Kinetics of Molybdenum Adsorption and Desorption in Soils.

PubMed

Sun, Wenguang; Selim, H Magdi

2018-05-01

Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Desorption kinetics of ciprofloxacin in municipal biosolids determined by diffusion gradient in thin films.

PubMed

D'Angelo, E; Starnes, D

2016-12-01

Ciprofloxacin (CIP) is a commonly-prescribed antibiotic that is largely excreted by the body, and is often found at elevated concentrations in treated sewage sludge (biosolids) at municipal wastewater treatment plants. When biosolids are applied to soils, they could release CIP to surface runoff, which could adversely affect growth of aquatic organisms that inhabit receiving water bodies. The hazard risk largely depends on the amount of antibiotic in the solid phase that can be released to solution (labile CIP), its diffusion coefficient, and sorption/desorption exchange rates in biosolids particles. In this study, these processes were evaluated in a Class A Exceptional Quality Biosolids using a diffusion gradient in thin films (DGT) sampler that continuously removed CIP from solution, which induced desorption and diffusion in biosolids. Mass accumulation of antibiotic in the sampler over time was fit by a diffusion transport and exchange model available in the software tool 2D-DIFS to derive the distribution coefficient of labile CIP (K dl ) and sorption/desorption rate constants in the biosolids. The K dl was 13 mL g -1 , which equated to 16% of total CIP in the labile pool. Although the proportion of labile CIP was considerable, release rates to solution were constrained by slow desorption kinetics (desorption rate constant = 4 × 10 -6 s -1 ) and diffusion rate (effective diffusion coefficient = 6 × 10 -9  cm 2  s -1 . Studies are needed to investigate how changes in temperature, water content, pH and other physical and chemical characteristics can influence antibiotic release kinetics and availability and mobility in biosolid-amended soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance

DOE PAGES

Dittrich, Timothy M.; Reimus, Paul W.

2015-09-29

In this study, batch adsorption and breakthrough column experiments were conducted to evaluate uranium transport through altered material that fills fractures in a granite rock system at the Grimsel Test Site in Switzerland at pH 6.9 and 7.9. The role of adsorption and desorption kinetics was evaluated with reactive transport modeling by comparing one-, two-, and three-site models. Emphasis was placed on describing long desorption tails that are important for upscaling in time and distance. The effect of increasing pH in injection solutions was also evaluated. For pH 6.9, a three-site model with forward rate constants between 0.07 and 0.8more » ml g –1 h –1, reverse rate constants between 0.001 and 0.06 h –1, and site densities of 1.3, 0.104, and 0.026 μmol g –1 for ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. For pH 7.9, a three-site model with forward rate constants between 0.05 and 0.8 mL g –1 h –1, reverse rate constants between 0.001 and 0.6 h –1, and site densities of 1.3, 0.039, and 0.013 μmol g –1 for a ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. Column retardation coefficients (R d) were 80 for pH 6.9 and 10.3 for pH 7.9. Model parameters determined from the batch and column experiments were used in 50 year large-scale simulations for continuous and pulse injections and indicated that a three-site model is necessary at pH 6.9, although a K d-type equilibrium partition model with one-site was adequate for large scale predictions at pH 7.9. Batch experiments were useful for predicting early breakthrough times in the columns while column experiments helped differentiate the relative importance of sorption sites and desorption rate constants on transport.« less

Grain-Size Based Additivity Models for Scaling Multi-rate Uranyl Surface Complexation in Subsurface Sediments

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

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

The additivity model assumed that field-scale reaction properties in a sediment including surface area, reactive site concentration, and reaction rate can be predicted from field-scale grain-size distribution by linearly adding reaction properties estimated in laboratory for individual grain-size fractions. This study evaluated the additivity model in scaling mass transfer-limited, multi-rate uranyl (U(VI)) surface complexation reactions in a contaminated sediment. Experimental data of rate-limited U(VI) desorption in a stirred flow-cell reactor were used to estimate the statistical properties of the rate constants for individual grain-size fractions, which were then used to predict rate-limited U(VI) desorption in the composite sediment. The resultmore » indicated that the additivity model with respect to the rate of U(VI) desorption provided a good prediction of U(VI) desorption in the composite sediment. However, the rate constants were not directly scalable using the additivity model. An approximate additivity model for directly scaling rate constants was subsequently proposed and evaluated. The result found that the approximate model provided a good prediction of the experimental results within statistical uncertainty. This study also found that a gravel-size fraction (2 to 8 mm), which is often ignored in modeling U(VI) sorption and desorption, is statistically significant to the U(VI) desorption in the sediment.« less

pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

PubMed

Esarey, Samuel L; Bartlett, Bart M

2018-04-17

The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

Grain-Size Based Additivity Models for Scaling Multi-rate Uranyl Surface Complexation in Subsurface Sediments

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

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

This study statistically analyzed a grain-size based additivity model that has been proposed to scale reaction rates and parameters from laboratory to field. The additivity model assumed that reaction properties in a sediment including surface area, reactive site concentration, reaction rate, and extent can be predicted from field-scale grain size distribution by linearly adding reaction properties for individual grain size fractions. This study focused on the statistical analysis of the additivity model with respect to reaction rate constants using multi-rate uranyl (U(VI)) surface complexation reactions in a contaminated sediment as an example. Experimental data of rate-limited U(VI) desorption in amore » stirred flow-cell reactor were used to estimate the statistical properties of multi-rate parameters for individual grain size fractions. The statistical properties of the rate constants for the individual grain size fractions were then used to analyze the statistical properties of the additivity model to predict rate-limited U(VI) desorption in the composite sediment, and to evaluate the relative importance of individual grain size fractions to the overall U(VI) desorption. The result indicated that the additivity model provided a good prediction of the U(VI) desorption in the composite sediment. However, the rate constants were not directly scalable using the additivity model, and U(VI) desorption in individual grain size fractions have to be simulated in order to apply the additivity model. An approximate additivity model for directly scaling rate constants was subsequently proposed and evaluated. The result found that the approximate model provided a good prediction of the experimental results within statistical uncertainty. This study also found that a gravel size fraction (2-8mm), which is often ignored in modeling U(VI) sorption and desorption, is statistically significant to the U(VI) desorption in the sediment.« less

Competitive adsorption/desorption of tetracycline, oxytetracycline and chlortetracycline on two acid soils: Stirred flow chamber experiments.

PubMed

Fernández-Calviño, David; Bermúdez-Couso, Alipio; Arias-Estévez, Manuel; Nóvoa-Muñoz, Juan Carlos; Fernández-Sanjurjo, Maria J; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino

2015-09-01

The objective of this work was to study the competitive adsorption/desorption of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) on two acid soils. We used the stirred flow chamber technique to obtain experimental data on rapid kinetic processes affecting the retention/release of the antibiotics. Both adsorption and desorption were higher on soil 1 (which showed the highest carbon, clay and Al and Fe oxides content) than on soil 2. Moreover, hysteresis affected the adsorption/desorption processes. Experimental data were fitted to a pseudo-first order equation, resulting qamax (adsorption maximum) values that were higher for soil 1 than for soil 2, and indicating that CTC competed with TC more intensely than OTC in soil 1. Regarding soil 2, the values corresponding to the adsorption kinetics constants (ka) and desorption kinetics constants for fast sites (kd1), followed a trend inverse to qamax and qdmax respectively. In conclusion, competition affected adsorption/desorption kinetics for the three antibiotics assayed, and thus retention/release and subsequent transport processes in soil and water environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

In situ measurements of fuel retention by laser induced desorption spectroscopy in TEXTOR

NASA Astrophysics Data System (ADS)

Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Stoschus, H.; Brezinsek, S.; Samm, U.; TEXTOR Team

2011-12-01

In future fusion devices such as ITER tritium retention due to tritium co-deposition in mixed material layers can be a serious safety problem. Laser induced desorption spectroscopy (LIDS) can measure the hydrogen content of hydrogenic carbon layers locally on plasma-facing components, while hydrogen is used as a tritium substitute. For several years, this method has been applied in the TEXTOR tokamak in situ during plasma operation to monitor the hydrogen content in space and time. This work shows the LIDS signal reproducibility and studies the effects of different plasma conditions, desorption distances from the plasma and different laser energies using a dedicated sample with constant hydrogen amount. Also the LIDS signal evaluation procedure is described in detail and the detection limits for different conditions in the TEXTOR tokamak are estimated.

Desorption of biocides from renders modified with acrylate and silicone.

PubMed

Styszko, Katarzyna; Bollmann, Ulla E; Wangler, Timothy P; Bester, Kai

2014-01-01

Biocides are used in the building industry to prevent algal, bacterial and fungal growth on polymericrenders and thus to protect buildings. However, these biocides are leached into the environment. To better understand this leaching, the sorption/desorption of biocides in polymeric renders was assessed. In this study the desorption constants of cybutryn, carbendazim, iodocarb, isoproturon, diuron, dichloro-N-octylisothiazolinone and tebuconazole towards acrylate and silicone based renders were assessed at different pH values. At pH 9.5 (porewater) the constants for an acrylate based render varied between 8 (isoproturon) and 9634 (iodocarb) and 3750 (dichloro-N-octylisothiazolinone), respectively. The values changed drastically with pH value. The results for the silicone based renders were in a similar range and usually the compounds with high sorption constants for one polymer also had high values for the other polymer. Comparison of the octanol water partitioning constants (Kow) with the render/water partitioning constants (Kd) revealed similarities, but no strong correlation. Adding higher amounts of polymer to the render material changed the equilibria for dichloro-N-octylisothiazolinone, tebuconazole, cybutryn, carbendazim but not for isoproturon and diuron. Copyright © 2013 Elsevier Ltd. All rights reserved.

