms of burnout for both low and high volatile coals. The typical phenomena related to coal combustion along the coal plume are simulated and analyzed. The effects of some operational parameters on combustion behavior are also investigated. The results indicate that oxygen as a cooling gas gives a higher coal burnout than methane and air. The underlying mechanism of coalmore » combustion is explored. It is shown that under the conditions examined, coal burnout strongly depends on the availability of oxygen and residence time. Moreover, the influences of two related issues, i.e. the treatment of volatile matter (VM) and geometric setting in modeling, are investigated. The results show that the predictions of final burnouts using three different VM treatments are just slightly different, but all comparable to the measurements. However, the influence of the geometric setting is not negligible when numerically examining the combustion of pulverized coal under blast furnace conditions.« less

Electrothermal adsorption and desorption of volatile organic compounds on activated carbon fiber cloth.

PubMed

Son, H K; Sivakumar, S; Rood, M J; Kim, B J

2016-01-15

Adsorption is an effective means to selectively remove volatile organic compounds (VOCs) from industrial gas streams and is particularly of use for gas streams that exhibit highly variable daily concentrations of VOCs. Adsorption of such gas streams by activated carbon fiber cloths (ACFCs) and subsequent controlled desorption can provide gas streams of well-defined concentration that can then be more efficiently treated by biofiltration than streams exhibiting large variability in concentration. In this study, we passed VOC-containing gas through an ACFC vessel for adsorption and then desorption in a concentration-controlled manner via electrothermal heating. Set-point concentrations (40-900 ppm(v)) and superficial gas velocity (6.3-9.9 m/s) were controlled by a data acquisition and control system. The results of the average VOC desorption, desorption factor and VOC in-and-out ratio were calculated and compared for various gas set-point concentrations and superficial gas velocities. Our results reveal that desorption is strongly dependent on the set-point concentration and that the VOC desorption rate can be successfully equalized and controlled via an electrothermal adsorption system. Copyright © 2015 Elsevier B.V. All rights reserved.

Origin of particulate matter and gaseous precursors in the Paris Megacity: Results from intensive campaigns, long term measurements and modelling

NASA Astrophysics Data System (ADS)

Beekmann, Matthias; Petetin, Hervé; Zhang, Qijie; Prevot, André S. H.; Sciare, Jean; Gros, Valérie; Ghersi, Véronique; Rosso, Amandine; Crippa, Monica; Zotter, Peter; Freutel, Fredericke; Poulain, Laurent; Freney, Evelyne; Sellegri, Karine; Drewnick, Frank; Borbon, Agnès; Wiedensohler, Aflred; Pandis, Spyros N.; Baltensperger, Urs

2016-04-01

Uncertainties on the origin of primary and secondary particulate matter and its gaseous precursors in megacities is still large and needs to be reduced. A detailed characterization of air quality in Paris (France), a megacity of more than 10 million inhabitants, during two one month intensive campaigns (MEGAPOLI) and from additional one year observations (PARTICULATE and FRANCIPOL), revealed that about 70% of the fine particulate matter (PM) at urban background is transported on average into the megacity from upwind regions. While advection of sulfate is well documented for other megacities, there was a surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The data set of urban local and advected PM concentrations in the Paris area were used for a thorough evaluation of the CHIMERE model and revealed error compensation for the local and advected components of organic matter and nitrate. During spring time, CHIMERE simulations overestimate the sensitivity of ammonium nitrate peaks to NH3, because (i) they underestimate the urban background NH3 levels, probably due to neglecting enhanced NH3 emissions for larger temperatures, and because they overestimate HNO3. However, from an ensemble of mobile Max-DOAS NO2 column and airborne NOy measurements around Paris, no clear sign on a NOx emission bias in the TNO-Airparif data set was made evident. The origin of organic PM was investigated by a comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions contributed less than 20% in winter and 40% in summer to carbonaceous fine PM, unexpectedly little for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e. from biogenic precursors and from wood burning. Implementation of different configurations of the volatility basis set into the CHIMERE model allowed correctly representing summertime organic aerosol (OA) peaks within the agglomeration and attributing them to biogenic secondary OA as a major source. OA build-up from anthropogenic precursors within the plume was also correctly simulated, but it was not possible to attribute it specifically to oxidation of aromatic or of semi/ intermediate volatile organic compounds. Plume build-up of PM significantly contributes to regional air quality around the Paris region.

MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS IN EXHALED BREATH AS COLLECTED IN EVACUATED ELECTROPOLISHED CANISTERS

EPA Science Inventory

A set of three complementary analytical methods were developed specifically for exhaled breath as collected in evacuated stainless steel canisters using gas chromatography - mass spectrometry detection. The first is a screening method to quantify the carbon dioxide component (gen...

Three-way principal component analysis of the volatile fraction by HS-SPME/GC of aceto balsamico tradizionale of modena.

PubMed

Cocchi, Marina; Durante, Caterina; Grandi, Margherita; Manzini, Daniela; Marchetti, Andrea

2008-01-15

The present research is aimed at monitoring the evolution of the volatile organic compounds of different samples of aceto balsamico tradizionale of modena (ABTM) during ageing. The flavouring compounds, headspace fraction, of the vinegars of four batterie were sampled by solid phase microextraction technique (SPME), and successively analysed by gas chromatography. Obtaining a data set characterized by different sources of variability such as, different producers, samples of different age and chromatographic profile. The gas chromatographic signals were processed by a three-way data analysis method (Tucker3), which allows an easy visualisation of the data by furnishing a distinct set of graphs for each source of variability. The obtained results indicate that the samples can be separated according to their age highlighting the chemical constituents, which play a major role for their differentiation. The present study represents an example of how the application of Tucker3 models, on gas chromatographic signals may help to follow the transformation processes of food products.

42 CFR 415.170 - Conditions for payment on a fee schedule basis for physician services in a teaching setting.

Code of Federal Regulations, 2010 CFR

2010-10-01

... physician services in a teaching setting. 415.170 Section 415.170 Public Health CENTERS FOR MEDICARE... BY PHYSICIANS IN PROVIDERS, SUPERVISING PHYSICIANS IN TEACHING SETTINGS, AND RESIDENTS IN CERTAIN SETTINGS Physician Services in Teaching Settings § 415.170 Conditions for payment on a fee schedule basis...

New PLS analysis approach to wine volatile compounds characterization by near infrared spectroscopy (NIR).

PubMed

Genisheva, Z; Quintelas, C; Mesquita, D P; Ferreira, E C; Oliveira, J M; Amaral, A L

2018-04-25

This work aims to explore the potential of near infrared (NIR) spectroscopy to quantify volatile compounds in Vinho Verde wines, commonly determined by gas chromatography. For this purpose, 105 Vinho Verde wine samples were analyzed using Fourier transform near infrared (FT-NIR) transmission spectroscopy in the range of 5435 cm -1 to 6357 cm -1 . Boxplot and principal components analysis (PCA) were performed for clusters identification and outliers removal. A partial least square (PLS) regression was then applied to develop the calibration models, by a new iterative approach. The predictive ability of the models was confirmed by an external validation procedure with an independent sample set. The obtained results could be considered as quite good with coefficients of determination (R 2 ) varying from 0.94 to 0.97. The current methodology, using NIR spectroscopy and chemometrics, can be seen as a promising rapid tool to determine volatile compounds in Vinho Verde wines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Detection of coffee flavour ageing by solid-phase microextraction/surface acoustic wave sensor array technique (SPME/SAW).

PubMed

Barié, Nicole; Bücking, Mark; Stahl, Ullrich; Rapp, Michael

2015-06-01

The use of polymer coated surface acoustic wave (SAW) sensor arrays is a very promising technique for highly sensitive and selective detection of volatile organic compounds (VOCs). We present new developments to achieve a low cost sensor setup with a sampling method enabling the highly reproducible detection of volatiles even in the ppb range. Since the VOCs of coffee are well known by gas chromatography (GC) research studies, the new sensor array was tested for an easy assessable objective: coffee ageing during storage. As reference method these changes were traced with a standard GC/FID set-up, accompanied by sensory panellists. The evaluation of GC data showed a non-linear characteristic for single compound concentrations as well as for total peak area values, disabling prediction of the coffee age. In contrast, the new SAW sensor array demonstrates a linear dependency, i.e. being capable to show a dependency between volatile concentration and storage time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Non-volatile Clocked Spin Wave Interconnect for Beyond-CMOS Nanomagnet Pipelines

PubMed Central

Dutta, Sourav; Chang, Sou-Chi; Kani, Nickvash; Nikonov, Dmitri E.; Manipatruni, Sasikanth; Young, Ian A.; Naeemi, Azad

2015-01-01

The possibility of using spin waves for information transmission and processing has been an area of active research due to the unique ability to manipulate the amplitude and phase of the spin waves for building complex logic circuits with less physical resources and low power consumption. Previous proposals on spin wave logic circuits have suggested the idea of utilizing the magneto-electric effect for spin wave amplification and amplitude- or phase-dependent switching of magneto-electric cells. Here, we propose a comprehensive scheme for building a clocked non-volatile spin wave device by introducing a charge-to-spin converter that translates information from electrical domain to spin domain, magneto-electric spin wave repeaters that operate in three different regimes - spin wave transmitter, non-volatile memory and spin wave detector, and a novel clocking scheme that ensures sequential transmission of information and non-reciprocity. The proposed device satisfies the five essential requirements for logic application: nonlinearity, amplification, concatenability, feedback prevention, and complete set of Boolean operations. PMID:25955353

Multicriteria adaptation principle on example of groups of mobile robots

NASA Astrophysics Data System (ADS)

Nelyubin, A. P.; Misyurin, S. Yu

2017-12-01

The article presents a multicriteria approach to the adaptation of groups of search, explore or research robots to unknown and volatile environment conditions. The basis of this approach is the application of multicriteria analysis both at the design stage of a group of mobile robots and at the stage of its adaptation in real-time conditions. It is proposed to maintain a variety of robots by properties and by optimality criteria in order to take into account the preferred mode of operation.

