|
|
|
| Registros recuperados: 68 | |
|
|
| Sierra Rayne; Kaya Forest; Ken J. Friesen. |
| A statistical analysis was conducted on long-term climate records in the Okanagan Valley wine grape growing region of British Columbia, Canada. No observable trends for average annual temperatures were found in the region. Analyses of monthly mean and extreme temperatures show wide spatial and temporal heterogeneity, indicating that future studies using downscaling of global climate models for this region will require resolutions on the order of several kilometers. Mean winter temperatures are increasing throughout the valley, and extreme minimum temperatures are also increasing during the winter at the central and northern sites which have historically presented the most risk of winter damage to grapevines. Only the most southern and northern sub-regions... |
| Tipo: Manuscript |
Palavras-chave: Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3162/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Gas phase standard state (298.15 K, 1 atm) structures, enthalpies of formation, and ionization energies (IEs) were calculated at the G4MP2 composite method level of theory for the parent and binary mixed carbon, silicon, nitrogen, and phosphorus cubane derivatives. Increasing nitrogen content increases the enthalpies of formation for the carbon-nitrogen, nitrogen-phosphorus, and silicon-nitrogen binary cubanes, with the opposite enthalpies of formation trend for increasing phosphorus content within the carbon-phosphorus, nitrogen-phosphorus, and silicon-phosphorus derivatives. Varying carbon/silicon content in the carbon-silicon cubanes results in no general trends for enthalpies of formation. Isomerization enthalpies within the homolog groups having more... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/5154/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| A hydrometric analysis over the available historical record (1973-2010) was conducted for the Moose Jaw River station near Burdick in south-central Saskatchewan, Canada. Frequency analyses on mean monthly, average annual, monthly minimum/maximum, and annual minimum flows generally yielded poor fits, and problems with negative flow predictions for mid- to long-term return periods regardless of distribution type. The annual maximum streamflow time series is reasonably well-described by linear and log Pearson Type III distributions, although both distribution types underestimate extreme maximum flows. Mann-Kendall linear time series analysis on mean monthly and annual streamflows reveals no trend in annual water yields, nor in mean monthly flows between March... |
| Tipo: Poster |
Palavras-chave: Earth & Environment. |
| Ano: 2011 |
URL: http://precedings.nature.com/documents/6697/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| A time trend study of groundwater monitoring well levels was conducted in British Columbia, Canada. Trend data was available for a total of 210 groundwater monitoring well stations throughout the province with end-of-month water levels over the period of record. Significant temporal trends in groundwater levels were found at 67 stations (40.4% of all stations amenable to statistical examination, and 31.9% of all available stations). Of these 67 stations, 10 had increasing groundwater level trends and the remaining 57 had declining groundwater level trends. Thus, 34.3% of stations with a sufficiently long time series for analysis displayed declining groundwater level trends, while 6.0% have increasing trends, and 59.6% of these stations appear to have no... |
| Tipo: Manuscript |
Palavras-chave: Earth & Environment. |
| Ano: 2012 |
URL: http://precedings.nature.com/documents/6844/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Historical trends in streamflow and climate were investigated for the Coldwater River watershed in south-central British Columbia, Canada. Temporal increases in rainfall and total precipitation during the spring, summer, and autumn periods, as well as on an annual basis, at the city of Merritt near the mouth of the watershed, and year-round temperature increases at this site, compare with declining summertime and annual streamflows at the nearby Merritt hydrometric station on the Coldwater River. Declining summer flows at this site could reflect the dominance of temporally increasing evaporation that is offsetting increased precipitation over the same periods of the hydrologic year. Alternatively, increased water abstractions, altered regulation regimes,... |
| Tipo: Manuscript |
Palavras-chave: Earth & Environment. |
| Ano: 2012 |
URL: http://precedings.nature.com/documents/6785/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Gas phase standard state (298.15 K, 1 atmosphere) relative enthalpies and free energies of formation were calculated for all mono- through hepta-halogenated (X=F, Cl, Br) anthraquinone congeners using the B3LYP, BHandHLYP, M062X, PBE0, and B97D density functionals with the 6-311++G(d,p) basis set. All levels of theory yielded similar results with strong intra- and inter-method correlations for both the relative enthalpy and free energy values and the corresponding thermodynamic stability rank. Within each homolog group, the most thermodynamically stable isomers are those which maximize substitution at the lateral positions (2, 3, 7, and 8) versus the less stabilizing peri positions (1, 4, 6, and 9), while also minimizing destabilizing adjacent substitution... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/5153/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| A molecular mechanics force field method (MMFF94) systematic rotor conformational search was conducted on the well known environmental contaminant n-perfluorooctanoic acid (n-PFOA). The MMFF94 conformational search yielded 2915 separate low- through high-energy conformers of n-PFOA. Ranking of these structures gave the 94 lowest MMFF94 energy conformations that were subjected to subsequent density functional theory (DFT) computational investigations at the B3LYP/6-311++G(d,p) level of theory. Application of a thermodynamic cycle approach, coupled with aqueous and gas phase DFT calculations on the molecular and anionic forms for each of the 94 lowest energy n-PFOA conformers, gave estimated acidity constants (pK~a~ values) for a final converged set of... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3837/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Aroma compounds in the Flavornet database were screened for potentially hydrolyzable carboxylic acid ester functionalities. Of the 738 aroma compounds listed in this database, 140 molecules contain carboxylic acid ester groups that may be amenable to hydrolysis in various food and beverage products. Acid- (k~A~) and base- (k~B~) catalyzed and neutral (k~N~) hydrolysis rate constants in pure water at 25°C were estimated for these aroma compounds. Where available, good agreement between theoretical and experimental hydrolytic half-lives was obtained at various pH values. Wide ranges and broad frequency distributions for k~A~, k~B~, and k~N~ are expected among the various hydrolyzable aroma compounds, with estimated k~A~ ranging from... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Plant Biology. |
| Ano: 2011 |
URL: http://precedings.nature.com/documents/6471/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Semiempirical, ab initio, and density functional theory (DFT) studies were conducted on a homologous series of straight chain perfluoroalkyl carboxylic acids (PFCAs) ranging in chain length from C~1~ (trifluoroacetic acid; TFA) to C~9~ (perfluorodecanoic acid). Regardless of perfluoroalkyl chain length and computational method and level employed, no significant change in the electrostatic or steric characteristics of the carboxylate head group was found between C~2~ and C~9~. Application of a thermodynamic cycle to calculations at the B3LYP/6-311++G(3df,2p) level provided an accurate prediction of the experimental monomeric pK~a~ for TFA. At this – and similar – levels of theory, monomeric pK~a~ values of longer straight chain PFCAs... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3829/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| The octanol/water distribution coefficients (log D~ow~) of the C~1~ through C~7~ perfluoro-n-alkyl sulfonates (PFSAs) were calculated using the M062X/6-311++G(d,p) and MP2/6-311++G(d,p)//M062X/6-311++G(d,p) levels of theory and the IEFPCM-UFF, CPCM, and SMD solvation models. At both levels of theory with all solvation models, absolute log D~ow~ calculated for the straight chain C~1~ through C~7~ PFSAs display a substantial negative bias against available experimental data and expected trends by several log units. However, the SMD solvation model achieves accurate relative log D~ow~ accuracy, yielding fragmental contributions of a -CF~2~- group towards the log D~ow~ of 0.51+/-0.02 to 0.54+/-0.01 units (-3.0+/-0.1 to -3.1+/-0.1 kJ/mol), in good agreement... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/5103/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| The KOWWIN and ALOGPS octanol-water partition coefficient (K~ow~) estimation software programs were compared for their capacity to accurately predict log K~ow~ values of 1545 organic compounds on the publicly available Domestic Substances List (DSL) from Environment Canada for which experimental data is available. Approximately equivalent log K~ow~ error statistics were observed between KOWWIN and ALOGPS against available experimental data. Substantial predictive differences were observed between the two programs for 6529 compounds not having experimental K~ow~ data on the Canadian DSL. Predictive differences of up to 40 log K~ow~ units were found between KOWWIN and ALOGPS, and in some cases, the discrepancies were sufficiently large that strongly opposing... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Pharmacology; Earth & Environment. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/3882/version/2 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| CBS-Q//B3, G4MP2, and G4 composite method calculations were used to estimate gas phase standard state (298.15 K, 1 atm) free energies of hydration (Δ~hydr~G°~(g)~), hydration equilibrium constants (log K~hydr,(g)~), bond dissociation enthalpies (BDEs), and enthalpies (Δ~d~H°~(g)~) and free energies (Δ~d~G°~(g)~) of aldehydic proton acid dissociation for various substituted aldehydes with electron withdrawing and electron releasing groups. Good quality log K~hydr,(g)~ correlations with the Swain-Lupton resonance effect parameters R and R^+^ were found, allowing extension of the model to predict log K~hydr,(g)~ values for 487 substituted aldehydes having available R-values and 108 substituted aldehydes... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/5084/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Temperature dependent rate constants were estimated for the acid- and base-catalyzed and neutral hydrolysis reactions of perfluorinated telomer acrylates (FTAcrs) and phosphate esters (FTPEs), and the SN1 and SN2 hydrolysis reactions of fluorotelomer iodides (FTIs). Under some environmental conditions, hydrolysis of monomeric FTAcrs could be rapid (half-lives of several years in marine systems and as low as several days in some landfills) and represent a dominant portion of their overall degradation. Abiotic hydrolysis of monomeric FTAcrs may be a significant contributor to current environmental loadings of fluorotelomer alcohols (FTOHs) and perfluoroalkyl carboxylic acids (PFCAs). Polymeric FTAcrs are expected to be hydrolyzed more slowly, with estimated... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3728/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Gas phase standard state (298.15 K, 1 atm) calculations were conducted at the B3LYP/6-311++G(d,p) density functional and the Gaussian-4 (G4) composite method levels of theory to estimate the acidity of various carbon acids. Excellent agreement was found between the G4 gas phase enthalpies and free energies of carbon acid dissociation and corresponding experimental values. The B3LYP/6-311++G(d,p) level of theory displayed a significantly lower accuracy for gas phase acidity prediction, but with similar qualitative trends as the G4 calculations. Good correlations using both theoretical methods were found with corresponding carbon acid aqueous pK~a~ values. However, the pK~a~ prediction accuracy of carbon acids based on correlations with theoretical gas phase... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2010 |