Measurement of Passive Uptake Rates for Volatile Organic Compounds on Commercial Thermal Desorption Tubes and the Effect of Ozone on Sampling

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

Maddalena, Randy; Parra, Amanda; Russell, Marion

Diffusive or passive sampling methods using commercially filled axial-sampling thermal desorption tubes are widely used for measuring volatile organic compounds (VOCs) in air. The passive sampling method provides a robust, cost effective way to measure air quality with time-averaged concentrations spanning up to a week or more. Sampling rates for VOCs can be calculated using tube geometry and Fick’s Law for ideal diffusion behavior or measured experimentally. There is evidence that uptake rates deviate from ideal and may not be constant over time. Therefore, experimentally measured sampling rates are preferred. In this project, a calibration chamber with a continuous stirredmore » tank reactor design and constant VOC source was combined with active sampling to generate a controlled dynamic calibration environment for passive samplers. The chamber air was augmented with a continuous source of 45 VOCs ranging from pentane to diethyl phthalate representing a variety of chemical classes and physiochemical properties. Both passive and active samples were collected on commercially filled Tenax TA thermal desorption tubes over an 11-day period and used to calculate passive sampling rates. A second experiment was designed to determine the impact of ozone on passive sampling by using the calibration chamber to passively load five terpenes on a set of Tenax tubes and then exposing the tubes to different ozone environments with and without ozone scrubbers attached to the tube inlet. During the sampling rate experiment, the measured diffusive uptake was constant for up to seven days for most of the VOCs tested but deviated from linearity for some of the more volatile compounds between seven and eleven days. In the ozone experiment, both exposed and unexposed tubes showed a similar decline in terpene mass over time indicating back diffusion when uncapped tubes were transferred to a clean environment but there was no indication of significant loss by ozone reaction.« less

Desorption of plutonium from montmorillonite: An experimental and modeling study

DOE PAGES

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-15

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

Desorption of plutonium from montmorillonite: An experimental and modeling study

NASA Astrophysics Data System (ADS)

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-01

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. We evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with Kd values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in Kd, indicating that true sorption equilibrium was not achieved within the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. A conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50-100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

COMPARISON OF 24H AVERAGE VOC MONITORING RESULTS FOR RESIDENTIAL INDOOR AND OUTDOOR AIR USING CARBOPACK X-FILLED DIFFUSIVE SAMPLERS AND ACTIVE SAMPLING - A PILOT STUDY

EPA Science Inventory

Analytical results obtained by thermal desorption GC/MS for 24h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive samp...

A study of the kinetics of isothermal nicotine desorption from silicon dioxide

NASA Astrophysics Data System (ADS)

Adnadjevic, Borivoj; Lazarevic, Natasa; Jovanovic, Jelena

2010-12-01

The isothermal kinetics of nicotine desorption from silicon dioxide (SiO 2) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters ( Ea, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the "model-fitting" method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, Ea,α and ln Aα, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.

Sorption-desorption and biosorption of bisphenol A, triclosan, and 17α-ethinylestradiol to sewage sludge.

PubMed

Banihashemi, Bahman; Droste, Ronald L

2014-07-15

To better understand the fate of microconstituents (MCs) in an activated sludge (AS) system, sorption, biosorption, and desorption studies were investigated at μg/L range for 17α-ethinylestradiol (EE2), bisphenol A (BPA), and triclosan (TCS). Batch experiments with activated and deactivated sludge originating from continuous flow porous pot reactors operating at solid retention times (SRTs) of 5, 10, and 15 days were conducted in order to investigate the sorption kinetics and distinguish physicochemical sorption and biosorption. The effect of SRT and the biomass concentration on sorption kinetics were also studied. Selected MCs showed high sorption affinity to the non-viable biomass during the first 30 min of the experiment, which was gradually reduced until equilibrium was reached. Desorption results showed two distinct stages, a very rapid desorption within 20 min followed by a slow desorption stage. Biosorption study indicated that the soluble concentrations of target compounds decreased rapidly for selected MCs similar to the sorption study; however, the soluble and solid phase concentrations continued to decrease slowly during the length of the experiment which indicates the possible biodegradation of these compounds in both phases. Finally, mathematical models were applied to describe the sorption mechanism and Freundlich sorption isotherms with values of 1/n close to 1 were found to best fit the results which demonstrate that all tested concentrations result on the linear part of the Freundlich isotherm. Calculation of the Freundlich constant, KF and distribution coefficient, Kd exhibited the greater tendency of EE2 and TCS for sorption, compared to BPA. The results of this study indicated that the SRT had a clear effect on the sorption kinetics where the highest sorption rate constant was achieved for a SRT of 10 days for all three target substances. This could be due to change of the morphology of the biomass from reactors operating at different SRTs. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

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

Paxton, W. F., E-mail: william.f.paxton@vanderbilt.edu; Howell, M.; Kang, W. P.

2014-06-21

The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classicalmore » processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.« less

Is energy pooling necessary in ultraviolet matrix-assisted laser desorption/ionization?

PubMed

Lin, Hou-Yu; Song, Botao; Lu, I-Chung; Hsu, Kuo-Tung; Liao, Chih-Yu; Lee, Yin-Yu; Tseng, Chien-Ming; Lee, Yuan-Tseh; Ni, Chi-Kung

2014-01-15

Energy pooling has been suggested as the key process for generating the primary ions during ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI). In previous studies, decreases in fluorescence quantum yields as laser fluence increased for 2-aminobenzoic acid, 2,5-dihydroxybenzoic acid (2,5-DHB), and 3-hydroxypicolinic acid were used as evidence of energy pooling. This work extends the research to other matrices and addresses whether energy pooling is a universal property in UV-MALDI. Energy pooling was investigated in a time-resolved fluorescence experiment by using a short laser pulse (355 nm, 20 ps pulse width) for excitation and a streak camera (1 ps time resolution) for fluorescence detection. The excited-state lifetime of 2,5-DHB decreased with increases in laser fluence. This suggests that a reaction occurs between two excited molecules, and that energy pooling may be one of the possible reactions. However, the excited-state lifetime of 2,4,6-trihydroxyacetophenone (THAP) did not change with increases in laser fluence. The upper limit of the energy pooling rate constant for THAP is estimated to be approximately 100-500 times smaller than that of 2,5-DHB. The small energy pooling rate constant for THAP indicates that the potential contribution of the energy pooling mechanism to the generation of THAP matrix primary ions should be reconsidered. Copyright © 2013 John Wiley & Sons, Ltd.

Counterion adsorption and desorption rate of a charged macromolecule

NASA Astrophysics Data System (ADS)

Shi, Yu; Yang, Jingfa; Zhao, Jiang

The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

Ion Yields in the Coupled Chemical and Physical Dynamics Model of Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Knochenmuss, Richard

2015-08-01

The Coupled Chemical and Physical Dynamics (CPCD) model of matrix assisted laser desorption ionization has been restricted to relative rather than absolute yield comparisons because the rate constant for one step in the model was not accurately known. Recent measurements are used to constrain this constant, leading to good agreement with experimental yield versus fluence data for 2,5-dihydroxybenzoic acid. Parameters for alpha-cyano-4-hydroxycinnamic acid are also estimated, including contributions from a possible triplet state. The results are compared with the polar fluid model, the CPCD is found to give better agreement with the data.

Broad spectrum infrared thermal desorption of wipe-based explosive and narcotic samples for trace mass spectrometric detection.

PubMed

Forbes, Thomas P; Staymates, Matthew; Sisco, Edward

2017-08-07

Wipe collected analytes were thermally desorbed using broad spectrum near infrared heating for mass spectrometric detection. Employing a twin tube filament-based infrared emitter, rapid and efficiently powered thermal desorption and detection of nanogram levels of explosives and narcotics was demonstrated. The infrared thermal desorption (IRTD) platform developed here used multi-mode heating (direct radiation and secondary conduction from substrate and subsequent convection from air) and a temperature ramp to efficiently desorb analytes with vapor pressures across eight orders of magnitude. The wipe substrate experienced heating rates up to (85 ± 2) °C s -1 with a time constant of (3.9 ± 0.2) s for 100% power emission. The detection of trace analytes was also demonstrated from complex mixtures, including plastic-bonded explosives and exogenous narcotics, explosives, and metabolites from collected artificial latent fingerprints. Manipulation of the emission power and duration directly controlled the heating rate and maximum temperature, enabling differential thermal desorption and a level of upstream separation for enhanced specificity. Transitioning from 100% power and 5 s emission duration to 25% power and 30 s emission enabled an order of magnitude increase in the temporal separation (single seconds to tens of seconds) of the desorption of volatile and semi-volatile species within a collected fingerprint. This mode of operation reduced local gas-phase concentrations, reducing matrix effects experienced with high concentration mixtures. IRTD provides a unique platform for the desorption of trace analytes from wipe collections, an area of importance to the security sector, transportation agencies, and customs and border protection.

Modeling and experiments for the time-dependent diffusion coefficient during methane desorption from coal

NASA Astrophysics Data System (ADS)

Cheng-Wu, Li; Hong-Lai, Xue; Cheng, Guan; Wen-biao, Liu

2018-04-01

Statistical analysis shows that in the coal matrix, the diffusion coefficient for methane is time-varying, and its integral satisfies the formula μt κ /(1 + β κ ). Therefore, a so-called dynamic diffusion coefficient model (DDC model) is developed. To verify the suitability and accuracy of the DDC model, a series of gas diffusion experiments were conducted using coal particles of different sizes. The results show that the experimental data can be accurately described by the DDC and bidisperse models, but the fit to the DDC model is slightly better. For all coal samples, as time increases, the effective diffusion coefficient first shows a sudden drop, followed by a gradual decrease before stabilizing at longer times. The effective diffusion coefficient has a negative relationship with the size of the coal particle. Finally, the relationship between the constants of the DDC model and the effective diffusion coefficient is discussed. The constant α (μ/R 2 ) denotes the effective coefficient at the initial time, and the constants κ and β control the attenuation characteristic of the effective diffusion coefficient.

Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

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

Danilchenko, B. A., E-mail: danil@iop.kiev.ua; Yaskovets, I. I.; Uvarova, I. Y.

2014-04-28

The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or γ-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10–300 K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent withmore » theoretical prediction.« less

The feasibility of desorption on Zeolite-water pair using dry gas

NASA Astrophysics Data System (ADS)

Oktariani, E.; Nakashima, K.; Noda, A.; Xue, B.; Tahara, K.; Nakaso, K.; Fukai, J.

2018-04-01

The increase in temperature, reduction in partial pressure, reduction in concentration, purging with an inert fluid, and displacement with a more strongly adsorbing species are the basic things that occur in the practical method of desorption. In this study, dry gas at constant temperature and pressure was employed as the aid to reduce the partial pressure in the water desorption on the zeolite 13X. The objective of this study is to confirm the feasibility of desorption using dry gas experimentally and numerically. The implication of heat and mass transfers were numerically investigated to find the most influential. The results of numerical simulation agree with the experimental ones for the distribution of local temperature and average water adsorbed in the packed bed.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

The properties of water in swollen cross-linked polystyrene sulfo acids

NASA Astrophysics Data System (ADS)

Gagarin, A. N.; Tokmachev, M. G.; Kovaleva, S. S.; Ferapontov, N. B.

2008-11-01

The properties of water in polystyrene sulfo acid gels with various cross-linking degrees were studied by optical volumetry and dynamic desorption porosimetry. The isotherms of water desorption obtained by dynamic desorption porosimetry coincided with isopiestic isotherms, which allowed this method to be recommended for the determination of the amount of water in polymer gels. Joint optical volumetry and dynamic desorption porosimetry studies showed that the interphase boundary in the cross-liked hydrophilic polymer-water system did not coincide with the visible gel boundary, because gels were two-phase systems, which contained water of two types, “free” and “bound.” The influence of the degree of polymer cross-linking on the amounts and properties of water of the two types was studied. It was shown that constants of water distribution in the polymer could be calculated from the dynamic desorption porosimetry data.