Evaluation of Integrated Anaerobic Digestion and Hydrothermal Carbonization for Bioenergy Production

PubMed Central

Reza, M. Toufiq; Werner, Maja; Pohl, Marcel; Mumme, Jan

2014-01-01

Lignocellulosic biomass is one of the most abundant yet underutilized renewable energy resources. Both anaerobic digestion (AD) and hydrothermal carbonization (HTC) are promising technologies for bioenergy production from biomass in terms of biogas and HTC biochar, respectively. In this study, the combination of AD and HTC is proposed to increase overall bioenergy production. Wheat straw was anaerobically digested in a novel upflow anaerobic solid state reactor (UASS) in both mesophilic (37 °C) and thermophilic (55 °C) conditions. Wet digested from thermophilic AD was hydrothermally carbonized at 230 °C for 6 hr for HTC biochar production. At thermophilic temperature, the UASS system yields an average of 165 LCH4/kgVS (VS: volatile solids) and 121 L CH4/kgVS at mesophilic AD over the continuous operation of 200 days. Meanwhile, 43.4 g of HTC biochar with 29.6 MJ/kgdry_biochar was obtained from HTC of 1 kg digestate (dry basis) from mesophilic AD. The combination of AD and HTC, in this particular set of experiment yield 13.2 MJ of energy per 1 kg of dry wheat straw, which is at least 20% higher than HTC alone and 60.2% higher than AD only. PMID:24962786

Projected Hybrid Orbitals: A General QM/MM Method

PubMed Central

2015-01-01

A projected hybrid orbital (PHO) method was described to model the covalent boundary in a hybrid quantum mechanical and molecular mechanical (QM/MM) system. The PHO approach can be used in ab initio wave function theory and in density functional theory with any basis set without introducing system-dependent parameters. In this method, a secondary basis set on the boundary atom is introduced to formulate a set of hybrid atomic orbtials. The primary basis set on the boundary atom used for the QM subsystem is projected onto the secondary basis to yield a representation that provides a good approximation to the electron-withdrawing power of the primary basis set to balance electronic interactions between QM and MM subsystems. The PHO method has been tested on a range of molecules and properties. Comparison with results obtained from QM calculations on the entire system shows that the present PHO method is a robust and balanced QM/MM scheme that preserves the structural and electronic properties of the QM region. PMID:25317748

A novel Gaussian-Sinc mixed basis set for electronic structure calculations

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

Jerke, Jonathan L.; Lee, Young; Tymczak, C. J.

2015-08-14

A Gaussian-Sinc basis set methodology is presented for the calculation of the electronic structure of atoms and molecules at the Hartree–Fock level of theory. This methodology has several advantages over previous methods. The all-electron electronic structure in a Gaussian-Sinc mixed basis spans both the “localized” and “delocalized” regions. A basis set for each region is combined to make a new basis methodology—a lattice of orthonormal sinc functions is used to represent the “delocalized” regions and the atom-centered Gaussian functions are used to represent the “localized” regions to any desired accuracy. For this mixed basis, all the Coulomb integrals are definablemore » and can be computed in a dimensional separated methodology. Additionally, the Sinc basis is translationally invariant, which allows for the Coulomb singularity to be placed anywhere including on lattice sites. Finally, boundary conditions are always satisfied with this basis. To demonstrate the utility of this method, we calculated the ground state Hartree–Fock energies for atoms up to neon, the diatomic systems H{sub 2}, O{sub 2}, and N{sub 2}, and the multi-atom system benzene. Together, it is shown that the Gaussian-Sinc mixed basis set is a flexible and accurate method for solving the electronic structure of atomic and molecular species.« less

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

Hill, J. Grant, E-mail: grant.hill@sheffield.ac.uk, E-mail: kipeters@wsu.edu; Peterson, Kirk A., E-mail: grant.hill@sheffield.ac.uk, E-mail: kipeters@wsu.edu

New correlation consistent basis sets, cc-pVnZ-PP-F12 (n = D, T, Q), for all the post-d main group elements Ga–Rn have been optimized for use in explicitly correlated F12 calculations. The new sets, which include not only orbital basis sets but also the matching auxiliary sets required for density fitting both conventional and F12 integrals, are designed for correlation of valence sp, as well as the outer-core d electrons. The basis sets are constructed for use with the previously published small-core relativistic pseudopotentials of the Stuttgart-Cologne variety. Benchmark explicitly correlated coupled-cluster singles and doubles with perturbative triples [CCSD(T)-F12b] calculations of themore » spectroscopic properties of numerous diatomic molecules involving 4p, 5p, and 6p elements have been carried out and compared to the analogous conventional CCSD(T) results. In general the F12 results obtained with a n-zeta F12 basis set were comparable to conventional aug-cc-pVxZ-PP or aug-cc-pwCVxZ-PP basis set calculations obtained with x = n + 1 or even x = n + 2. The new sets used in CCSD(T)-F12b calculations are particularly efficient at accurately recovering the large correlation effects of the outer-core d electrons.« less

Gas/Particle Partitioning of Organic Acids and Organic Aerosols in a Ponderosa Pine Forest in Colorado during BEACHON-RoMBAS 2011

NASA Astrophysics Data System (ADS)

Jimenez, J. L.; Yatavelli, L.; Stark, H.; Hayes, P. L.; Campuzano-Jost, P.; Thompson, S.; Kimmel, J. R.; Day, D. A.; Cubison, M. J.; Thornton, J. A.; Jayne, J.; Worsnop, D. R.

2012-12-01

The Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) took place at Manitou Forest, CO, during July-Aug. 2011. Gas and particle-phase organic acids were analyzed in real time using a micro-orifice volatilization impactor chemical ionization high-resolution time-of-flight mass spectrometer (MOVI-HRToF-CIMS; Yatavelli et al., AS&T 2012; Yatavelli & Thornton, AS&T 2010) with acetate as the reagent ion. During the gas sampling phase (when the MOVI was at room temperature) aerosol was collected on the MOVI impactor, and was subsequently thermally desorbed over 10 min. under nitrogen, allowing the collection of temperature-programmed thermal desorption (TPTD) mass spectra of particle-phase species. The high resolution of the instrument allows the determination of the elemental composition of most detected ions. Positive Matrix Factorization (PMF) is shown to be very useful to quantify the CIMS backgrounds during the different phases of operation. Two methods were used to estimate the volatility of the detected species. First, the fraction of each species in the particle phase (Fp) vs carbon number was found to approximately follow partitioning theory, both for the alkanoic acids and also for the total acid signal, after accounting for the effect of the oxidation state on vapor pressure. Fp was found to respond on timescales of ~1 h to changes in ambient temperature, indicating that diffusion limitations to evaporation are not major for the aerosol at this site. Preliminary results suggest that Fp depends more strongly on vapor pressure and temperature than on RH, suggesting preferential partitioning for the organic phase rather than the water phase. Secondly, the volatility of individual or groups of acids can be quantified based on the TPTD signal based on calibration with multiple acids of known vapor pressure at concentrations similar to ambient, analogous to the methods of Chattopadhyay and Ziemann (Anal. Chem. 2001) and Faulhaber et al. (AMT, 2009) for other TPTD techniques. The log of the vapor pressure of each compound is shown to be strongly related to the inverse of the desorption temperature for standards spanning 6 orders of magnitude in vapor pressure. A shift in the calibration curve when compared to other techniques is attributed to differences in time available for evaporation and physical arrangement of the particles on the aerosol collection surface. A method to remove the broadening of the transfer function is used to produce more accurate volatility distributions ("basis sets", VBS). Results of both methods are compared, also focusing on key species such as pinic, pinonic, tricarballylic, and oxalic acids. The effects of gas-phase adsorption on the thermogram signal are estimated based on tests sampling through a teflon filter. In addition, an Aerodyne Aerosol Mass Spectrometer (AMS) sampled ambient air and also air that had been thermally denuded at different temperatures. The method of Faulhaber et al is used to derive an estimated volatility distribution for the total organic aerosol and the organic acid fraction (based on m/z 44, CO2+), which are compared to the CIMS results.

Comparison of fMRI analysis methods for heterogeneous BOLD responses in block design studies

PubMed Central

Bernal-Casas, David; Fang, Zhongnan; Lee, Jin Hyung

2017-01-01

A large number of fMRI studies have shown that the temporal dynamics of evoked BOLD responses can be highly heterogeneous. Failing to model heterogeneous responses in statistical analysis can lead to significant errors in signal detection and characterization and alter the neurobiological interpretation. However, to date it is not clear that, out of a large number of options, which methods are robust against variability in the temporal dynamics of BOLD responses in block-design studies. Here, we used rodent optogenetic fMRI data with heterogeneous BOLD responses and simulations guided by experimental data as a means to investigate different analysis methods’ performance against heterogeneous BOLD responses. Evaluations are carried out within the general linear model (GLM) framework and consist of standard basis sets as well as independent component analysis (ICA). Analyses show that, in the presence of heterogeneous BOLD responses, conventionally used GLM with a canonical basis set leads to considerable errors in the detection and characterization of BOLD responses. Our results suggest that the 3rd and 4th order gamma basis sets, the 7th to 9th order finite impulse response (FIR) basis sets, the 5th to 9th order B-spline basis sets, and the 2nd to 5th order Fourier basis sets are optimal for good balance between detection and characterization, while the 1st order Fourier basis set (coherence analysis) used in our earlier studies show good detection capability. ICA has mostly good detection and characterization capabilities, but detects a large volume of spurious activation with the control fMRI data. PMID:27993672

Conventional and Explicitly Correlated ab Initio Benchmark Study on Water Clusters: Revision of the BEGDB and WATER27 Data Sets.

PubMed

Manna, Debashree; Kesharwani, Manoj K; Sylvetsky, Nitai; Martin, Jan M L

2017-07-11

Benchmark ab initio energies for BEGDB and WATER27 data sets have been re-examined at the MP2 and CCSD(T) levels with both conventional and explicitly correlated (F12) approaches. The basis set convergence of both conventional and explicitly correlated methods has been investigated in detail, both with and without counterpoise corrections. For the MP2 and CCSD-MP2 contributions, rapid basis set convergence observed with explicitly correlated methods is compared to conventional methods. However, conventional, orbital-based calculations are preferred for the calculation of the (T) term, since it does not benefit from F12. CCSD(F12*) converges somewhat faster with the basis set than CCSD-F12b for the CCSD-MP2 term. The performance of various DFT methods is also evaluated for the BEGDB data set, and results show that Head-Gordon's ωB97X-V and ωB97M-V functionals outperform all other DFT functionals. Counterpoise-corrected DSD-PBEP86 and raw DSD-PBEPBE-NL also perform well and are close to MP2 results. In the WATER27 data set, the anionic (deprotonated) water clusters exhibit unacceptably slow basis set convergence with the regular cc-pVnZ-F12 basis sets, which have only diffuse s and p functions. To overcome this, we have constructed modified basis sets, denoted aug-cc-pVnZ-F12 or aVnZ-F12, which have been augmented with diffuse functions on the higher angular momenta. The calculated final dissociation energies of BEGDB and WATER27 data sets are available in the Supporting Information. Our best calculated dissociation energies can be reproduced through n-body expansion, provided one pushes to the basis set and electron correlation limit for the two-body term; for the three-body term, post-MP2 contributions (particularly CCSD-MP2) are important for capturing the three-body dispersion effects. Terms beyond four-body can be adequately captured at the MP2-F12 level.