URL: http://precedings.nature.com/documents/4381/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest; Ken J. Friesen. |
| The pK~a~ estimation ability of the semiempirical PM6 method was evaluated across a broad range of oxyacids and compared to results obtained using the SPARC software program. Compound classes under consideration included acetic acids, alicyclic and aromatic heterocyclic acids, benzoic acids, boronic acids, hydroxamic acids, oximes, peroxides, peroxyacids, phenols, α-saturated acids, α-saturated alcohols, sulfinic acids, α-unsaturated acids, and α-unsaturated alcohols. PM6 accurately predicts the acidity of acetic and benzoic acids and their derivatives, but is less reliable for alicyclic and aromatic heterocyclic acids and phenols. α-Saturated acids are reliably modeled by PM6 except for polyacid... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Pharmacology; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/2981/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Organic carbon normalized soil and sediment-water partitioning (Koc) coefficients were estimated for all C1 through C8 perfluorinated alkylsulfonic acid (PFSA) and alkylcarboxylic acids (PFCA) congeners. The limited experimental Koc dataset for the straight chain C7 through C10 PFCAs and C8 and C10 PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning constants and used to predict Koc values for both branched and linear C1 through C8 isomers. All branched and linear congeners in this homologue range are expected to have Koc values>1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3011/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Saskatchewan, Canada, with a total land area of 651,900 km^2^, is one of the world’s most productive agricultural cropping regions. Approximately 44% of Canada's total cultivated farmland is in the province. In 2008, the total export value of crops was CAD$8.34 billion. Over the past century, changing industry economics and advances in scientific, technical, and engineering knowledge and practices have affected the amount and type of crops produced. The current work examines time trends for agricultural crop production since Saskatchewan was created in 1905. While yields of all crops have generally increased over time, total production trends vary widely by crop, warranting more detailed investigations into the socio-economical and... |
| Tipo: Poster |
Palavras-chave: Earth & Environment; Plant Biology. |
| Ano: 2011 |
URL: http://precedings.nature.com/documents/6712/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| Potential historical temporal trends in monthly, seasonal, and annual mean, minimum, and maximum streamflows and date of the spring freshet runoff peak were investigated for the Okanagan and Similkameen Rivers in south-central British Columbia, Canada. There appears to be no compelling evidence that streamflow patterns in the Okanagan and Similkameen Rivers have changed over the available hydrometric record, nor does there appear to be evidence that future changes in streamflow patterns are imminent or likely. |
| Tipo: Manuscript |
Palavras-chave: Earth & Environment. |
| Ano: 2011 |
URL: http://precedings.nature.com/documents/6584/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| SPARC, KOWWIN, and ALOGPS octanol-water partitioning (log K~ow~) and distribution (log D) constants were calculated for all C~1~ through C~8~ and the straight chain C~9~ through C~15~ perfluoroalkyl sulfonic acids (PFSAs) and carboxylic acids (PFCAs). Application of five established models for estimating bioconcentration factors (BCFs) were applied to the PFSA and PFCA log K~ow~ and log D data and compared to available field and laboratory BCF data. Wide variability was observed between the methods for estimating log K~ow~ and log D values, ranging up to several log units for particular congeners, and which was further compounded by additional variability introduced by the different BCF equations applied. With the exception of n-perfluorooctanecarboxylic... |
| Tipo: Manuscript |
Palavras-chave: Chemistry; Earth & Environment. |
| Ano: 2009 |
URL: http://precedings.nature.com/documents/3256/version/1 |
| |
|
|
| Sierra Rayne; Kaya Forest. |
| The gas and solution phase relative thermodynamic stabilities of the 39 linear and branched perfluorooctanoic acid (PFOA) congeners in both their acid and anionic forms were calculated at various levels of density functional (B3LYP, wB97XD, and M062X functionals with the 6-311++G(d,p) basis set) and second order Moller-Plesset perturbation (MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)) theory using the SMD implicit solvation model. The B3LYP functional does not accurately model the expected trends in thermodynamic stability of PFOA isomers with linear versus branched perfluoroalkyl chains. Calculations obtained with the M062X and MP2 model chemistries suggest these theoretical methods may be more appropriate for relative thermodynamic stability studies on... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2011 |
URL: http://precedings.nature.com/documents/5528/version/1 |
| |
| Registros recuperados: 68 | |
|
|
|