A new beaded carbon molecular sieve sorbent for {sup 222}Rn monitoring

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

Scarpitta, S.C.

1996-05-01

A new commercially available beaded carbon molecular sieve sorbent, Carboxen-564 (20/45 mesh), was tested and compared to Calgon-PCB (40/80) activated carbon for its adsorptive and desorptive characteristics under controlled conditions of temperature (25{degrees})C and relative humidity (RH). The amount of water vapor adsorbed by the beaded carbon molecular sieve material was typically a factor of 4 lower than the activated carbon, with a concomitant fourfold increase in the {sup 222}Rn adsorption coefficient, K{sub Rn}. The maximum K{sub Rn} value for a thin layer of Carboxen-564, following a 2-d exposure at 40% RH, was 7.2 Bq kg{sup {minus}1} per Bq m{supmore » {minus}3}. The K{sub Rn} for a 1-cm bed, following a 2-d exposure was 5.5 Bq m{sup {minus}3}, a 25% reduction. under dynamic sampling conditions, where 0.4 g of the beaded carbon molecular sieve was contained in a 6 cm x 0.4 cm diameter tube, the maximum K{sub Rn} value was 6.5 Bq m{sup {minus}3} after 2.5 h of sampling at 29% RH when the input flow rate was 4.2 x 10{sup {minus}3} m{sup 3} h{sup {minus}1}. Kinetic studies were also conducted under passive sampling conditions. The data show that the {sup 222}Rn buildup time-constant for a thin layer of the beaded carbon molecular sieve material was 1.3 h, whereas that of a 1 cm bed was 13 h. The {sup 222}Rn desorption time-constants, from gram amounts of the beaded carbon molecular sieve material was 1.3 h, whereas that of a 1 cm bed was 13 h. The {sup 222}Rn desorption time-constants, from gram amounts of the beaded carbon molecular sieve material into air and into a commercially available toluene based liquid scintillation cocktail, were 2 h and 3 h, respectively. Carboxen`s high {sup 222}Rn adsorbing capacity, rapid kinetics, hydrophobicity and physical properties makes it an attractive alternative to other commercially available activated carbon used in passive and dynamic sampling devices. 18 refs., 7 figs.« less

Charge transfer and adsorption-desorption kinetics in carbon nanotube and graphene gas sensing

NASA Astrophysics Data System (ADS)

Liang, Sang-Zi; Chen, Gugang; Harutyunyan, Avetik; Cole, Milton; Sofo, Jorge

2014-03-01

Detection of molecules in the gas phase by carbon nanotube and graphene has great application potentials due to the high sensitivity and surface-to-volume ratio. In chemiresistor, the conductance of the materials has been proposed to change as a result of charge transfer from the adsorbed molecules. Due to self-interaction errors, calculations using LDA or GGA density functionals have an innate disadvantage in dealing with charge transfer situations. A model which takes into consideration the dielectric interaction between the graphene surface and the molecule is employed to estimate the distance where charge transfer becomes favorable. Adsorption-desorption kinetics is studied with a modified Langmuir model, including sites from which the molecules do not desorb within the experimental time. Assuming a constant mobility, the model reproduces existing experimental conductance data. Its parameters provide information about the microscopic process during the detection and varying them allows optimization of aspects of sensor performance, including sensitivity, detection limit and response time. This work is supported by Honda Research Institute USA, Inc.

Constant-Distance Mode Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging of Biological Samples with Complex Topography

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

Nguyen, Son N.; Liyu, Andrey V.; Chu, Rosalie K.

A new approach for constant distance mode mass spectrometry imaging of biological samples using nanospray desorption electrospray ionization (nano-DESI MSI) was developed by integrating a shear-force probe with nano-DESI probe. The technical concept and basic instrumental setup as well as general operation of the system are described. Mechanical dampening of resonant oscillations due to the presence of shear forces between the probe and the sample surface enables constant-distance imaging mode via a computer controlled closed feedback loop. The capability of simultaneous chemical and topographic imaging of complex biological samples is demonstrated using living Bacillus Subtilis ATCC 49760 colonies on agarmore » plates. The constant-distance mode nano-DESI MSI enabled imaging of many metabolites including non-ribosomal peptides (surfactin, plipastatin and iturin) and iron-bound heme on the surface of living bacterial colonies ranging in diameter from 10 mm to 13 mm with height variations of up to 0.8 mm above the agar plate. Co-registration of ion images to topographic images provided higher-contrast images. Constant-mode nano-DESI MSI is ideally suited for imaging biological samples of complex topography in their native state.« less

Real-Time Monitoring of Azo Dye Interfacial Adsorption at Silica-Water Interface by Total Internal Reflection-Induced Surface Evanescent Wave.

PubMed

Xiong, Yan; Wang, Qing; Duan, Ming; Tan, Jun; Fang, Shenwen; Wu, Jiayi

2018-06-19

An interface research method based on total internal reflection induced evanescent wave (TIR-EW) is developed to monitor the adsorption behavior of azo dye at the silica-water interface. The monitoring system is constructed by employing silica optical fiber (SOF) as both charged substrate for dye adsorption and light transmission waveguide for evanescent wave production. According to the change of evanescent wave intensity and followed by Beer's law, the methylene blue (MB) adsorption behavior can be real-time monitored at the silica-water interface. Langmuir adsorption model and pseudo-first-order model are applied to obtain the related thermodynamic and kinetic data. The adsorption equilibrium constant ( K ads ) and adsorption free energy (Δ G) of MB at the silica-water interface are determined to be (3.3 ± 0.5) × 10 4 M -1 and -25.7 ± 1.7 kJ mol -1 . Meanwhile, this method is highlighted to isolate elementary processes of adsorption and desorption under steady-state conditions, and gives adsorption rate constant ( k a ) and desorption rate constant ( k d ) of 8585 ± 19.8 min -1 and 0.26 ± 0.0006 min -1 for 15 r/min flow rate. The surface interaction process is revealed and adsorption mechanism is proposed, indicating MB first adsorbed on Si-O - sites through electrostatic attraction and then on Si-OH sites through hydrogen bond with increasing MB concentrations. Our findings from this study provided molecular-level interpretation of azo dye adsorption at silica-water interface, and the results provide important insight into how MB adsorption can be controlled at the interface.

Sorption and reemission of formaldehyde by gypsum wallboard. Report for June 1990-August 1992

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

Chang, J.C.S.

1993-01-01

The paper gives results of an analysis of the sorption and desorption of formaldehyde by unpainted wallboard, using a mass transfer model based on the Langmuir sorption isotherm. The sorption and desorption rate constants are determined by short-term experimental data. Long-term sorption and desorption curves are developed by the mass transfer model without any adjustable parameters. Compared with other empirically developed models, the mass transfer model has more extensive applicability and provides an elucidation of the sorption and desorption mechanism that empirical models cannot. The mass transfer model is also more feasible and accurate than empirical models for applications suchmore » as scale-up and exposure assessment. For a typical indoor environment, the model predicts that gypsum wallboard is a much stronger sink for formaldehyde than for other indoor air pollutants such as tetrachloroethylene and ethylbenzene. The strong sink effects are reflected by the high equilibrium capacity and slow decay of the desorption curve.« less

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

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

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

DOE PAGES

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera; ...

2018-03-06

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

C incorporation and segregation during Si 1- yC y/Si( 0 0 1 ) gas-source molecular beam epitaxy from Si 2H 6 and CH 3SiH 3

NASA Astrophysics Data System (ADS)

Foo, Y. L.; Bratland, K. A.; Cho, B.; Soares, J. A. N. T.; Desjardins, P.; Greene, J. E.

2002-08-01

We have used in situ D 2 temperature-programmed desorption (TPD) to probe C incorporation and surface segregation kinetics, as well as hydrogen desorption pathways, during Si 1- yC y(0 0 1) gas-source molecular beam epitaxy from Si 2H 6/CH 3SiH 3 mixtures at temperatures Ts between 500 and 650 °C. Parallel D 2 TPD results from C-adsorbed Si(0 0 1) wafers exposed to varying CH 3SiH 3 doses serve as reference data. Si 1- yC y(0 0 1) layer spectra consist of three peaks: first-order β 1 at 515 °C and second-order β 2 at 405 °C, due to D 2 desorption from Si monodeuteride and dideuteride phases, as well as a new second-order C-induced γ 1 peak at 480 °C. C-adsorbed Si(0 0 1) samples with very high CH 3SiH 3 exposures yielded a higher-temperature TPD feature, corresponding to D 2 desorption from surface C atoms, which was never observed in Si 1- yC y(0 0 1) layer spectra. The Si 1- yC y(0 0 1) γ 1 peak arises due to desorption from Si monodeuteride species with C backbonds. γ 1 occurs at a lower temperature than β 1 reflecting the lower D-Si * bond strength, where Si * represents surface Si atoms bonded to second-layer C atoms, as a result of charge transfer from dangling bonds. The total integrated monohydride (β 1+γ 1) intensity, and hence the dangling bond density, remains constant with y indicating that C does not deactivate surface dangling bonds as it segregates to the second-layer during Si 1- yC y(0 0 1) growth. Si * coverages increase with y at constant Ts and with Ts at constant y. The positive Ts-dependence shows that C segregation is kinetically limited at Ts⩽650 °C. D 2 desorption activation energies from β 1, γ 1 and β 2 sites are 2.52, 2.22 and 1.88 eV.

Preliminary studies of using preheated carrier gas for on-line membrane extraction of semivolatile organic compounds.

PubMed

Liu, Xinyu; Pawliszyn, Janusz

2007-04-01

In this paper, we present results for the on-line determination of semivolatile organic compounds (SVOCs) in air using membrane extraction with a sorbent interface-ion mobility spectrometry (MESI-IMS) system with a preheated carrier (stripping) gas. The mechanism of the mass transfer of SVOCs across a membrane was initially studied. In comparison with the extraction of volatile analytes, the mass transfer resistance that originated from the slow desorption from the internal membrane surface during the SVOC extraction processes should be taken into account. A preheated carrier gas system was therefore built to facilitate desorption of analytes from the internal membrane surface. With the benefit of a temperature gradient existing between the internal and external membrane surfaces, an increase in the desorption rate of a specific analyte at the internal surface and the diffusion coefficient within the membrane could be achieved while avoiding a decrease of the distribution constant on the external membrane interface. This technique improved both the extraction rate and response times of the MESI-IMS system for the analysis of SVOCs. Finally, the MESI-IMS system was shown to be capable of on-site measurement by monitoring selected polynuclear aromatic hydrocarbons emitted from cigarette smoke.