VOLATILIZATION RATES FROM WATER TO INDOOR AIR ...

EPA Pesticide Factsheets

Contaminated water can lead to volatilization of chemicals to residential indoor air. Previous research has focused on only one source (shower stalls) and has been limited to chemicals in which gas-phase resistance to mass transfer is of marginal significance. As a result, attempts to extrapolate chemical emissions from high-volatility chemicals to lower volatility chemicals, or to sources other than showers, have been difficult or impossible. This study involved the development of two-phase, dynamic mass balance models for estimating chemical emissions from washing machines, dishwashers, and bathtubs. An existing model was adopted for showers only. Each model required the use of source- and chemical-specific mass transfer coefficients. Air exchange (ventilation) rates were required for dishwashers and washing machines as well. These parameters were estimated based on a series of 113 experiments involving 5 tracer chemicals (acetone, ethyl acetate, toluene, ethylbenzene, and cyclohexane) and 4 sources (showers, bathtubs, washing machines, and dishwashers). Each set of experiments led to the determination of chemical stripping efficiencies and mass transfer coefficients (overall, liquid-phase, gas-phase), and to an assessment of the importance of gas- phase resistance to mass transfer. Stripping efficiencies ranged from 6.3% to 80% for showers, 2.6% to 69% for bathtubs, 18% to 100% for dishwashers, and 3.8% to 100% for washing machines. Acetone and cyclohexane al

Volatile metabolomic signature of human breast cancer cell lines

PubMed Central

Silva, Catarina L.; Perestrelo, Rosa; Silva, Pedro; Tomás, Helena; Câmara, José S.

2017-01-01

Breast cancer (BC) remains the most prevalent oncologic pathology in women, causing huge psychological, economic and social impacts on our society. Currently, the available diagnostic tools have limited sensitivity and specificity. Metabolome analysis has emerged as a powerful tool for obtaining information about the biological processes that occur in organisms, and is a useful platform for discovering new biomarkers or make disease diagnosis using different biofluids. Volatile organic compounds (VOCs) from the headspace of cultured BC cells and normal human mammary epithelial cells, were collected by headspace solid-phase microextraction (HS-SPME) and analyzed by gas chromatography combined with mass spectrometry (GC–MS), thus defining a volatile metabolomic signature. 2-Pentanone, 2-heptanone, 3-methyl-3-buten-1-ol, ethyl acetate, ethyl propanoate and 2-methyl butanoate were detected only in cultured BC cell lines. Multivariate statistical methods were used to verify the volatomic differences between BC cell lines and normal cells in order to find a set of specific VOCs that could be associated with BC, providing comprehensive insight into VOCs as potential cancer biomarkers. The establishment of the volatile fingerprint of BC cell lines presents a powerful approach to find endogenous VOCs that could be used to improve the BC diagnostic tools and explore the associated metabolomic pathways. PMID:28256598

On the Use of a Mixed Gaussian/Finite-Element Basis Set for the Calculation of Rydberg States

NASA Technical Reports Server (NTRS)

Thuemmel, Helmar T.; Langhoff, Stephen (Technical Monitor)

1996-01-01

Configuration-interaction studies are reported for the Rydberg states of the helium atom using mixed Gaussian/finite-element (GTO/FE) one particle basis sets. Standard Gaussian valence basis sets are employed, like those, used extensively in quantum chemistry calculations. It is shown that the term values for high-lying Rydberg states of the helium atom can be obtained accurately (within 1 cm -1), even for a small GTO set, by augmenting the n-particle space with configurations, where orthonormalized interpolation polynomials are singly occupied.

Petrographic and Vitrinite Reflectance Analyses of a Suite of High Volatile Bituminous Coal Samples from the United States and Venezuela

USGS Publications Warehouse

Hackley, Paul C.; Kolak, Jonathan J.

2008-01-01

This report presents vitrinite reflectance and detailed organic composition data for nine high volatile bituminous coal samples. These samples were selected to provide a single, internally consistent set of reflectance and composition analyses to facilitate the study of linkages among coal composition, bitumen generation during thermal maturation, and geochemical characteristics of generated hydrocarbons. Understanding these linkages is important for addressing several issues, including: the role of coal as a source rock within a petroleum system, the potential for conversion of coal resources to liquid hydrocarbon fuels, and the interactions between coal and carbon dioxide during enhanced coalbed methane recovery and(or) carbon dioxide sequestration in coal beds.

Carbon Concentration Excursions in Apatite Phenocrysts from the Cerro Galan Ignimbrite: A SIMS View into the Transient pre-Eruptive Volatile History of a Supervolcano

NASA Astrophysics Data System (ADS)

Boyce, J. W.; Hervig, R. L.

2006-12-01

In nearly all igneous rock compositions, apatite is the most abundant mineral that regularly incorporates significant quantities of volatile elements into its structure, making it a potentially useful tool for exploring magmatic processing of volatiles (as well as REEs, Sr, Nd, and Pb isotopes, all of which are typically abundant in apatite). We have developed an analytical protocol that permits measurement of C, H, F, S, and Cl in ~8μm diameter regions of apatite using the Cameca 6f SIMS. A primary Cs+ beam (4-10 nA) is used in conjunction with electron gun charge-compensation to sputter negative ions from polished sections and unpolished crystal faces mounted in volatile-free indium mounts. We operated at mass resolving powers sufficient to separate all potential interferences (such as ^{31}PH and 16O2 from ^{32}S, and 17O from 16OH). Quantifying the SIMS data requires a set of standards that are 1) homogeneous at the few-micron scale; and 2) well-calibrated with multiple, reliable, independent volatile content measurements. Using values combed from the literature and other unpublished sources, we have assembled a set of apatite standards, none of which are proven to meet either criteria. Nevertheless, these materials allow us to create calibration curves for all of the volatile elements listed above. Traverses across polished basal sections of apatite phenocrysts from the ~1000 km3 Cerro Galan ignimbrite, Argentina (courtesy of C. Schirnick) yield the following results: Apatites are fluorine-rich, and contain significant and reproducible intracrystalline variations in C, H, S, and Cl. Positive carbon concentration excursions (up to 360 ppm) are factors of 2-7 greater than apatite baseline concentrations (40-60 ppm), the largest of which correlate with position in different grains. In the majority of the traverses, these carbon excursions also correlate spatially with 25-30% increases in sulfur concentration. We suggest that these dramatic increases in carbon and sulfur concentrations record a transient increase in magmatic SO4^{2- } and CO2 activities, perhaps the result of an underplating/recharge event, followed by a return to baseline magma chemistry. Hydrogen-poor rims are observed in all studied crystals, and are accompanied by chlorine-impoverished rims in a majority of the traverses, perhaps recording the pre- or syn-eruption exsolution of a vapor phase enriched in H and Cl.

Complex Anisotropic Structure of the Mantle Wedge Beneath Kamchatka Volcanoes

NASA Astrophysics Data System (ADS)

Levin, V.; Park, J.; Gordeev, E.; Droznin, D.

2002-12-01

A wedge of mantle material above the subducting lithospheric plate at a convergent margin is among the most dynamic environments of the Earth's interior. Deformation and transport of solid and volatile phases within this region control the fundamental process of elemental exchange between the surficial layers and the interior of the planet. A helpful property in the study of material deformation and transport within the upper mantle is seismic anisotropy, which may reflect both microscopic effects of preferentialy aligned crystals of olivine and orthopyroxene and macroscopic effects of systematic cracks, melt lenses, layering etc. Through the mapping of anisotropic properties within the mantle wedge we can establish patterns of deformation. Volatile content affects olivine alignment, so regions of anomalous volatile content may be evident. Indicators of seismic anisotropy commonly employed in upper mantle studies include shear wave birefringence and mode-conversion between compressional and shear body waves. When combined together, these techniques offer complementary constraints on the location and intensity of anisotropic properties. The eastern coast of southern Kamchatka overlies a vigorous convergent margin where the Pacific plate descends at a rate of almost 80 mm/yr towards the northwest. We extracted seismic anisotropy indicators from two data sets sensitive to the anisotropic properties of the uppermost mantle. Firstly, we evaluated teleseismic receiver functions for a number of sites, and found ample evidence for anisotropicaly-influenced P-to-S mode conversion. Secondly, we measured splitting in S waves of earthquakes with sources within the downgoing slab. The first set of observations provides constraints on the depth ranges where strong changes in anisotropic properties take place. The local splitting data provides constraints on the cumulative strength of anisotropic properties along specific pathways through the mantle wedge and possibly parts of the slab. To explain the vertical stratification of anisotropy implied from receiver functions, and the strong lateral dependence of shear-wave splitting observations, we cannot rely on simple models of mantle wedge behaviour e.g., olivine-crystal alignment through subduction-driven corner flow. Diverse mechanisms can contribute to the observed pattern of anisotropic properties, with volatiles likely being a key influence. For instance, we find evidence in favor of a slow-symmetry-axis anisotropy within the uppermost 10-20 km of the mantle wedge, implying either excessive hydration of the mantle or else a presence of systematically aligned volatile-filled cracks or lenses. Also, shear-wave splitting is weak beneath the Avachinsky-Koryaksky volcanic center, suggesting either vertical flow or the influence of volatiles and/or thermally-enhanced diffusion creep.

Perturbation corrections to Koopmans' theorem. V - A study with large basis sets

NASA Technical Reports Server (NTRS)

Chong, D. P.; Langhoff, S. R.

1982-01-01

The vertical ionization potentials of N2, F2 and H2O were calculated by perturbation corrections to Koopmans' theorem using six different basis sets. The largest set used includes several sets of polarization functions. Comparison is made with measured values and with results of computations using Green's functions.

A new basis set for molecular bending degrees of freedom.

PubMed

Jutier, Laurent

2010-07-21

We present a new basis set as an alternative to Legendre polynomials for the variational treatment of bending vibrational degrees of freedom in order to highly reduce the number of basis functions. This basis set is inspired from the harmonic oscillator eigenfunctions but is defined for a bending angle in the range theta in [0:pi]. The aim is to bring the basis functions closer to the final (ro)vibronic wave functions nature. Our methodology is extended to complicated potential energy surfaces, such as quasilinearity or multiequilibrium geometries, by using several free parameters in the basis functions. These parameters allow several density maxima, linear or not, around which the basis functions will be mainly located. Divergences at linearity in integral computations are resolved as generalized Legendre polynomials. All integral computations required for the evaluation of molecular Hamiltonian matrix elements are given for both discrete variable representation and finite basis representation. Convergence tests for the low energy vibronic states of HCCH(++), HCCH(+), and HCCS are presented.

Volatile element loss during planetary magma ocean phases

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Moynier, Frédéric

2018-01-01

Moderately volatile elements (MVE) are key tracers of volatile depletion in planetary bodies. Zinc is an especially useful MVE because of its generally elevated abundances in planetary basalts, relative to other MVE, and limited evidence for mass-dependent isotopic fractionation under high-temperature igneous processes. Compared with terrestrial basalts, which have δ66Zn values (per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) similar to some chondrite meteorites (∼+0.3‰), lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ (2 st. dev.). Furthermore, mare basalts have average Zn concentrations ∼50 times lower than in typical terrestrial basaltic rocks. Late-stage lunar magmatic products, including ferroan anorthosite, Mg- and Alkali-suite rocks have even higher δ66Zn values (+3 to +6‰). Differences in Zn abundance and isotopic compositions between lunar and terrestrial rocks have previously been interpreted to reflect evaporative loss of Zn, either during the Earth-Moon forming Giant Impact, or in a lunar magma ocean (LMO) phase. To explore the mechanisms and processes under which volatile element loss may have occurred during a LMO phase, we developed models of Zn isotopic fractionation that are generally applicable to planetary magma oceans. Our objective was to identify conditions that would yield a δ66Zn signature of ∼+1.4‰ within the lunar mantle. For the sake of simplicity, we neglect possible Zn isotopic fractionation during the Giant Impact, and assumed a starting composition equal to the composition of the present-day terrestrial mantle, assuming both the Earth and Moon had zinc 'consanguinity' following their formation. We developed two models: the first simulates evaporative fractionation of Zn only prior to LMO mixing and crystallization; the second simulates continued evaporative fractionation of Zn that persists until ∼75% LMO crystallization. The first model yields a relatively homogenous bulk solid LMO δ66Zn value, while the second results in a stratification of δ66Zn values within the LMO sequence. Loss and/or isolation mechanisms for volatiles are critical to these models; hydrodynamic escape was not a dominant process, but loss of a nascent lunar atmosphere or separation of condensates into a proto-lunar crust are possible mechanisms by which volatiles could be separated from the lunar interior. The results do not preclude models that suggest a lunar volatile depletion episode related to the Giant Impact. Conversely, LMO models for volatile loss do not require loss of volatiles prior to lunar formation. Outgassing during planetary magma ocean phases likely played a profound role in setting the volatile inventories of planets, particularly for low mass bodies that experienced the greatest volatile loss. In turn, our results suggest that the initial compositions of planets that accreted from smaller, highly differentiated planetesimals were likely to be severely volatile depleted.

Aroma profile and sensory characteristics of a sulfur dioxide-free mulberry (Morus nigra) wine subjected to non-thermal accelerating aging techniques.

PubMed

Tchabo, William; Ma, Yongkun; Kwaw, Emmanuel; Zhang, Haining; Xiao, Lulu; Tahir, Haroon Elrasheid

2017-10-01

The present study was undertaken to assess accelerating aging effects of high pressure, ultrasound and manosonication on the aromatic profile and sensorial attributes of aged mulberry wines (AMW). A total of 166 volatile compounds were found amongst the AMW. The outcomes of the investigation were presented by means of geometric mean (GM), cluster analysis (CA), principal component analysis (PCA), partial least squares regressions (PLSR) and principal component regression (PCR). GM highlighted 24 organoleptic attributes responsible for the sensorial profile of the AMW. Moreover, CA revealed that the volatile composition of the non-thermal accelerated aged wines differs from that of the conventional aged wines. Besides, PCA discriminated the AMW on the basis of their main sensorial characteristics. Furthermore, PLSR identified 75 aroma compounds which were mainly responsible for the olfactory notes of the AMW. Finally, the overall quality of the AMW was noted to be better predicted by PLSR than PCR. Copyright © 2017 Elsevier Ltd. All rights reserved.

Contaminants in Liquid Organic Fertilizers Used for Agriculture in Japan.

PubMed

Hai, Dao M; Qiu, Xuchun; Xu, Hai; Honda, Masato; Yabe, Mitsuyasu; Kadokami, Kiwao; Shimasaki, Yohei; Oshima, Yuji

2017-07-01

To provide an overview of anthropogenic contaminants in liquid organic fertilizers (LOFs), products from four biogas plants in Kyushu, Japan, were analyzed for a wide range of contaminants, including copper, cadmium, tributyltin (TBT), dibutyltin (DBT), perfluorooctane sulfonate, 952 semi-volatile organic compounds, and 89 antibiotics. The highest concentrations of copper (31.1 mg/L) and cadmium (0.08 mg/L) were found in LOFs from the Hita biogas plant. Only ofloxacin and sulfapyridine were detected in total 89 antibiotics screened. TBT, DBT, and perfluorooctane sulfonate were present at low concentrations in the LOFs from all four locations. Among the 952 semi-volatile organic compounds, 78 compounds were detected in at least one sample and were present at concentrations between 1.2 and 139.6 mg/L. On the basis of comparisons with previous studies and quality standards for the use of organic fertilizers, the concentrations of contaminants in the studied LOFs indicate that they might be safe for agricultural purposes.

Removal of volatile fatty acids and ammonia recovery from unstable anaerobic digesters with a microbial electrolysis cell.

PubMed

Cerrillo, Míriam; Viñas, Marc; Bonmatí, August

2016-11-01

Continuous assays with a microbial electrolysis cell (MEC) fed with digested pig slurry were performed to evaluate its stability and robustness to malfunction periods of an anaerobic digestion (AD) reactor and its feasibility as a strategy to recover ammonia. When performing punctual pulses of volatile fatty acids (VFA) in the anode compartment of the MEC, simulating a malfunction of the AD process, an increase in the current density was produced (up to 14 times, reaching values of 3500mAm(-2)) as a result of the added chemical oxygen demand (COD), especially when acetate was used. Furthermore, ammonium diffusion from the anode to the cathode compartment was enhanced and the removal efficiency achieved up to 60% during daily basis VFA pulses. An AD-MEC combined system has proven to be a robust and stable configuration to obtain a high quality effluent, with a lower organic and ammonium content. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of biochar on volatile fatty acids accumulation and microbial community succession during biosolids composting.

PubMed

Awasthi, Mukesh Kumar; Awasthi, Sanjeev Kumar; Wang, Quan; Wang, Zhen; Lahori, Altaf Hussain; Ren, Xiuna; Chen, Hongyu; Wang, Meijing; Zhao, Junchao; Zhang, Zengqiang

2018-03-01

The impact of biochar amendment on volatile fatty acids (VFAs) and odor generation during the biosolids-wheat straw composting was investigated. Five treatments were design using the same mixture of biosolids-wheat straw with different dosage of biochar blending (2%, 4%, 8% and 12% on dry weight basis) and without biochar applied treatment served as control. The results of VFAs and Odour Index (OI) profile designated that compost with 8-12% biochar became more rapidly humified with less quantity of VFAs and OI generation content compared to control. Consequently, the VFAs degrading and total bacterial abundance are also significantly higher recorded in 8-12% biochar than 2% biochar and control. In addition, 8-12% biochar applied treatment has significantly maximum close correlation among the all physicochemical and gaseous emission parameters. Finally, results designated that higher dosage of biochar (8-12% biochar) was more feasible approach for biosolids composting. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimization of the co-digestion of catch crops with manure using a central composite design and reactor operation.

PubMed

Molinuevo-Salces, Beatriz; Ahring, Birgitte K; Uellendahl, Hinrich

2015-02-01

This study investigates the effect of catch crops as co-substrate on manure-based anaerobic digestion. Batch experiments were carried out for two catch crops, namely Italian ryegrass (IR) and oil seed radish (OSR), in co-digestion with manure. Methane yields in the range of 271-558 and 216-361 ml CH4/g volatile solids (VS) were obtained for OSR and IR in co-digestion, respectively. OSR co-digestion was chosen for semi-continuous reactor experiments. The addition of 50 % of OSR to manure (on VS basis) in semi-continuous anaerobic digestion resulted in a methane yield of 348 ml CH4/g VS, an improvement of 1.46 times compared to manure alone. Adaptation to OSR was observed, and no ammonia or volatile fatty acid-mediated inhibition was detected. The results prove that it is feasible to use catch crops as co-substrate for manure-based biogas production, obtaining a stable process with significantly higher methane yields than that of manure alone.

Dependence of absolute photon flux on infrared absorbance alteration and surface roughness on photoresist polymers irradiated with vacuum ultraviolet photons emitted from HBr plasma

NASA Astrophysics Data System (ADS)

Zhang, Yan; Takeuchi, Takuya; Ishikawa, Kenji; Hayashi, Toshio; Takeda, Keigo; Sekine, Makoto; Hori, Masaru

2017-12-01

The absolute fluxes of vacuum ultraviolet (VUV) photons emitted from HBr plasma were analyzed and the effects of VUV photons on a photoresist polymer in ArF-excimer-laser (193 nm) lithography were quantitatively investigated on the basis of the infrared spectra attributed to the C=O region. The spectral peak intensity assigned to the methacrylic acid (MAA) in the photoresist drastically decreased owing to the loss of this monomer caused by the irradiation of VUV photons at dosages below 16 × 1016 photons/cm2. X-ray photoelectron spectroscopy observation showed that the removed monomer moved to the surface and generated volatile products that induced a decrease in film thickness. As a consequence, the surface became rough during the early-stage irradiation at dosages lower than 16 × 1016 photons/cm2 owing to the monomer loss of MAA with volatile product formation and subsequent cross-linking reactions.

Safety and quality of food contact materials. Part 1: evaluation of analytical strategies to introduce migration testing into good manufacturing practice.

PubMed

Feigenbaum, A; Scholler, D; Bouquant, J; Brigot, G; Ferrier, D; Franzl, R; Lillemarktt, L; Riquet, A M; Petersen, J H; van Lierop, B; Yagoubi, N

2002-02-01

The results of a research project (EU AIR Research Programme CT94-1025) aimed to introduce control of migration into good manufacturing practice and into enforcement work are reported. Representative polymer classes were defined on the basis of chemical structure, technological function, migration behaviour and market share. These classes were characterized by analytical methods. Analytical techniques were investigated for identification of potential migrants. High-temperature gas chromatography was shown to be a powerful method and 1H-magnetic resonance provided a convenient fingerprint of plastic materials. Volatile compounds were characterized by headspace techniques, where it was shown to be essential to differentiate volatile compounds desorbed from those generated during the thermal desorption itself. For metal trace analysis, microwave mineralization followed by atomic absorption was employed. These different techniques were introduced into a systematic testing scheme that is envisaged as being suitable both for industrial control and for enforcement laboratories. Guidelines will be proposed in the second part of this paper.