Gas identification by dynamic measurements of SnO2 sensors

NASA Astrophysics Data System (ADS)

Vorobioff, Juan; Rodriguez, Daniel; Boselli, Alfredo; Lamagna, Alberto; Rinaldi, Carlos

2011-09-01

It is well know that the use of chambers with the sensors in the e-nose improves the measurements, due to a constant gas flow and the controlled temperature sensors[1]. Normally, the chamber temperature is above room temperature due to the heat generated by the heater of sensors. Also, the chamber takes a long time to reach a stable equilibrium temperature and it depends on enviromental conditions. Besides, the temperature variations modify the humidity producing variations in resistance measurements[2]. In this work using a heater system that controls the temperature of the chamber, the desorption process on SnO2 sensor array was study[3]. Also, it was fitted the data signal sensors using a two exponential decay functions in order to determine the desorbing constant process. These constants were used to classify and identify different alcohols and their concentrations.

Rapid detection of terbufos in stomach contents using desorption electrospray ionization mass spectrometry.

PubMed

Wilson, Christina R; Mulligan, Christopher C; Strueh, Kurt D; Stevenson, Gregory W; Hooser, Stephen B

2014-05-01

Desorption electrospray ionization mass spectrometry (DESI-MS) is an emerging analytical technique that permits the rapid and direct analysis of biological or environmental samples under ambient conditions. Highlighting the versatility of this technique, DESI-MS has been used for the rapid detection of illicit drugs, chemical warfare agents, agricultural chemicals, and pharmaceuticals from a variety of sample matrices. In diagnostic veterinary toxicology, analyzing samples using traditional analytical instrumentation typically includes extensive sample extraction procedures, which can be time consuming and labor intensive. Therefore, efforts to expedite sample analyses are a constant goal for diagnostic toxicology laboratories. In the current report, DESI-MS was used to directly analyze stomach contents from a dog exposed to the organophosphate insecticide terbufos. The total DESI-MS analysis time required to confirm the presence of terbufos and diagnose organophosphate poisoning in this case was approximately 5 min. This highlights the potential of this analytical technique in the field of veterinary toxicology for the rapid diagnosis and detection of toxicants in biological samples. © 2014 The Author(s).

Desorption kinetics of hydrophobic organic chemicals from sediment to water: a review of data and models.

PubMed

Birdwell, Justin; Cook, Robert L; Thibodeaux, Louis J

2007-03-01

Resuspension of contaminated sediment can lead to the release of toxic compounds to surface waters where they are more bioavailable and mobile. Because the timeframe of particle resettling during such events is shorter than that needed to reach equilibrium, a kinetic approach is required for modeling the release process. Due to the current inability of common theoretical approaches to predict site-specific release rates, empirical algorithms incorporating the phenomenological assumption of biphasic, or fast and slow, release dominate the descriptions of nonpolar organic chemical release in the literature. Two first-order rate constants and one fraction are sufficient to characterize practically all of the data sets studied. These rate constants were compared to theoretical model parameters and functionalities, including chemical properties of the contaminants and physical properties of the sorbents, to determine if the trends incorporated into the hindered diffusion model are consistent with the parameters used in curve fitting. The results did not correspond to the parameter dependence of the hindered diffusion model. No trend in desorption rate constants, for either fast or slow release, was observed to be dependent on K(OC) or aqueous solubility for six and seven orders of magnitude, respectively. The same was observed for aqueous diffusivity and sediment fraction organic carbon. The distribution of kinetic rate constant values was approximately log-normal, ranging from 0.1 to 50 d(-1) for the fast release (average approximately 5 d(-1)) and 0.0001 to 0.1 d(-1) for the slow release (average approximately 0.03 d(-1)). The implications of these findings with regard to laboratory studies, theoretical desorption process mechanisms, and water quality modeling needs are presented and discussed.

Long-term Kinetics of Uranyl Desorption from Sediments Under Advective Conditions

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

Shang, Jianying; Liu, Chongxuan; Wang, Zheming

2014-02-15

Long-term (> 4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge (IFRC) site at the US Department of Energy (DOE) Hanford 300 Area. The experimental results were used to evaluate alternative multi-rate surface complexation reaction (SCR) approaches to describe the short- and long-term kinetics of U(VI) desorption under flow conditions. The SCR stoichiometry, equilibrium constants, and multi-rate parameters were independently characterized in batch and stirred flow-cell reactors. Multi-rate SCR models that were either additively constructed using the SCRs for individual size fractions (e.g., Shang et al.,more » 2011), or composite in nature could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using a labile U concentration measured by carbonate extraction under-estimated desorbable U(VI) and the long-term rate of U(VI) desorption. An alternative modeling approach using total U as the desorbable U(VI) concentration was proposed to overcome this difficulty. This study also found that the gravel size fraction (2-8 mm), which is typically treated as non-reactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application, and identifies important parameters and uncertainties affecting model predictions.« less

Reversible dielectric property degradation in moisture-contaminated fiber-reinforced laminates

NASA Astrophysics Data System (ADS)

Rodriguez, Luis A.; García, Carla; Fittipaldi, Mauro; Grace, Landon R.

2016-03-01

The potential for recovery of dielectric properties of three water-contaminated fiber-reinforced laminates is investigated using a split-post dielectric resonant technique at X-band (10 GHz). The three material systems investigated are bismaleimide (BMI) reinforced with an eight-harness satin weave quartz fabric, an epoxy resin reinforced with an eight- harness satin weave glass fabric (style 7781), and the same epoxy reinforced with a four-harness woven glass fabric (style 4180). A direct correlation between moisture content, dielectric constant, and loss tangent was observed during moisture absorption by immersion in distilled water at 25 °C for five equivalent samples of each material system. This trend is observed through at least 0.72% water content by weight for all three systems. The absorption of water into the BMI, 7781 epoxy, and 4180 epoxy laminates resulted in a 4.66%, 3.35%, and 4.01% increase in dielectric constant for a 0.679%, 0.608%, and 0.719% increase in water content by weight, respectively. Likewise, a significant increase was noticed in loss tangent for each material. The same water content is responsible for a 228%, 71.4%, and 64.1% increase in loss tangent, respectively. Subsequent to full desorption through drying at elevated temperature, the dielectric constant and loss tangent of each laminate exhibited minimal change from the dry, pre-absorption state. The dielectric constant and loss tangent change after the absorption and desorption cycle, relative to the initial state, was 0.144 % and 2.63% in the BMI, 0.084% and 1.71% in the style 7781 epoxy, and 0.003% and 4.51% in the style 4180 epoxy at near-zero moisture content. The similarity of dielectric constant and loss tangent in samples prior to absorption and after desorption suggests that any chemical or morphological changes induced by the presence of water have not caused irreversible changes in the dielectric properties of the laminates.

Recognizing Physisorption and Chemisorption in Carbon Nanotubes Gas Sensors by Double Exponential Fitting of the Response.

PubMed

Calvi, Andrea; Ferrari, Alberto; Sbuelz, Luca; Goldoni, Andrea; Modesti, Silvio

2016-05-19

Multi-walled carbon nanotubes (CNTs) have been grown in situ on a SiO 2 substrate and used as gas sensors. For this purpose, the voltage response of the CNTs as a function of time has been used to detect H 2 and CO 2 at various concentrations by supplying a constant current to the system. The analysis of both adsorptions and desorptions curves has revealed two different exponential behaviours for each curve. The study of the characteristic times, obtained from the fitting of the data, has allowed us to identify separately chemisorption and physisorption processes on the CNTs.

Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids.

PubMed

Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

2015-10-01

Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater-bentonite-fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L(-1)) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10(-10) M (241)Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k(f)) of 0.01-0.02 h(-1). Am recoveries in each column were 55-60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h(-1) in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because of the ability of the fracture materials to rapidly strip Am from the bentonite colloids and the apparent lack of a strong binding site that would keep a fraction of the Am strongly-associated with the colloids. Published by Elsevier Ltd.

Effects of relative humidity on chloroacetanilide and dinitroaniline herbicide desorption from agricultural PM2.5 on quartz fiber filters.

PubMed

Yang, Wenli; Holmén, Britt A

2007-06-01

This study quantified the release of seven relatively polar preemergence herbicides to the gas phase from soil-generated PM2.5-loaded quartz fiber filters (QFFs) and bare QFF as a function of relative humidity (RH). A 48-hour desorption fraction, F48, was defined to evaluate the relative desorption behavior of herbicides from two families, chloroacetanilide (alachlor, butachlor, metolachlor, and propachlor) and dinitroaniline (pendimethalin, prodiamine, and trifluralin) using temperature- (8 degrees C) and humidity- (10-64% RH) controlled air at a flow rate of 4 L/min. With increasing RH, an increase in F48 by a factor of 2-8 was observed for all herbicides, except metolachlor and butachlor, which showed significantly strong sorption to both sorbents. The conjugate carbonyl oxygen and amide nitrogen in the chloroacetanilide structure enables stronger specific interactions with the sorbents, leading to lower desorption compared to the dinitroaniline herbicides. Desorption of chloroacetanilides decreased in the order propachlor > alachlor > metolachlor approximately butachlor, and desorption of dinitroanilines decreased in the order trifluralin > pendimethalin > prodiamine. These orders are consistent with the different substituents in the herbicide molecules for each family and their relative tendencies to coordinate with surface moieties as indicated by electron-donating capacity. Henry's law constant and Abraham's H-acceptor parameter were found to be useful empirical parameters for describing the F48 desorption behavior for all seven herbicides.

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

NASA Astrophysics Data System (ADS)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

NASA Astrophysics Data System (ADS)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

Colloid-Facilitated Transport of 137Cs in Fracture-Fill Material. Experiments and Modeling

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

Dittrich, Timothy M.; Reimus, Paul William

2015-10-29

In this study, we demonstrate how a combination of batch sorption/desorption experiments and column transport experiments were used to effectively parameterize a model describing the colloid-facilitated transport of Cs in the Grimsel granodiorite/FFM system. Cs partition coefficient estimates onto both the colloids and the stationary media obtained from the batch experiments were used as initial estimates of partition coefficients in the column experiments, and then the column experiment results were used to obtain refined estimates of the number of different sorption sites and the adsorption and desorption rate constants of the sites. The desorption portion of the column breakthrough curvesmore » highlighted the importance of accounting for adsorption-desorption hysteresis (or a very nonlinear adsorption isotherm) of the Cs on the FFM in the model, and this portion of the breakthrough curves also dictated that there be at least two different types of sorption sites on the FFM. In the end, the two-site model parameters estimated from the column experiments provided excellent matches to the batch adsorption/desorption data, which provided a measure of assurance in the validity of the model.« less

Matrix-Assisted Laser Desorption Ionization–Time of Flight (MALDI-TOF) Mass Spectrometry for Detection of Antibiotic Resistance Mechanisms: from Research to Routine Diagnosis

PubMed Central

Chudáčková, Eva; Walková, Radka

2013-01-01

Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) has been successfully applied as an identification procedure in clinical microbiology and has been widely used in routine laboratory practice because of its economical and diagnostic benefits. The range of applications of MALDI-TOF MS has been growing constantly, from rapid species identification to labor-intensive proteomic studies of bacterial physiology. The purpose of this review is to summarize the contribution of the studies already performed with MALDI-TOF MS concerning antibiotic resistance and to analyze future perspectives in this field. We believe that current research should continue in four main directions, including the detection of antibiotic modifications by degrading enzymes, the detection of resistance mechanism determinants through proteomic studies of multiresistant bacteria, and the analysis of modifications of target sites, such as ribosomal methylation. The quantification of antibiotics is suggested as a new approach to study influx and efflux in bacterial cells. The results of the presented studies demonstrate that MALDI-TOF MS is a relevant tool for the detection of antibiotic resistance and opens new avenues for both clinical and experimental microbiology. PMID:23297261

Effects of wind-wave disturbances on adsorption and desorption of tetracycline and sulfadimidine in water-sediment systems.