A commercialized, continuous flow fiber optic sensor for trichloroethylene and haloforms

NASA Technical Reports Server (NTRS)

Wells, James C.; Johnson, Mark D.

1994-01-01

Purus, Inc. has commercialized a fiber optic chemical sensor using technology developed by Lawrence Livermore National Laboratory and licensed from The University of California. The basis for the sensor is the development of color within a reagent when exposed to an analyte. The sensor consists of an optrode, reagent delivery and recover system, fiber optic transmitter-receiver, controller, and display. Reagent is pumped through the optrode. Analyte diffuses across a gas permeable membrane and reacts with the reagent to form a colored product. The colored product is detected by measuring the absorbance of light from a 568 nm diode. Reagents are currently available for TCE and trihalomethanes. Initial reagent chemistry is based on the Fujiwara alkaline pyridine reaction. The optrode contacts only gas streams, but the volatility of the current analytes also allows measurements of aqueous streams, without being affected by aqueous interferents that are non-volatile. Sensitivity of the sensor has been demonstrated to 5 ppb aqueous solutions and 0.1 ppmv in flowing gas streams.

Gas Chromatography-Mass Spectrometry-Olfactometry To Control the Aroma Fingerprint of Extra Virgin Olive Oil from Three Tunisian Cultivars at Three Harvest Times.

PubMed

Ben Brahim, Samia; Amanpour, Asghar; Chtourou, Fatma; Kelebek, Hasim; Selli, Serkan; Bouaziz, Mohamed

2018-03-21

Gas chromatography-mass spectrometry-olfactometry was used for the analysis of volatile compounds and key odorants of three less studied Tunisian olive oil cultivars for the first time. A total of 42 aroma compounds were identified and quantified in extra virgin olive oils. The present study revealed that the most dominant volatiles in olive oil samples qualitatively and quantitatively were aldehydes and alcohols, followed by terpenes and esters. Indeed, chemometric analysis has shown a correlation between chemical compounds and sensory properties. The determination of aroma-active compounds of olive oil samples was carried out using aroma extract dilution analysis. A total of 15 aroma-active compounds were detected in the aromatic extract of extra virgin olive oil, of which 14 were identified. On the basis of the flavor dilution (FD) factor, the most potent aromatic active compound was hexanal (FD = 512) in Fakhari olive oil, (FD = 256) in Touffehi oils, and (FD = 128) in Jemri olive oil.

Flavor characteristics of seven grades of black tea produced in Turkey.

PubMed

Alasalvar, Cesarettin; Topal, Bahar; Serpen, Arda; Bahar, Banu; Pelvan, Ebru; Gökmen, Vural

2012-06-27

Seven grades of black tea [high-quality black tea (grades 1-3) and low-quality black tea (grades 4-7)], processed by ÇAYKUR Tea Processing Plant (Rize, Turkey), were compared for their differences in descriptive sensory analysis (DSA), aroma-active compounds (volatile compounds), and taste-active compounds (sugar, organic acid, and free amino acid compositions). Ten flavor attributes such as 'after taste', 'astringency', 'bitter', 'caramel-like', 'floral/sweet', 'green/grassy', 'hay-like', 'malty', 'roasty', and 'seaweed' were identified. Intensities for a number of flavor attributes ('after taste', 'caramel-like', 'malty', and 'seaweed') were not significantly different (p > 0.05) among seven grades of black tea. A total of 57 compounds in seven grades of black tea (14 aldehydes, eight alcohols, eight ketones, two esters, four aromatic hydrocarbons, five aliphatic hydrocarbons, nine terpenes, two pyrazines, one furan, two acids, and two miscellaneous compounds) were tentatively identified. Of these, aldeyhdes comprised more than 50% to the total volatile compounds identified. In general, high-grade quality tea had more volatiles than low-grade quality tea. With respect to taste-active compounds, five sugars, six organic acids, and 18 free amino acids were positively identified in seven grades of black tea, of which fructose, tannic acid, and theanine predominated, respectively. Some variations (p < 0.05), albeit to different extents, were observed among volatile compounds, sugars, organic acids, and free amino acids in seven grades of black tea. The present study suggests that a certain flavor attributes correlate well with taste- and aroma-active compounds. High- and low-quality black teas should not be distinguished solely on the basis of their DSA and taste- and aroma-active compounds. The combination of taste-active compounds together with aroma-active compounds renders combination effects that provide the characteristic flavor of each grade of black tea.

Hydrothermal pretreatment of coal

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

Ross, D.S.

1989-12-21

We have examined changes in Argonne Premium samples of Wyodak coal following 30 min treatment in liquid water at autogenous pressures at 150{degrees}, 250{degrees}, and 350{degrees}C. In most runs the coal was initially dried at 60{degrees}C/1 torr/20 hr. The changes were monitored by pyrolysis field ionization mass spectrometry (py-FIMS) operating at 2.5{degrees}C/min from ambient to 500{degrees}C. We recorded the volatility patterns of the coal tars evolved over that temperature range, and in all cases the tar yields were 25%--30% of the starting coal on mass basis. There was essentially no change after the 150{degrees}C treatment. Small increases in volatility weremore » seen following the 250{degrees}C treatment, but major effects were seen in the 350{degrees} work. The tar quantity remained unchanged; however, the volatility increased so the temperature of half volatility for the as-received coal of 400{degrees}C was reduced to 340{degrees}C. Control runs with no water showed some thermal effect, but the net effect from the presence of liquid water was clearly evident. The composition was unchanged after the 150{degrees} and 250{degrees}C treatments, but the 350{degrees} treatment brought about a 30% loss of oxygen. The change corresponded to loss of the elements of water, although loss of OH'' seemed to fit the analysis data somewhat better. The water loss takes place both in the presence and in the absence of added water, but it is noteworthy that the loss in the hydrothermal runs occurs at p(H{sub 2}O) = 160 atm. We conclude that the process must involve the dehydration solely of chemically bound elements of water, the dehydration of catechol is a specific, likely candidate.« less

Investigating the present and past glacial and frost activity on Pluto with a volatile transport model

NASA Astrophysics Data System (ADS)

Bertrand, Tanguy; Forget, Francois

2016-10-01

The high obliquity and eccentricity of the orbit of Pluto induce seasonal cycles of condensation and sublimation of the main volatile ices: N2, CH4, and CO. The New Horizons spacecraft, which flew by Pluto in July 2015, revealed a complex surface composition including a thousand-kilometre nitrogen glacier in the "Sputnik Planum" plain near the Anti-Charon longitude, extensive methane frosts at mid and high latitudes, and equatorial ice-free regions. We present numerical simulations designed to model the evolution of Pluto's volatiles over thousands of years on the basis of straightforward universal physical equations.Our results explain the observed distribution of ices on the surface and the quantities of volatiles in the atmosphere. In particular the model predicts the N2 ice accumulation in the deepest low-latitude basin and the 3-fold increase of pressure observed to occur since 1988. This points to atmospheric-topographic processes at the origin of the Sputnik Planum's nitrogen glacier. The same simulations also show frosts of methane, and sometimes nitrogen, that seasonally cover the mid and high latitudes, explaining the bright northern polar cap reported in the 1990s and the observed ice distribution in 2015. The model also predicts that most of these seasonal frosts should disappear in the next decade, and thus could be tested observationally in the near future.Using prior orbital parameters of Pluto and a realistic glacial flow parametrization, we also simulate past climates of Pluto. The results show that Pluto undergoes cycles of glacial activity (over timescales of few million years) that may explain the rugged eroded-mountain landscapes surrounding Sputnik Planum and the "bladed" methane terrains east of "Tombaugh Regio".

The Terpene Synthase Gene Family of Carrot (Daucus carota L.): Identification of QTLs and Candidate Genes Associated with Terpenoid Volatile Compounds

PubMed Central

Keilwagen, Jens; Lehnert, Heike; Berner, Thomas; Budahn, Holger; Nothnagel, Thomas; Ulrich, Detlef; Dunemann, Frank

2017-01-01

Terpenes are an important group of secondary metabolites in carrots influencing taste and flavor, and some of them might also play a role as bioactive substances with an impact on human physiology and health. Understanding the genetic and molecular basis of terpene synthases (TPS) involved in the biosynthesis of volatile terpenoids will provide insights for improving breeding strategies aimed at quality traits and for developing specific carrot chemotypes possibly useful for pharmaceutical applications. Hence, a combination of terpene metabolite profiling, genotyping-by-sequencing (GBS), and genome-wide association study (GWAS) was used in this work to get insights into the genetic control of terpene biosynthesis in carrots and to identify several TPS candidate genes that might be involved in the production of specific monoterpenes. In a panel of 85 carrot cultivars and accessions, metabolite profiling was used to identify 31 terpenoid volatile organic compounds (VOCs) in carrot leaves and roots, and a GBS approach was used to provide dense genome-wide marker coverage (>168,000 SNPs). Based on this data, a total of 30 quantitative trait loci (QTLs) was identified for 15 terpenoid volatiles. Most QTLs were detected for the monoterpene compounds ocimene, sabinene, β-pinene, borneol and bornyl acetate. We identified four genomic regions on three different carrot chromosomes by GWAS which are both associated with high significance (LOD ≥ 5.91) to distinct monoterpenes and to TPS candidate genes, which have been identified by homology-based gene prediction utilizing RNA-seq data. In total, 65 TPS candidate gene models in carrot were identified and assigned to known plant TPS subfamilies with the exception of TPS-d and TPS-h. TPS-b was identified as largest subfamily with 32 TPS candidate genes. PMID:29170675

Characterization of diesel particles: effects of fuel reformulation, exhaust aftertreatment, and engine operation on particle carbon composition and volatility.

PubMed

Alander, Timo J A; Leskinen, Ari P; Raunemaa, Taisto M; Rantanen, Leena

2004-05-01

Diesel exhaust particles are the major constituent of urban carbonaceous aerosol being linked to a large range of adverse environmental and health effects. In this work, the effects of fuel reformulation, oxidation catalyst, engine type, and engine operation parameters on diesel particle emission characteristics were investigated. Particle emissions from an indirect injection (IDI) and a direct injection (DI) engine car operating under steady-state conditions with a reformulated low-sulfur, low-aromatic fuel and a standard-grade fuel were analyzed. Organic (OC) and elemental (EC) carbon fractions of the particles were quantified by a thermal-optical transmission analysis method and particle size distributions measured with a scanning mobility particle sizer (SMPS). The particle volatility characteristics were studied with a configuration that consisted of a thermal desorption unit and an SMPS. In addition, the volatility of size-selected particles was determined with a tandem differential mobility analyzer technique. The reformulated fuel was found to produce 10-40% less particulate carbon mass compared to the standard fuel. On the basis of the carbon analysis, the organic carbon contributed 27-61% to the carbon mass of the IDI engine particle emissions, depending on the fuel and engine operation parameters. The fuel reformulation reduced the particulate organic carbon emissions by 10-55%. In the particles of the DI engine, the organic carbon contributed 14-26% to the total carbon emissions, the advanced engine technology, and the oxidation catalyst, thus reducing the OC/EC ratio of particles considerably. A relatively good consistency between the particulate organic fraction quantified with the thermal optical method and the volatile fraction measured with the thermal desorption unit and SMPS was found.

Chemical and biological characterization of products of incomplete combustion from the simulated field burning of agricultural plastic.

PubMed

Linak, W P; Ryan, J V; Perry, E; Williams, R W; DeMarini, D M

1989-06-01

Chemical and biological analyses were performed to characterize products of incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenic properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, semi-volatile, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were identified in either combustion emission samples or dichloromethane washes of the used plastic. When mutagenicity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/particulate emissions, no toxic or mutagenic effects were observed. However, organic extracts of the particulate samples were moderately mutagenic. This mutagenicity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds identified in samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.

Differential Binding between Volatile Ligands and Major Urinary Proteins Due to Genetic Variation in Mice

DTIC Science & Technology

2012-06-20

a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. a ...previous studies have examined only one of the classes at a time. No study has analyzed these two sets simultaneously, and consequently binding...previous studies have examined only one of the classes at a time. No study has analyzed these two sets simultaneously, and consequently binding

Prediction of breast cancer risk with volatile biomarkers in breath.

PubMed

Phillips, Michael; Cataneo, Renee N; Cruz-Ramos, Jose Alfonso; Huston, Jan; Ornelas, Omar; Pappas, Nadine; Pathak, Sonali

2018-03-23

Human breath contains volatile organic compounds (VOCs) that are biomarkers of breast cancer. We investigated the positive and negative predictive values (PPV and NPV) of breath VOC biomarkers as indicators of breast cancer risk. We employed ultra-clean breath collection balloons to collect breath samples from 54 women with biopsy-proven breast cancer and 124 cancer-free controls. Breath VOCs were analyzed with gas chromatography (GC) combined with either mass spectrometry (GC MS) or surface acoustic wave detection (GC SAW). Chromatograms were randomly assigned to a training set or a validation set. Monte Carlo analysis identified significant breath VOC biomarkers of breast cancer in the training set, and these biomarkers were incorporated into a multivariate algorithm to predict disease in the validation set. In the unsplit dataset, the predictive algorithms generated discriminant function (DF) values that varied with sensitivity, specificity, PPV and NPV. Using GC MS, test accuracy = 90% (area under curve of receiver operating characteristic in unsplit dataset) and cross-validated accuracy = 77%. Using GC SAW, test accuracy = 86% and cross-validated accuracy = 74%. With both assays, a low DF value was associated with a low risk of breast cancer (NPV > 99.9%). A high DF value was associated with a high risk of breast cancer and PPV rising to 100%. Analysis of breath VOC samples collected with ultra-clean balloons detected biomarkers that accurately predicted risk of breast cancer.

Extrapolating MP2 and CCSD explicitly correlated correlation energies to the complete basis set limit with first and second row correlation consistent basis sets

NASA Astrophysics Data System (ADS)

Hill, J. Grant; Peterson, Kirk A.; Knizia, Gerald; Werner, Hans-Joachim

2009-11-01

Accurate extrapolation to the complete basis set (CBS) limit of valence correlation energies calculated with explicitly correlated MP2-F12 and CCSD(T)-F12b methods have been investigated using a Schwenke-style approach for molecules containing both first and second row atoms. Extrapolation coefficients that are optimal for molecular systems containing first row elements differ from those optimized for second row analogs, hence values optimized for a combined set of first and second row systems are also presented. The new coefficients are shown to produce excellent results in both Schwenke-style and equivalent power-law-based two-point CBS extrapolations, with the MP2-F12/cc-pV(D,T)Z-F12 extrapolations producing an average error of just 0.17 mEh with a maximum error of 0.49 for a collection of 23 small molecules. The use of larger basis sets, i.e., cc-pV(T,Q)Z-F12 and aug-cc-pV(Q,5)Z, in extrapolations of the MP2-F12 correlation energy leads to average errors that are smaller than the degree of confidence in the reference data (˜0.1 mEh). The latter were obtained through use of very large basis sets in MP2-F12 calculations on small molecules containing both first and second row elements. CBS limits obtained from optimized coefficients for conventional MP2 are only comparable to the accuracy of the MP2-F12/cc-pV(D,T)Z-F12 extrapolation when the aug-cc-pV(5+d)Z and aug-cc-pV(6+d)Z basis sets are used. The CCSD(T)-F12b correlation energy is extrapolated as two distinct parts: CCSD-F12b and (T). While the CCSD-F12b extrapolations with smaller basis sets are statistically less accurate than those of the MP2-F12 correlation energies, this is presumably due to the slower basis set convergence of the CCSD-F12b method compared to MP2-F12. The use of larger basis sets in the CCSD-F12b extrapolations produces correlation energies with accuracies exceeding the confidence in the reference data (also obtained in large basis set F12 calculations). It is demonstrated that the use of the 3C(D) Ansatz is preferred for MP2-F12 CBS extrapolations. Optimal values of the geminal Slater exponent are presented for the diagonal, fixed amplitude Ansatz in MP2-F12 calculations, and these are also recommended for CCSD-F12b calculations.

An Alternate Set of Basis Functions for the Electromagnetic Solution of Arbitrarily-Shaped, Three-Dimensional, Closed, Conducting Bodies Using Method of Moments

NASA Technical Reports Server (NTRS)

Mackenzie, Anne I.; Baginski, Michael E.; Rao, Sadasiva M.

2008-01-01

In this work, we present an alternate set of basis functions, each defined over a pair of planar triangular patches, for the method of moments solution of electromagnetic scattering and radiation problems associated with arbitrarily-shaped, closed, conducting surfaces. The present basis functions are point-wise orthogonal to the pulse basis functions previously defined. The prime motivation to develop the present set of basis functions is to utilize them for the electromagnetic solution of dielectric bodies using a surface integral equation formulation which involves both electric and magnetic cur- rents. However, in the present work, only the conducting body solution is presented and compared with other data.

40 CFR Appendix A to Subpart D of... - Determination of Volatile Matter Content of Methacrylate Multicomponent Coatings Used as Traffic...

Code of Federal Regulations, 2010 CFR

2010-07-01

... the film of the coating using the metal paper clip. Weigh dish to within 1 mg. Return to forced draft... analyses in pairs (duplicate sets for each coating mixture until the criterion in section 4.3 of Method 24...

SMOG CHAMBERS: A TOOL TO EXAMINE EFFECTS OF PHOTOCHEMICALLY AGED AIR POLLUTANTS ON BIOLOGICAL SYSTEMS

EPA Science Inventory

Irradiative exposure chambers or 'Smog chambers' have been used at the University of North Carolina for over 30 years to study photochemically active mixtures of volatile organic compounds and their transformation products (a significant sub-set of Hazardous Air Pollutants, HAPs)...

Correction of energy-dependent systematic errors in dual-energy X-ray CT using a basis material coefficients transformation method

NASA Astrophysics Data System (ADS)

Goh, K. L.; Liew, S. C.; Hasegawa, B. H.

1997-12-01

Computer simulation results from our previous studies showed that energy dependent systematic errors exist in the values of attenuation coefficient synthesized using the basis material decomposition technique with acrylic and aluminum as the basis materials, especially when a high atomic number element (e.g., iodine from radiographic contrast media) was present in the body. The errors were reduced when a basis set was chosen from materials mimicking those found in the phantom. In the present study, we employed a basis material coefficients transformation method to correct for the energy-dependent systematic errors. In this method, the basis material coefficients were first reconstructed using the conventional basis materials (acrylic and aluminum) as the calibration basis set. The coefficients were then numerically transformed to those for a more desirable set materials. The transformation was done at the energies of the low and high energy windows of the X-ray spectrum. With this correction method using acrylic and an iodine-water mixture as our desired basis set, computer simulation results showed that accuracy of better than 2% could be achieved even when iodine was present in the body at a concentration as high as 10% by mass. Simulation work had also been carried out on a more inhomogeneous 2D thorax phantom of the 3D MCAT phantom. The results of the accuracy of quantitation were presented here.

Dispersion corrected hartree-fock and density functional theory for organic crystal structure prediction.

PubMed

Brandenburg, Jan Gerit; Grimme, Stefan

2014-01-01

We present and evaluate dispersion corrected Hartree-Fock (HF) and Density Functional Theory (DFT) based quantum chemical methods for organic crystal structure prediction. The necessity of correcting for missing long-range electron correlation, also known as van der Waals (vdW) interaction, is pointed out and some methodological issues such as inclusion of three-body dispersion terms are discussed. One of the most efficient and widely used methods is the semi-classical dispersion correction D3. Its applicability for the calculation of sublimation energies is investigated for the benchmark set X23 consisting of 23 small organic crystals. For PBE-D3 the mean absolute deviation (MAD) is below the estimated experimental uncertainty of 1.3 kcal/mol. For two larger π-systems, the equilibrium crystal geometry is investigated and very good agreement with experimental data is found. Since these calculations are carried out with huge plane-wave basis sets they are rather time consuming and routinely applicable only to systems with less than about 200 atoms in the unit cell. Aiming at crystal structure prediction, which involves screening of many structures, a pre-sorting with faster methods is mandatory. Small, atom-centered basis sets can speed up the computation significantly but they suffer greatly from basis set errors. We present the recently developed geometrical counterpoise correction gCP. It is a fast semi-empirical method which corrects for most of the inter- and intramolecular basis set superposition error. For HF calculations with nearly minimal basis sets, we additionally correct for short-range basis incompleteness. We combine all three terms in the HF-3c denoted scheme which performs very well for the X23 sublimation energies with an MAD of only 1.5 kcal/mol, which is close to the huge basis set DFT-D3 result.