PubMed

Liao, Qianjiahua; Huang, Zheng; Li, Shu; Wang, Yi; Liu, Yuqing; Luo, Ran; Shang, Jingge

2018-05-28

Wind-wave disturbances frequently disperse sediment particles into overlying water, which facilitates the adsorption and desorption of contaminants in aquatic ecosystems. Tetracycline (TC) and sulfadimidine (SM2) are common antibiotics that are frequently found in aquatic environments. This study utilized microcosms, comprising sediment and water from Lake Taihu, China, to examine the adsorption and desorption of TC and SM2 under different wind-wave disturbances in a shallow lake environment. The adsorption experiments were conducted with three different concentrations (1, 5, 10 mg/L) of TC and SM2 in the overlying water, and two different (background and strong) wind-wave conditions for 72 h. Subsequently, four microcosms were employed in a 12-h desorption study. Analysis of adsorption progress showed that TC concentration in the overlying water decreased quickly, while SM2 remained almost constant. In the desorption experiments, SM2 released to the overlying water was an order of magnitude greater than TC. These results indicate that sediment particles strongly adsorb TC but weakly adsorb SM2. Compared to background conditions, the strong wind-wave conditions resulted in higher concentrations of TC and SM2 in sediment and facilitated their migration to deeper sediment during adsorption, correspondingly promoting greater release of TC and SM2 from sediment particles into the overlying water during desorption.

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm.

PubMed

Yu, Yun Long; Wu, Xiao Mao; Li, Shao Nan; Fang, Hua; Zhan, Hai Yan; Yu, Jing Quan

2006-06-01

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.

SORPTION KINETICS OF PAHS IN METHANOL-WATER SYSTEMS

EPA Science Inventory

The objectives of this study were to evaluate the relationships between the equilibrium sorption constant (Kp), the first-order desorption rate coefficient (k2), and the volumetric fraction of water miscible solvent (fc); and to utilize SPARC-calculated (SPARC Performs Automatic ...

Cadmium mobility in sediments and soils from a coal mining area on Tibagi River watershed: environmental risk assessment.

PubMed

Galunin, Evgeny; Ferreti, Jeferson; Zapelini, Iago; Vieira, Isadora; Ricardo Teixeira Tarley, César; Abrão, Taufik; Santos, Maria Josefa

2014-01-30

The risk of cadmium contamination in the Tibagi River watershed (Parana State, Brazil) affected by past coal mining activities was assessed through sorption-desorption modeling for sediment and soil samples. The acidic character of the samples resulted in more competition between the cadmium ions and protons, thereby influencing the cadmium sorption-desorption. The sorption isotherms were fitted to the Langmuir and Freundlich single models and to the dual-site Langmuir-Freundlich (or Sips) model. The single-site models indicated a low-energy character of sorption sites on the sample sorption sites, whereas the dual-site model explained the availability of higher-affinity and lower-affinity non-specific sites. The correlation of the sorption and desorption constants with the physicochemical and mineralogical characteristics of the samples showed that the cadmium sorption behavior was significantly affected by the pH, point of zero charge, and also by the magnesium, aluminum, calcium and manganese amounts. Besides, the desorption rate and hysteresis index suggested a high risk of cadmium mobilization along the Tibagi River basin. Copyright © 2013 Elsevier B.V. All rights reserved.

Change in desorption mechanism from pore blocking to cavitation with temperature for nitrogen in ordered silica with cagelike pores.

PubMed

Morishige, Kunimitsu; Tateishi, Masayoshi; Hirose, Fumi; Aramaki, Kenji

2006-10-24

To verify pore blocking controlled desorption in ink-bottle pores, we measured the temperature dependence of the adsorption-desorption isotherms of nitrogen on four kinds of KIT-5 samples with expanded cavities hydrothermally treated for different periods of time at 393 K. In the samples, almost spherical cavities are arranged in a face-centered cubic array and the cavities are connected through small channels. The pore size of the channels increased with an increase in the hydrothermal treatment time. At lower temperatures a steep desorption branch changed to a gradual one as the hydrothermal treatment was prolonged. For the sample hydrothermally treated only for 1 day, the rectangular hysteresis loop shrank gradually with increasing temperature while keeping its shape. The temperature dependence of the evaporation pressure observed was identical with that expected for cavitation-controlled desorption. On the other hand, for the samples hydrothermally treated for long times, the gradual desorption branch became a sharp one with increasing temperature. This strongly suggests that the desorption mechanism is altered from pore blocking to cavitation with temperature. Application of percolation theory to the pore blocking controlled desorption observed here is discussed.

Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

DOE PAGES

Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; ...

2015-07-13

Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. Themore » colloidal suspension (100 mg L –1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10 –10 M 241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k f) of 0.01–0.02 h –1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h –1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because of the ability of the fracture materials to rapidly strip Am from the bentonite colloids and the apparent lack of a strong binding site that would keep a fraction of the Am strongly-associated with the colloids.« less

Properties of Two-Variety Natural Luffa Sponge Columns as Potential Mattress Filling Materials

PubMed Central

Chen, Yuxia; Zhang, Kaiting; Yuan, Fangcheng; Zhang, Tingting; Weng, Beibei; Wu, Shanshan; Huang, Aiyue; Su, Na; Guo, Yong

2018-01-01

Luffa sponge (LS) is a resourceful material with fibro-vascular reticulated structure and extremely high porosity, which make it a potential candidate for manufacturing light mattress. In this study, two types of LS columns, namely high-density (HD) and low-density (LD) columns, were investigated as materials for filling the mattress. The results showed that the compressive strength of HD LS columns was significantly greater than that of LD LS columns. However, the densification strains of the two types of LS column were both in the range of 0.6 to 0.7. Besides, HD LS columns separately pressed to the smooth plateau region and the initial densification region exhibited a partial recovery of instant height when they were unloaded, and then both of them showed no more than 4.2% of height recovery after being allowed to rest at a constant temperature and humidity for 24 h. In contrast, when LD LS columns were compressed to the smooth plateau region, the height recovery was less than 1.62% compared to when they were pressed to the initial densification region, and that was more than 15.62%. Similar to other plant fibers used as mattress fillers, the two types of LS columns also showed good water absorption capacity—both of them could absorb water from as much as 2.07 to 3.45 times their own weight. At the same time, the two types of LS columns also showed good water desorption. The water desorption ratio of HD and LD LS columns separately reached 76.86 and 91.44%, respectively, after being let rest at a constant temperature and humidity for 13 h. PMID:29614744

Fundamental data on the desorption of pure interstellar ices

NASA Astrophysics Data System (ADS)

Brown, Wendy A.; Bolina, Amandeep S.

2007-01-01

The desorption of molecular ices from grain surfaces is important in a number of astrophysical environments including dense molecular clouds, cometary nuclei and the surfaces and atmospheres of some planets. With this in mind, we have performed a detailed investigation of the desorption of pure water, pure methanol and pure ammonia ices from a model dust-grain surface. We have used these results to determine the desorption energy, order of desorption and the pre-exponential factor for the desorption of these molecular ices from our model surface. We find good agreement between our desorption energies and those determined previously; however, our values for the desorption orders, and hence also the pre-exponential factors, are different to those reported previously. The kinetic parameters derived from our data have been used to model desorption on time-scales relevant to astrophysical processes and to calculate molecular residence times, given in terms of population half-life as a function of temperature. These results show the importance of laboratory data for the understanding of astronomical situations whereby icy mantles are warmed by nearby stars and by other dynamical events.

Determination of T-2 and HT-2 toxins from maize by direct analysis in real time - mass spectrometry (DART-MS)

USDA-ARS?s Scientific Manuscript database

Ambient desorption ionization techniques, such as laser desorption with electrospray ionization assistance (ELDI), direct analysis in real time (DART) and desorption electrospray ionization (DESI) have been developed as alternatives to traditional mass spectrometric-based methods. Such techniques al...

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

PubMed Central

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

The characteristics of phosphorus adsorption and desorption in gray desert soil of Xinjiang, China

NASA Astrophysics Data System (ADS)

Wang, B.; Sun, J. S.; Liu, H.; Ma, Y. B.

2017-07-01

The characteristics of phosphorus (P) adsorption and desorption in Xinjiang gray desert soil (0 - 200 mm) of China in the long-term fertilization condition is affected by the level of soil P content which studied through an isothermal adsorption and desorption experiments of P. The results stated that within the experimental concentration range, with the increase of the amount of outer-source phosphorus, P adsorption, desorption and desorption rate increased and adsorption rate decreased gradually in different Olsen-P levels of gray desert soil in Xinjiang, China. Olsen-P content is significantly correlated with the P adsorption saturation (DPS) of gray desert soil. The maximum adsorption capacity (Xm ) of the treatments followed an extremely significant decreasing order of CK>NPK≈NPKM>PK≈NPKS. The maximum buffer capacity (MBC) and adsorption constant (K) of the NPK treatment was much higher than NPKM, NPKS, PK and CK treatments. And, MBC value of CK treatment was extremely higher than NPKS and PK, however, the differences between NPKM and CK, NPKS and PK were not significant. The comparison between NPKM, NPKS, PK and CK treatments showed no significant difference in K value, but these four showed significantly lower than NPK treatments. The value of soil easy desorption P (RDP) of NPKS and NPKM was significantly higher than NPK and PK, and the chemical fertilizer with organic fertilizer was a best way to release the phosphorus for Xinjiang agricultural production, China.

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents.

PubMed

Fayad, Paul B; Zamyadi, Arash; Broseus, Romain; Prévost, Michèle; Sauvé, Sébastien

2013-01-01

This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens.

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor.