Comparison of fMRI analysis methods for heterogeneous BOLD responses in block design studies.

PubMed

Liu, Jia; Duffy, Ben A; Bernal-Casas, David; Fang, Zhongnan; Lee, Jin Hyung

2017-02-15

A large number of fMRI studies have shown that the temporal dynamics of evoked BOLD responses can be highly heterogeneous. Failing to model heterogeneous responses in statistical analysis can lead to significant errors in signal detection and characterization and alter the neurobiological interpretation. However, to date it is not clear that, out of a large number of options, which methods are robust against variability in the temporal dynamics of BOLD responses in block-design studies. Here, we used rodent optogenetic fMRI data with heterogeneous BOLD responses and simulations guided by experimental data as a means to investigate different analysis methods' performance against heterogeneous BOLD responses. Evaluations are carried out within the general linear model (GLM) framework and consist of standard basis sets as well as independent component analysis (ICA). Analyses show that, in the presence of heterogeneous BOLD responses, conventionally used GLM with a canonical basis set leads to considerable errors in the detection and characterization of BOLD responses. Our results suggest that the 3rd and 4th order gamma basis sets, the 7th to 9th order finite impulse response (FIR) basis sets, the 5th to 9th order B-spline basis sets, and the 2nd to 5th order Fourier basis sets are optimal for good balance between detection and characterization, while the 1st order Fourier basis set (coherence analysis) used in our earlier studies show good detection capability. ICA has mostly good detection and characterization capabilities, but detects a large volume of spurious activation with the control fMRI data. Copyright © 2016 Elsevier Inc. All rights reserved.

Point Set Denoising Using Bootstrap-Based Radial Basis Function.

PubMed

Liew, Khang Jie; Ramli, Ahmad; Abd Majid, Ahmad

2016-01-01

This paper examines the application of a bootstrap test error estimation of radial basis functions, specifically thin-plate spline fitting, in surface smoothing. The presence of noisy data is a common issue of the point set model that is generated from 3D scanning devices, and hence, point set denoising is one of the main concerns in point set modelling. Bootstrap test error estimation, which is applied when searching for the smoothing parameters of radial basis functions, is revisited. The main contribution of this paper is a smoothing algorithm that relies on a bootstrap-based radial basis function. The proposed method incorporates a k-nearest neighbour search and then projects the point set to the approximated thin-plate spline surface. Therefore, the denoising process is achieved, and the features are well preserved. A comparison of the proposed method with other smoothing methods is also carried out in this study.

Volatile organic compounds from fungi isolated after hurricane katrina induce developmental defects and apoptosis in a Drosophila melanogaster model.

PubMed

Inamdar, Arati A; Bennett, Joan W

2015-05-01

In previous work, our laboratory developed a Drosophila model for studying the adverse effects of fungal volatile organic compounds (VOCs) emitted by growing cultures of molds. In this report, we have extended these studies and compared the toxic effects of fungal VOCs emitted from living cultures of four molds isolated after Hurricane Katrina from a flooded home in New Orleans. Strains of Aspergillus, Mucor, Penicillium, and Trichoderma were grown with wild-type larvae and the toxic effects of volatile products on the developmental stages of Drosophila larvae were evaluated. Furthermore, heterozygous mutants of Drosophila carrying the apoptotic genes, reaper and dronc, were used to assess the role of apoptosis in fungal VOCs mediated toxicity. Third-instar larvae of Drosophila carrying these apoptotic genes were exposed to fungal VOCs emitted from growing mold cultures for 10 days. The larval strains carrying apoptopic genes survived longer than the control wild type larvae; moreover, of those that survived, heterozygous reaper and dronc strains progressed to pupae and adult phases more rapidly, suggesting that fungal VOCs may induce apoptotic changes in flies. These data lend support to the use of Drosophila as an inexpensive and genetically versatile toxicological model to investigate the mechanistic basis for some of the human illnesses/symptoms associated with exposure to mold-contaminated indoor air, especially after hurricanes. © 2013 Wiley Periodicals, Inc.

Three-dimensional illumination and thermal model of the Abydos region on comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Kömle, Norbert I.; Macher, Wolfgang; Tiefenbacher, Patrick; Kargl, Günter; Pelivan, Ivanka; Knollenberg, Jörg; Spohn, Tilman; Jorda, Laurent; Capanna, Claire; Lommatsch, Valentina; Cozzoni, Barbara; Finke, Felix

2017-07-01

On 2014 November 12 Rosetta's comet lander Philae arrived on the surface of Comet 67P/Churyumov-Gerasimenko. Among the data collected by the instruments on board are images from the panorama camera CIVA and the down looking camera ROLIS, as well as temperature measurements recorded by the sensors of the MUPUS experiment and by various housekeeping sensors. In combination with remote observations by the cameras OSIRIS and NAVCAM and other instruments on the Rosetta Orbiter, it was possible to construct a reasonable model of the terrain in the close vicinity of the landing site Abydos. We have collected all available information on the position and orientation of Philae, as well as on Abydos, where the terrain can be partially reconstructed with a resolution in the decimetre range. On this basis, a 3D model for the determination of solar irradiation and thermal evolution of the region was developed. Our calculations comprise the heating and cooling process of the local surface features around Philae. Two different scenarios are studied: non-volatile material (dust mantle) covering the whole surface, and a non-volatile surface containing spots of volatile water ice where free sublimation is possible. The presented 3D model also has the potential to be applied to thermal evolution studies of other regions on the comet, for which high-resolution digital terrain models are available.

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds.

PubMed

Fusco, Zelio; Rahmani, Mohsen; Bo, Renheng; Verre, Ruggero; Motta, Nunzio; Käll, Mikael; Neshev, Dragomir; Tricoli, Antonio

2018-06-04

Advances in the understanding and fabrication of plasmonic nanostructures have led to a plethora of unprecedented optoelectronic and optochemical applications. Plasmon resonance has found widespread use in efficient optical transducers of refractive index changes in liquids. However, it has proven challenging to translate these achievements to the selective detection of gases, which typically adsorb non-specifically and induce refractive index changes below the detection limit. Here, it's shown that integration of tailored fractals of dielectric TiO 2 nanoparticles on a plasmonic metasurface strongly enhances the interaction between the plasmonic field and volatile organic molecules and provides a means for their selective detection. Notably, this superior optical response is due to the enhancement of the interaction between the dielectric fractals and the plasmonic metasurface for thickness of up to 1.8 μm, much higher than the evanescent plasmonic near-field (≈30 nm) . Optimal dielectric-plasmonic structures allow measurements of changes in the refractive index of the gas mixture down to <8 × 10 -6 at room temperature and selective identification of three exemplary volatile organic compounds. These findings provide a basis for the development of a novel family of dielectric-plasmonic materials with application extending from light harvesting and photocatalysts to contactless sensors for noninvasive medical diagnostics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Genome-wide association study unravels the genetic control of the apple volatilome and its interplay with fruit texture.

PubMed

Farneti, Brian; Di Guardo, Mario; Khomenko, Iuliia; Cappellin, Luca; Biasioli, Franco; Velasco, Riccardo; Costa, Fabrizio

2017-03-01

Fruit quality represents a fundamental factor guiding consumers' preferences. Among apple quality traits, volatile organic compounds and texture features play a major role. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS), coupled with an artificial chewing device, was used to profile the entire apple volatilome of 162 apple accessions, while the fruit texture was dissected with a TAXT-AED texture analyzer. The array of volatile compounds was classed into seven major groups and used in a genome-wide association analysis carried out with 9142 single nucleotide polymorphisms (SNPs). Marker-trait associations were identified on seven chromosomes co-locating with important candidate genes for aroma, such as MdAAT1 and MdIGS. The integration of volatilome and fruit texture data conducted with a multiple factor analysis unraveled contrasting behavior, underlying opposite regulation of the two fruit quality aspects. The association analysis using the first two principal components identified two QTLs located on chromosomes 10 and 2, respectively. The distinction of the apple accessions on the basis of the allelic configuration of two functional markers, MdPG1 and MdACO1, shed light on the type of interplay existing between fruit texture and the production of volatile organic compounds. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

On the connection between financial processes with stochastic volatility and nonextensive statistical mechanics

NASA Astrophysics Data System (ADS)

Queirós, S. M. D.; Tsallis, C.

2005-11-01

The GARCH algorithm is the most renowned generalisation of Engle's original proposal for modelising returns, the ARCH process. Both cases are characterised by presenting a time dependent and correlated variance or volatility. Besides a memory parameter, b, (present in ARCH) and an independent and identically distributed noise, ω, GARCH involves another parameter, c, such that, for c=0, the standard ARCH process is reproduced. In this manuscript we use a generalised noise following a distribution characterised by an index qn, such that qn=1 recovers the Gaussian distribution. Matching low statistical moments of GARCH distribution for returns with a q-Gaussian distribution obtained through maximising the entropy Sq=1-sumipiq/q-1, basis of nonextensive statistical mechanics, we obtain a sole analytical connection between q and left( b,c,qnright) which turns out to be remarkably good when compared with computational simulations. With this result we also derive an analytical approximation for the stationary distribution for the (squared) volatility. Using a generalised Kullback-Leibler relative entropy form based on Sq, we also analyse the degree of dependence between successive returns, zt and zt+1, of GARCH(1,1) processes. This degree of dependence is quantified by an entropic index, qop. Our analysis points the existence of a unique relation between the three entropic indexes qop, q and qn of the problem, independent of the value of (b,c).

Volatile and semivolatile organic compounds in laboratory peat fire emissions

NASA Astrophysics Data System (ADS)

George, Ingrid J.; Black, Robert R.; Geron, Chris D.; Aurell, Johanna; Hays, Michael D.; Preston, William T.; Gullett, Brian K.

2016-05-01

In this study, volatile and semi-volatile organic compound (VOCs and SVOCs) mass emission factors were determined from laboratory peat fire experiments. The peat samples originated from two National Wildlife Refuges on the coastal plain of North Carolina, U.S.A. Gas- and particle-phase organic compounds were quantified by gas chromatography-mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (∼60%) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. In the fine particle mass (PM2.5), the following organic compound classes were dominant: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for the organic acids in PM2.5 including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12%) of all speciated compound classes measured in this work. Levoglucosan contributed to 2-3% of the OC mass, while methoxyphenols represented 0.2-0.3% of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon (PAH). Total HAP VOC and particulate PAH emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions.

Experimental Infection of Plants with an Herbivore-Associated Bacterial Endosymbiont Influences Herbivore Host Selection Behavior

PubMed Central

Davis, Thomas Seth; Horton, David R.; Munyaneza, Joseph E.; Landolt, Peter J.

2012-01-01

Although bacterial endosymbioses are common among phloeophagous herbivores, little is known regarding the effects of symbionts on herbivore host selection and population dynamics. We tested the hypothesis that plant selection and reproductive performance by a phloem-feeding herbivore (potato psyllid, Bactericera cockerelli) is mediated by infection of plants with a bacterial endosymbiont. We controlled for the effects of herbivory and endosymbiont infection by exposing potato plants (Solanum tuberosum) to psyllids infected with “Candidatus Liberibacter solanacearum” or to uninfected psyllids. We used these treatments as a basis to experimentally test plant volatile emissions, herbivore settling and oviposition preferences, and herbivore population growth. Three important findings emerged: (1) plant volatile profiles differed with respect to both herbivory and herbivory plus endosymbiont infection when compared to undamaged control plants; (2) herbivores initially settled on plants exposed to endosymbiont-infected psyllids but later defected and oviposited primarily on plants exposed only to uninfected psyllids; and (3) plant infection status had little effect on herbivore reproduction, though plant flowering was associated with a 39% reduction in herbivore density on average. Our experiments support the hypothesis that plant infection with endosymbionts alters plant volatile profiles, and infected plants initially recruited herbivores but later repelled them. Also, our findings suggest that the endosymbiont may not place negative selection pressure on its host herbivore in this system, but plant flowering phenology appears correlated with psyllid population performance. PMID:23166641

FDATMOS16 non-linear partitioning and organic volatility distributions in urban aerosols

DOE PAGES

Madronich, Sasha; Kleinman, Larry; Conley, Andrew; ...

2015-12-17

Gas-to-particle partitioning of organic aerosols (OA) is represented in most models by Raoult’s law, and depends on the existing mass of particles into which organic gases can dissolve. This raises the possibility of non-linear response of particle-phase OA to the emissions of precursor volatile organic compounds (VOCs) that contribute to this partitioning mass. Implications for air quality management are evident: A strong non-linear dependence would suggest that reductions in VOC emission would have a more-than-proportionate benefit in lowering ambient OA concentrations. Chamber measurements on simple VOC mixtures generally confirm the non-linear scaling between OA and VOCs, usually stated as amore » mass-dependence of the measured OA yields. However, for realistic ambient conditions including urban settings, no single component dominates the composition of the organic particles, and deviations from linearity are presumed to be small. Here we re-examine the linearity question using volatility spectra from several sources: (1) chamber studies of selected aerosols, (2) volatility inferred for aerosols sampled in two megacities, Mexico City and Paris, and (3) an explicit chemistry model (GECKO-A). These few available volatility distributions suggest that urban OA may be only slightly super-linear, with most values of the sensitivity exponent in the range 1.1-1.3, also substantially lower than seen in chambers for some specific aerosols. Furthermore, the rather low values suggest that OA concentrations in megacities are not an inevitable convergence of non-linear effects, but can be addressed (much like in smaller urban areas) by proportionate reductions in emissions.« less

Computational study of the electronic spectra of the rare gas fluorohydrides HRgF (Rg = Ar, Kr, Xe, Rn)

NASA Astrophysics Data System (ADS)

van Hoeve, Miriam D.; Klobukowski, Mariusz

2018-03-01

Simulation of the electronic spectra of HRgF (Rg = Ar, Kr, Xe, Rn) was carried out using the time-dependent density functional method, with the CAMB3LYP functional and several basis sets augmented with even-tempered diffuse functions. A full spectral assignment for the HRgF systems was done. The effect of the rare gas matrix on the HRgF (Rg = Ar and Kr) spectra was investigated and it was found that the matrix blue-shifted the spectra. Scalar relativistic effects on the spectra were also studied and it was found that while the excitation energies of HArF and HKrF were insignificantly affected by relativistic effects, most of the excitation energies of HXeF and HRnF were red-shifted. Spin-orbit coupling was found to significantly affect excitation energies in HRnF. Analysis of performance of the model core potential basis set relative to all-electron (AE) basis sets showed that the former basis set increased computational efficiency and gave results similar to those obtained with the AE basis set.

Midbond basis functions for weakly bound complexes

NASA Astrophysics Data System (ADS)

Shaw, Robert A.; Hill, J. Grant

2018-06-01

Weakly bound systems present a difficult problem for conventional atom-centred basis sets due to large separations, necessitating the use of large, computationally expensive bases. This can be remedied by placing a small number of functions in the region between molecules in the complex. We present compact sets of optimised midbond functions for a range of complexes involving noble gases, alkali metals and small molecules for use in high accuracy coupled -cluster calculations, along with a more robust procedure for their optimisation. It is shown that excellent results are possible with double-zeta quality orbital basis sets when a few midbond functions are added, improving both the interaction energy and the equilibrium bond lengths of a series of noble gas dimers by 47% and 8%, respectively. When used in conjunction with explicitly correlated methods, near complete basis set limit accuracy is readily achievable at a fraction of the cost that using a large basis would entail. General purpose auxiliary sets are developed to allow explicitly correlated midbond function studies to be carried out, making it feasible to perform very high accuracy calculations on weakly bound complexes.

Rapid Detection of Volatile Oil in Mentha haplocalyx by Near-Infrared Spectroscopy and Chemometrics.

PubMed

Yan, Hui; Guo, Cheng; Shao, Yang; Ouyang, Zhen

2017-01-01

Near-infrared spectroscopy combined with partial least squares regression (PLSR) and support vector machine (SVM) was applied for the rapid determination of chemical component of volatile oil content in Mentha haplocalyx . The effects of data pre-processing methods on the accuracy of the PLSR calibration models were investigated. The performance of the final model was evaluated according to the correlation coefficient ( R ) and root mean square error of prediction (RMSEP). For PLSR model, the best preprocessing method combination was first-order derivative, standard normal variate transformation (SNV), and mean centering, which had of 0.8805, of 0.8719, RMSEC of 0.091, and RMSEP of 0.097, respectively. The wave number variables linking to volatile oil are from 5500 to 4000 cm-1 by analyzing the loading weights and variable importance in projection (VIP) scores. For SVM model, six LVs (less than seven LVs in PLSR model) were adopted in model, and the result was better than PLSR model. The and were 0.9232 and 0.9202, respectively, with RMSEC and RMSEP of 0.084 and 0.082, respectively, which indicated that the predicted values were accurate and reliable. This work demonstrated that near infrared reflectance spectroscopy with chemometrics could be used to rapidly detect the main content volatile oil in M. haplocalyx . The quality of medicine directly links to clinical efficacy, thus, it is important to control the quality of Mentha haplocalyx . Near-infrared spectroscopy combined with partial least squares regression (PLSR) and support vector machine (SVM) was applied for the rapid determination of chemical component of volatile oil content in Mentha haplocalyx . For SVM model, 6 LVs (less than 7 LVs in PLSR model) were adopted in model, and the result was better than PLSR model. It demonstrated that near infrared reflectance spectroscopy with chemometrics could be used to rapidly detect the main content volatile oil in Mentha haplocalyx . Abbreviations used: 1 st der: First-order derivative; 2 nd der: Second-order derivative; LOO: Leave-one-out; LVs: Latent variables; MC: Mean centering, NIR: Near-infrared; NIRS: Near infrared spectroscopy; PCR: Principal component regression, PLSR: Partial least squares regression; RBF: Radial basis function; RMSEC: Root mean square error of cross validation, RMSEC: Root mean square error of calibration; RMSEP: Root mean square error of prediction; SNV: Standard normal variate transformation; SVM: Support vector machine; VIP: Variable Importance in projection.

Møller-Plesset perturbation energies and distances for HeC(20) extrapolated to the complete basis set limit.

PubMed

Varandas, A J C

2009-02-01

The potential energy surface for the C(20)-He interaction is extrapolated for three representative cuts to the complete basis set limit using second-order Møller-Plesset perturbation calculations with correlation consistent basis sets up to the doubly augmented variety. The results both with and without counterpoise correction show consistency with each other, supporting that extrapolation without such a correction provides a reliable scheme to elude the basis-set-superposition error. Converged attributes are obtained for the C(20)-He interaction, which are used to predict the fullerene dimer ones. Time requirements show that the method can be drastically more economical than the counterpoise procedure and even competitive with Kohn-Sham density functional theory for the title system.

Exact exchange-correlation potentials of singlet two-electron systems

NASA Astrophysics Data System (ADS)

Ryabinkin, Ilya G.; Ospadov, Egor; Staroverov, Viktor N.

2017-10-01

We suggest a non-iterative analytic method for constructing the exchange-correlation potential, v XC ( r ) , of any singlet ground-state two-electron system. The method is based on a convenient formula for v XC ( r ) in terms of quantities determined only by the system's electronic wave function, exact or approximate, and is essentially different from the Kohn-Sham inversion technique. When applied to Gaussian-basis-set wave functions, the method yields finite-basis-set approximations to the corresponding basis-set-limit v XC ( r ) , whereas the Kohn-Sham inversion produces physically inappropriate (oscillatory and divergent) potentials. The effectiveness of the procedure is demonstrated by computing accurate exchange-correlation potentials of several two-electron systems (helium isoelectronic series, H2, H3 + ) using common ab initio methods and Gaussian basis sets.

Phenology Information Contributes to Reduce Temporal Basis Risk in Agricultural Weather Index Insurance.

PubMed

Dalhaus, Tobias; Musshoff, Oliver; Finger, Robert

2018-01-08

Weather risks are an essential and increasingly important driver of agricultural income volatility. Agricultural insurances contribute to support farmers to cope with these risks. Among these insurances, weather index insurances (WII) are an innovative tool to cope with climatic risks in agriculture. Using WII, farmers receive an indemnification not based on actual yield reductions but are compensated based on a measured weather index, such as rainfall at a nearby weather station. The discrepancy between experienced losses and actual indemnification, basis risk, is a key challenge. In particular, specifications of WII used so far do not capture critical plant growth phases adequately. Here, we contribute to reduce basis risk by proposing novel procedures how occurrence dates and shifts of growth phases over time and space can be considered and test for their risk reducing potential. Our empirical example addresses drought risks in the critical growth phase around the anthesis stage in winter wheat production in Germany. We find spatially explicit, public and open databases of phenology reports to contribute to reduce basis risk and thus improve the attractiveness of WII. In contrast, we find growth stage modelling based on growing degree days (thermal time) not to result in significant improvements.