PubMed

Efremov, Mikhail Yu; Nealey, Paul F

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor

NASA Astrophysics Data System (ADS)

Efremov, Mikhail Yu.; Nealey, Paul F.

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

A new desorption method for removing organic solvents from activated carbon using surfactant.

PubMed

Hinoue, Mitsuo; Ishimatsu, Sumiyo; Fueta, Yukiko; Hori, Hajime

2017-03-28

A new desorption method was investigated, which does not require toxic organic solvents. Efficient desorption of organic solvents from activated carbon was achieved with an ananionic surfactant solution, focusing on its washing and emulsion action. Isopropyl alcohol (IPA) and methyl ethyl ketone (MEK) were used as test solvents. Lauryl benzene sulfonic acid sodium salt (LAS) and sodium dodecyl sulfate (SDS) were used as the surfactant. Activated carbon (100 mg) was placed in a vial and a predetermined amount of organic solvent was added. After leaving for about 24 h, a predetermined amount of the surfactant solution was added. After leaving for another 72 h, the vial was heated in an incubator at 60°C for a predetermined time. The organic vapor concentration was then determined with a frame ionization detector (FID)-gas chromatograph and the desorption efficiency was calculated. A high desorption efficiency was obtained with a 10% surfactant solution (LAS 8%, SDS 2%), 5 ml desorption solution, 60°C desorption temperature, and desorption time of over 24 h, and the desorption efficiency was 72% for IPA and 9% for MEK. Under identical conditions, the desorption efficiencies for another five organic solvents were investigated, which were 36%, 3%, 32%, 2%, and 3% for acetone, ethyl acetate, dichloromethane, toluene, and m-xylene, respectively. A combination of two anionic surfactants exhibited a relatively high desorption efficiency for IPA. For toluene, the desorption efficiency was low due to poor detergency and emulsification power.

A new desorption method for removing organic solvents from activated carbon using surfactant

PubMed Central

Hinoue, Mitsuo; Ishimatsu, Sumiyo; Fueta, Yukiko; Hori, Hajime

2017-01-01

Objectives: A new desorption method was investigated, which does not require toxic organic solvents. Efficient desorption of organic solvents from activated carbon was achieved with an ananionic surfactant solution, focusing on its washing and emulsion action. Methods: Isopropyl alcohol (IPA) and methyl ethyl ketone (MEK) were used as test solvents. Lauryl benzene sulfonic acid sodium salt (LAS) and sodium dodecyl sulfate (SDS) were used as the surfactant. Activated carbon (100 mg) was placed in a vial and a predetermined amount of organic solvent was added. After leaving for about 24 h, a predetermined amount of the surfactant solution was added. After leaving for another 72 h, the vial was heated in an incubator at 60°C for a predetermined time. The organic vapor concentration was then determined with a frame ionization detector (FID)-gas chromatograph and the desorption efficiency was calculated. Results: A high desorption efficiency was obtained with a 10% surfactant solution (LAS 8%, SDS 2%), 5 ml desorption solution, 60°C desorption temperature, and desorption time of over 24 h, and the desorption efficiency was 72% for IPA and 9% for MEK. Under identical conditions, the desorption efficiencies for another five organic solvents were investigated, which were 36%, 3%, 32%, 2%, and 3% for acetone, ethyl acetate, dichloromethane, toluene, and m-xylene, respectively. Conclusions: A combination of two anionic surfactants exhibited a relatively high desorption efficiency for IPA. For toluene, the desorption efficiency was low due to poor detergency and emulsification power. PMID:28132972

Hydrophilic interaction chromatography coupled matrix assisted laser desorption/ionization mass spectrometry for molecular analysis of organic compounds in medicines, tea, and coffee.

PubMed

Wang, Ren-Qi; Bao, Kai; Croué, Jean-Philippe; Ng, Siu Choon

2013-11-21

Natural occurring organic compounds from food, natural organic matter, as well as metabolic products have received intense attention in current chemical and biological studies. Examination of unknown compounds in complex sample matrices is hampered by the limited choices for data readout and molecular elucidation. Herein, we report a generic method of hydrophilic interaction chromatography (HILIC) coupled with matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the rapid characterization of ingredients in pharmaceutical compounds, tea, and coffee. The analytes were first fractionated using a cationic HILIC column prior to MALDI-MS analyses. It was found that the retention times of a compound arising from different samples were consistent under the same conditions. Accordingly, molecules can be readily characterized by both the mass and chromatographic retention time. The retention behaviors of acidic and basic compounds on the cationic HILIC column were found to be significantly influenced by the pH of mobile phases, whereas neutral compounds depicted a constant retention time at different pH. The general HILIC-MALDI-MS method is feasible for fast screening of naturally occurring organic compounds. A series of homologs can be determined if they have the same retention behavior. Their structural features can be elucidated by considering their mass differences and hydrophilic properties as determined by HILIC chromatogram.

Possibility of a quasi-liquid layer of As on GaAs substrate grown by MBE as observed by enhancement of Ga desorption at high As pressure

NASA Astrophysics Data System (ADS)

Asai, K.; Feng, J. M.; Vaccaro, P. O.; Fujita, K.; Ohachi, T.

2000-06-01

The As vapor pressure dependence of the Ga desorption rate during molecular beam epitaxy (MBE) growth on GaAs( n11)A ( n=1-4 hereafter) substrates was studied by photoluminescence (PL) measurements at 12 K for undoped AlGaAs/GaAs asymmetric double quantum wells (ADQWs). Reflection high energy electron diffraction (RHEED) oscillation measurements on a GaAs(100) surface were also used. Two K-cells of As solid sources (corresponding to beam equivalent pressures (BEPs) of 9.0×10 -6 and 4.5×10 -5 Torr) were used to change the As pressure rapidly. The Ga flux and substrate temperature were kept constant at 0.76 ML/s and 12 K, respectively, while the As flux changed from 7.6 (BEP 9.0×10 -6 Torr) to 32 ML/s (4.5×10 -5 Torr). With increasing As pressure, two separated PL peaks for the wide well (WW) of high index substrates were observed. This peak separation is attributed to a reduced well depth from an increasing Ga desorption rate. The energy differences of the PL peak depending on the off-angle from (111)A to (100) plane indicates an orientation-dependent Ga desorption rate. Moreover, amongst all ( n11)A and (100) planes, the Ga desorption rate was smallest from the (111)A surface. The increase of Ga desorption from the surface at high As pressures probably arose from an increasing coverage with a quasi-liquid layer (QLL).

Desorption kinetics of cesium from Fukushima soils.

PubMed

Murota, Kento; Saito, Takumi; Tanaka, Satoru

2016-03-01

Understanding the behaviors of Cs(+) in soils is crucial for evaluation of the impacts of disposal of soils contaminated by radiocesium, (137)Cs. The desorption rate of Cs(+) evaluated in relatively short periods of time may not be adequate for such a purpose. In this study, we investigated long-term desorption kinetics of (137)Cs and (133)Cs from soils collected in Fukushima Prefecture by batch desorption experiments in the presence of cation exchange resin as a sorbent. The sorbent can keep the concentration of Cs(+) in the aqueous phase low and prevent re-sorption of desorbed Cs(+). Up to 60% of (137)Cs was desorbed after 139 d in dilute KCl media, which was larger than the desorption by conventional short-term extraction with 1 M ammonium acetate. Desorption of (137)Cs continued even after this period. It was also found that high concentration of K(+) prevented desorption of Cs(+) in the initial stage of desorption, but the effect was alleviated with time. The desorbed fraction of stable Cs was smaller than that of (137)Cs. This indicated that (137)Cs may gradually move to more stable states in soils. The half-life of (137)Cs desorption from the slowest sorption site was estimated to be at least two years by a three-site desorption model. Copyright © 2015 Elsevier Ltd. All rights reserved.

Desorption of isopropyl alcohol from adsorbent with non-thermal plasma.

PubMed

Shiau, Chen Han; Pan, Kuan Lun; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

2017-09-01

Effective desorption of isopropyl alcohol (IPA) from adsorbents with non-thermal plasma is developed. In this system, IPA is effectively adsorbed with activated carbon while dielectric barrier discharge is applied to replace the conventional thermal desorption process to achieve good desorption efficiency, making the treatment equipment smaller in size. Various adsorbents including molecular sieves and activated carbon are evaluated for IPA adsorption capacity. The results indicate that BAC has the highest IPA adsorption capacity (280.31 mg IPA/g) under the operating conditions of room temperature, IPA of 400 ppm, and residence time of 0.283 s among 5 adsorbents tested. For the plasma desorption process, the IPA selectivity of 89% is achieved with BAC as N 2 is used as desorbing gas. In addition, as air or O 2 is used as desorbing gas, the IPA desorption concentration is reduced, because air and O 2 plasmas generate active species to oxidize IPA to form acetone, CO 2 , and even CO. Furthermore, the results of the durability test indicate that the amount of IPA desorbed increases with increasing desorption times and plasma desorption process has a higher energy efficiency if compared with thermal desorption. Overall, this study indicates that non-thermal plasma is a viable process for removing VOCs to regenerate adsorbent.

In-situ regeneration of activated carbon with electric potential swing desorption (EPSD) for the H2S removal from biogas.

PubMed

Farooq, M; Almustapha, M N; Imran, M; Saeed, M A; Andresen, John M

2018-02-01

In-situ regeneration of a granular activated carbon was conducted for the first time using electric potential swing desorption (EPSD) with potentials up to 30 V. The EPSD system was compared against a standard non-potential system using a fixed-bed reactor with a bed of 10 g of activated carbon treating a gas mixture with 10,000 ppm H 2 S. Breakthrough times, adsorption desorption volume, capacities, effect of regeneration and desorption kinetics were investigated. The analysis showed that desorption of H 2 S using the new EPSD system was 3 times quicker compared with the no potential system. Hence, physical adsorption using EPSD over activated carbon is efficient, safe and environmental friendly and could be used for the in-situ regeneration of granular activated carbon without using a PSA and/or TSA system. Additionally, adsorption and desorption cycles can be obtained with a classical two column system, which could lead towards a more efficient and economic biogas to biomethane process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of delorazepam in urine by solid-phase microextraction coupled to high performance liquid chromatography.

PubMed

Aresta, Antonella; Monaci, Linda; Zambonin, Carlo Giorgio

2002-06-01

An SPME-HPLC-UV method for the determination of delorazepam, a representative benzodiazepine, in spiked human urine samples was developed for the first time. The performances of two commercially available fibers, a carbowax/templated resin (Carbowax/TPR-100) and a polydimethylsiloxane/divinylbenzene (PDMS/DVB), were compared, indicating the latter as the most suitable for urine samples analysis. All the aspects influencing adsorption (extraction time, pH, temperature, salt addition) and desorption (desorption and injection time, desorption solvent mixture composition) of the analyte on the fiber have been investigated. In particular, short extraction times were necessary to reach the equilibrium and very short desorption times were employed. The procedure required simple sample pre-treatment and was able to detect 5 ng/ml in spiked urine, regardless of the complexity of the matrix.

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

Podlivaev, A. I., E-mail: AIPodlivayev@mephi.ru; Openov, L. A.

The initial stage of hydrogen desorption from fully hydrogenated carbon nanotubes (3.0) and (2.2) is numerically studied by the molecular dynamics method. The temperature dependence of the desorption rate is directly determined at T = 1800–2500 K. The characteristic desorption times are determined at temperatures outside this range by extrapolation. It is shown that hydrogen desorption leads to the appearance of electronic states in the band gap.

Experimental studies and physically substantiated model of carbon dioxide emission from the exposed cultural layer of Velikii Novgorod

NASA Astrophysics Data System (ADS)

Smagin, A. V.; Dolgikh, A. V.; Karelin, D. V.

2016-04-01

The results of quantitative assessment and modeling of carbon dioxide emission from urban pedolithosediments (cultural layer) in the central part of Velikii Novgorod are discussed. At the first stages after the exposure of the cultural layer to the surface in archaeological excavations, very high CO2 emission values reaching 10-15 g C/(m2 h) have been determined. These values exceed the normal equilibrium emission from the soil surface by two orders of magnitude. However, they should not be interpreted as indications of the high biological activity of the buried urban sediments. A model based on physical processes shows that the measured emission values can be reliably explained by degassing of the soil water and desorption of gases from the urban sediments. This model suggests the diffusion mechanism of the transfer of carbon dioxide from the cultural layer into the atmosphere; in addition, it includes the equations to describe nonequilibrium interphase interactions (sorption-desorption and dissolution-degassing of CO2) with the first-order kinetics. With the use of statistically reliable data on physical parameters—the effective diffusion coefficient as dependent on the aeration porosity, the effective solubility, the Henry constant for the CO2 sorption, and the kinetic constants of the CO2 desorption and degassing of the soil solution—this model reproduces the experimental data on the dynamics of CO2 emission from the surface of the exposed cultural layer obtained by the static chamber method.

Photon-induced Processing of Interstellar Ices in the Laboratory. Focus on Their Non-thermal Desorption.

NASA Astrophysics Data System (ADS)

Martin-Domenech, Rafael; Munoz Caro, Guillermo; Cruz-Diaz, Gustavo A.; Oberg, Karin I.

2018-06-01

Some of the processes that take place in the interstellar medium (ISM)can be simulated in laboratories on Earth under astrophysically relevant conditions. For example, the energetic processing of the ice mantles that accrete on top of dust grains in the coldest regions of the ISM, leading to the production of new species and their desorption to the gas phase. In particular, observation of complex organic molecules (COMs) in cold interstellar environments stress the need for not only a solid state formation but also for non-thermal desorption mechanisms that can account for the observed abundances in regions where thermal desorption is inhibited. Laboratory Astrophysics can be used to test different non-thermal desorption processes and extract yields than can be extrapolated to the astrophysical scenario with theoretical models. 0th generation COMs like CH3OH and H2CO can be formed at very low temperatures. In this talk, we present laboratory simulations of the UV photoprocessing of a binary ice mixture composed by water (the main component of astrophysical ices) and methane. Formation of CO, CO2, CH3OH and H2CO was confirmed by IR spectroscopy and subsequent TPD. At the same time, photodesorption of CO and H2CO was detected by means of a Quadrupole Mass Spectrometer, with yields on the order of 10-4 and 10-5 molecules per incident photon, respectively. In general, photodesorption can take place through a direct mechanism, where the absorbing molecule (or its photofragments) are desorbed; or through an indirect mechanism where the absorbed energy is transferred to a surface molecule which is the one finally desorbing. In the case of photoproducts, the evolution of the photodesorption yield gives information on the photodesorption mechanism: a constant photodesorption yield is observed when the photoproducts are desorbed right after their formation; while an increasing yield is measured when the photoproducts are desorbed later after energy transfer from another absorbing molecule, allowing to roughly distinguish between different mechanisms.

Influence of low oxygen tensions and sorption to sediment black carbon on biodegradation of pyrene.

PubMed

Ortega-Calvo, José-Julio; Gschwend, Philip M

2010-07-01

Sorption to sediment black carbon (BC) may limit the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in resuspension events and intact sediment beds. We examined this hypothesis experimentally under conditions that were realistic in terms of oxygen concentrations and BC content. A new method, based on synchronous fluorescence observations of (14)C-pyrene, was developed for continuously measuring the uptake of dissolved pyrene by Mycobacterium gilvum VM552, a representative degrader of PAHs. The effect of oxygen and pyrene concentrations on pyrene uptake followed Michaelis-Menten kinetics, resulting in a dissolved oxygen half-saturation constant (K(om)) of 14.1 microM and a dissolved pyrene half-saturation constant (K(pm)) of 6 nM. The fluorescence of (14)C-pyrene in air-saturated suspensions of sediments and induced cells followed time courses that reflected simultaneous desorption and biodegradation of pyrene, ultimately causing a quasi-steady-state concentration of dissolved pyrene balancing desorptive inputs and biodegradation removals. The increasing concentrations of (14)CO(2) in these suspensions, as determined with liquid scintillation, evidenced the strong impact of sorption to BC-rich sediments on the biodegradation rate. Using the best-fit parameter values, we integrated oxygen and sorption effects and showed that oxygen tensions far below saturation levels in water are sufficient to enable significant decreases in the steady-state concentrations of aqueous-phase pyrene. These findings may be relevant for bioaccumulation scenarios that consider the effect of sediment resuspension events on exposure to water column and sediment pore water, as well as the direct uptake of PAHs from sediments.

Collective degrees of freedom involved in absorption and desorption of surfactant molecules in spherical non-ionic micelles

NASA Astrophysics Data System (ADS)

Ahn, Yong Nam; Mohan, Gunjan; Kopelevich, Dmitry I.

2012-10-01

Dynamics of absorption and desorption of a surfactant monomer into and out of a spherical non-ionic micelle is investigated by coarse-grained molecular dynamics (MD) simulations. It is shown that these processes involve a complex interplay between the micellar structure and the monomer configuration. A quantitative model for collective dynamics of these degrees of freedom is developed. This is accomplished by reconstructing a multi-dimensional free energy landscape of the surfactant-micelle system using constrained MD simulations in which the distance between the micellar and monomer centers of mass is held constant. Results of this analysis are verified by direct (unconstrained) MD simulations of surfactant absorption in the micelle. It is demonstrated that the system dynamics is likely to deviate from the minimum energy path on the energy landscape. These deviations create an energy barrier for the monomer absorption and increase an existing barrier for the monomer desorption. A reduced Fokker-Planck equation is proposed to model these effects.

Effect of Vaporizer Temperature on Ambient Non-Refractory Submicron Aerosol Composition and Mass Spectra Measured by the Aerosol Mass Spectrometer

EPA Science Inventory

Aerodyne Aerosol Mass Spectrometers (AMS) are routinely operated with a constant vaporizer temperature (Tvap) of 600^oC in order to facilitate quantitative detection of non-refractory submicron (NR-PM1) species. By analogy with other thermal desorption instrument...

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

PubMed Central

2013-01-01

Background This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. Results The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M-1 sec-1 in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M-1 sec-1 in ultrapure water and 26 to 149 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M-1 sec-1 in ultrapure water and 180 to 368 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L-1 after contact times of 10 to 60 min. Conclusion This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens. PMID:23675917

Molecular-Scale Description of SPAN80 Desorption from a Squalane-Water Interface.

PubMed

Tan, L; Pratt, L R; Chaudhari, M I

2018-04-05

Extensive all-atom molecular dynamics calculations on the water-squalane interface for nine different loadings with sorbitan monooleate (SPAN80), at T = 300 K, are analyzed for the surface tension equation of state, desorption free-energy profiles as they depend on loading, and to evaluate escape times for adsorbed SPAN80 into the bulk phases. These results suggest that loading only weakly affects accommodation of a SPAN80 molecule by this squalane-water interface. Specifically, the surface tension equation of state is simple through the range of high tension to high loading studied, and the desorption free-energy profiles are weakly dependent on loading here. The perpendicular motion of the centroid of the SPAN80 headgroup ring is well-described by a diffusional model near the minimum of the desorption free-energy profile. Lateral diffusional motion is weakly dependent on loading. Escape times evaluated on the basis of a diffusional model and the desorption free energies are 7 × 10 -2 s (into the squalane) and 3 × 10 2 h (into the water). The latter value is consistent with desorption times of related lab-scale experimental work.

Adsorption and desorption characteristics of endosulfan in two typical agricultural soils in Southwest China.

PubMed

Qian, Sheng; Zhu, Heng; Xiong, Bailian; Zheng, Guocan; Zhang, Jinzhong; Xu, Weihong

2017-04-01

Endosulfan is an organochlorine pesticide widely used in Southwest China. In this paper, the adsorption and desorption characteristics of endosulfan in two typical agricultural soils (latosol and lateritic red soil) in this area were studied. The results showed that Langmuir isothermal equation could well describe the adsorption thermodynamic characteristics of endosulfan in latosol and lateritic red soil, and the maximum adsorption capacities of α-endosulfan were 0.186 and 0.209 mg/g, while those of β-endosulfan were 0.140 and 0.148 mg/g, respectively. Endosulfan adsorption in the two soils was an exothermic physicochemical process, but dominated by physical process. The adsorption kinetic characteristics of endosulfan in the two soils could be well described by second-order kinetic equation, and the initial rate constants were 0.228 and 0.325 mg/(g min) for α-endosulfan, while those were 0.119 and 0.125 mg/(g min) for β-endosulfan, respectively. The adsorbed endosulfan in the two soils was difficult to be desorbed into the liquid phase, and showed weak desorption hysteresis. These results implied that endosulfan could be firmly adsorbed by the two soils, and their adsorption and desorption abilities may be related to the contents of soil clay and organic matter.

Nitrogen vacancy complexes in nitrogen irradiated metals

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

Veen, A. van; Westerduin, K.T.; Schut, H.

1996-12-31

Gas desorption and positron annihilation techniques have been employed to study the evolution of nitrogen associated defects in nitrogen irradiated metals: Fe, Ni, Mo and W. Nitrogen in these metals has a rather high affinity to vacancy type defects. The results obtained for low irradiation dose show that substitutional nitrogen (NV; with V = vacancy) is formed. The nitrogen vacancy complex dissociates at temperatures ranging from 350 K for Ni to 900 K for Mo and 1,100 K for W. At high doses defects are formed which can be characterized as nitrogen saturated vacancy clusters. These defect, as observed bymore » helium probing, disappear during annealing for nickel at 800 K, and for Mo at 1,100 K. The direct observation of the desorbing nitrogen for nickel and molybdenum reveals a very fast desorption transient at the dissociation temperature of the clusters. This is the characteristic desorption transient of a small nitride cluster, e.g., by shrinkage with constant rate. For iron the nitrogen desorption is more complicated because of a general background that continuously rises with temperature. With the positron beam technique depth information was obtained for defects in iron and the defect character could be established with the help of the information provided on annihilation with conduction and core electrons of the defect trapped positrons.« less

Near-equilibrium desorption of helium films

NASA Astrophysics Data System (ADS)

Weimer, M.; Housley, R. M.; Goodstein, D. L.

1987-10-01

The thermal desorption of helium films in the presence of their equilibrium vapor is studied experimentally for small but rapid departures from ambient temperature. The results are analyzed within the framework of a quasithermodynamic phenomenological model based on detailed balance. Under the usual experimental conditions, isothermal desorption at the temperature of the substrate is a general prediction of the model which seems to be substantiated. For realistic adsorption isotherms the time evolution of the net desorption flux nevertheless appears to be governed by a highly nonlinear equation. In such circumstances, a number of characteristic relaxation times may be identified. These time scales are distinct from, and in general unrelated to, the coverage-dependent mean lifetime of an atom on the surface. To characterize the overall nonlinear evolution towards steady state, a global time scale, defined in terms of both initial- and steady-state properties, is introduced to summarize the experimental data. Internal evidence suggests a criterion for judging when collisions among desorbed atoms are unimportant. When this condition is satisfied, data for near-equilibrium desorption agree well with the predictions of the model. Combining our results with earlier data at higher substrate temperatures and different ambient conditions, the overall picture is consistent with scaling properties implied by the theory. We show that the values of the parameters deduced from a Frenkel-Arrhenius parametrization of the global relaxation times, as well as a variety of other aspects of desorption kinetics, are actually consequences of the shape of the equilibrium adsorption isotherm.

A model for the catalytic reduction of NO with CO and N desorption

NASA Astrophysics Data System (ADS)

Díaz, J. J.; Buendía, G. M.

2018-02-01

In this work we have investigated by Monte Carlo simulations the dynamical behavior of a modified Yaldram-Khan (YK) model for the catalytic reduction of NO on a surface. Our model is simulated on a square lattice and includes the individual desorption of CO molecules and N atoms, processes associated with temperature effects. When CO desorption is added, strong fluctuations appear, which are associated with the spreading of N checkerboard structures on the surface. These structures take a long time to coalesce, allowing the existence of a unsteady but long lasting reactive state. N desorption also favors the reactivity of the system, this time by diminishing the size of the N structures and impeding their coalescence. The combined desorption of CO and N produces a reactive state as well, where reactive zones among N structures can take place on the surface.

Development and Characterization of a Laser-Induced Acoustic Desorption Source.

PubMed

Huang, Zhipeng; Ossenbrüggen, Tim; Rubinsky, Igor; Schust, Matthias; Horke, Daniel A; Küpper, Jochen

2018-03-20

A laser-induced acoustic desorption source, developed for use at central facilities, such as free-electron lasers, is presented. It features prolonged measurement times and a fixed interaction point. A novel sample deposition method using aerosol spraying provides a uniform sample coverage and hence stable signal intensity. Utilizing strong-field ionization as a universal detection scheme, the produced molecular plume is characterized in terms of number density, spatial extend, fragmentation, temporal distribution, translational velocity, and translational temperature. The effect of desorption laser intensity on these plume properties is evaluated. While translational velocity is invariant for different desorption laser intensities, pointing to a nonthermal desorption mechanism, the translational temperature increases significantly and higher fragmentation is observed with increased desorption laser fluence.

Intensification of ion exchange desorption of thiamine diphosphate by low-powered ultrasound.

PubMed

Pinchukova, Natalia A; Voloshko, Alexander Y; Merko, Maria A; Bondarenko, Yana A; Chebanov, Valentin A

2018-03-01

The process of ultrasound-assisted ion-exchange desorption of cocarboxylase (thiamine diphosphate (TDP)) from a strong acidic cation resin was studied. Kinetics studies revealed that ultrasound accelerates TDP desorption by 3 times. The optimal desorption parameters, viz. US power input, sonication time, eluent/resin ratio and the eluent (ammonium acetate buffer) concentration were established which were 15mW/cm 3 , 20min, 1:1 and 1M, respectively. The resin stability studies showed that the optimal ultrasonic power was less by the order than the resin degradation threshold which ensures durable and efficient resin exploitation during production. The resin sorption capacity remained unchanged even after 20 cycles of TDP sorption, ultrasonic desorption and resin regeneration. The recovery ratio of TDP was shown to increase non-linearly with decreasing the resin saturation factor, which can be attributed to diffusion limitations occurring during desorption. The optimal resin loading corresponding to more than 90 per cent of TDP recovery was found to be at the level of 10 per cent of the maximal sorption capacity. The study revealed 4-5-fold increase in concentrations of the recovered solutions, which together with process times shortening should result in considerable energy saving in downstream operations on production scale. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption and Desorption of Nickel(II) Ions from Aqueous Solution by a Lignocellulose/Montmorillonite Nanocomposite

PubMed Central

Zhang, Xiaotao; Wang, Ximing

2015-01-01

A new and inexpensive lignocellulose/montmorillonite (LNC/MMT) nanocomposite was prepared by a chemical intercalation of LNC into MMT and was subsequently investigated as an adsorbent in batch systems for the adsorption-desorption of Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the LNC/MMT nanocomposite were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and time. The results indicated that the maximum adsorption capacity of Ni(II) reached 94.86 mg/g at an initial Ni(II) concentration of 0.0032 mol/L, a solution pH of 6.8, an adsorption temperature of 70°C, and adsorption time of 40 min. The represented adsorption kinetics model exhibited good agreement between the experimental data and the pseudo-second-order kinetic model. The Langmuir isotherm equation best fit the experimental data. The structure of the LNC/MMT nanocomposite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), whereas the adsorption mechanism was discussed in combination with the results obtained from scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy analyses (FTIR). The desorption capacity of the LNC/MMT nanocomposite depended on parameters such as HNO3 concentration, desorption temperature, and desorption time. The satisfactory desorption capacity of 81.34 mg/g was obtained at a HNO3 concentration, desorption temperature, and desorption time of 0.2 mol/L, 60 ºC, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of the LNC/MMT nanocomposite was consistent for five cycles without any appreciable loss in the batch process and confirmed that the LNC/MMT nanocomposite was reusable. The overall study revealed that the LNC/MMT nanocomposite functioned as an effective adsorbent in the detoxification of Ni(II)-contaminated wastewater. PMID:25647398

A soil-column gas chromatography (SCGC) approach to explore the thermal desorption behavior of hydrocarbons from soils.

PubMed

Yu, Ying; Liu, Liang; Shao, Ziying; Ju, Tianyu; Sun, Bing; Benadda, Belkacem

2016-01-01

A soil-column gas chromatography approach was developed to simulate the mass transfer process of hydrocarbons between gas and soil during thermally enhanced soil vapor extraction (T-SVE). Four kinds of hydrocarbons-methylbenzene, n-hexane, n-decane, and n-tetradecane-were flowed by nitrogen gas. The retention factor k' and the tailing factor T f were calculated to reflect the desorption velocities of fast and slow desorption fractions, respectively. The results clearly indicated two different mechanisms on the thermal desorption behaviors of fast and slow desorption fractions. The desorption velocity of fast desorption fraction was an exponential function of the reciprocal of soil absolute temperature and inversely correlated with hydrocarbon's boiling point, whereas the desorption velocity of slow desorption fraction was an inverse proportional function of soil absolute temperature, and inversely proportional to the log K OW value of the hydrocarbons. The higher activation energy of adsorption was found on loamy soil with higher organic content. The increase of carrier gas flow rate led to a reduction in the apparent activation energy of adsorption of slow desorption fraction, and thus desorption efficiency was significantly enhanced. The obtained results are of practical interest for the design of high-efficiency T-SVE system and may be used to predict the remediation time.

The role of electronic mechanisms in surface erosion and glow phenomena

NASA Technical Reports Server (NTRS)

Haglund, Richard F., Jr.

1987-01-01

Experimental studies of desorption induced by electronic transitions (DIET) are described. Such studies are producing an increasingly complete picture of the dynamical pathways through which incident electronic energy is absorbed and rechanneled to produce macroscopic erosion and glow. These mechanistic studies can determine rate constants for erosion and glow processes in model materials and provide valuable guidance in materials selection and development. Extensive experiments with electron, photon, and heavy particle irradiation of alkali halides and other simple model materials have produced evidence showing that: (1) surface erosion, consisting primarily in the ejection or desorption of ground-state neutral atoms, occurs with large efficiencies for all irradiated species; (2) surface glow, resulting from the radiative decay of desorbed atoms, likewise occurs for all irradiating species; (3) the typical mechanism for ground-state neutral desorption is exciton formation, followed by relaxation to a permanent, mobile electronic defect which is the precursor to bond-breaking in the surface or near-surface bulk of the material; and (4) the mechanisms for excited atom formation may include curve crossing in atomic collisions, interactions with surface defect or impurity states, or defect diffusion.

Studies on desorption and regeneration of natural pumice for iron removal from aqueous solution.

PubMed

Indah, S; Helard, D; Binuwara, A

2018-05-01

To make the adsorption process more economic and environmental friendly, it is necessary to study desorption and reutilization of the adsorbents. In the present study, the effectiveness of natural pumice in removal of iron from aqueous solution was investigated in several sorption-desorption cycles. The desorption characteristics of previously adsorbed iron ions on natural pumice were tested by various desorbing agents such as HCl, NaOH and aquadest. Among them, HCl showed the highest desorption efficiency (37.89%) with 0.1 M of concentration and 60 min of contact time. The removal efficiency of iron ions in reused natural pumice could be maintained up to 90% in the third cycle of adsorption. The results indicate that although complete desorption was not achieved, natural pumice from Sungai Pasak, West Sumatra, Indonesia, can be sufficiently reused up to three cycles of adsorption-desorption.

Mesoporous aluminium organophosphonates: a reusable chemsensor for the detection of explosives

NASA Astrophysics Data System (ADS)

Li, Dongdong; Yu, Xiang

2016-07-01

Rapid and sensitive detection of explosives is in high demand for homeland security and public safety. In this work, electron-rich of anthracene functionalized mesoporous aluminium organophosphonates (En-AlPs) were synthesized by a one-pot condensation process. The mesoporous structure and strong blue emission of En-AlPs were confirmed by the N2 adsorption-desorption isotherms, transmission electron microscopy images and fluorescence spectra. The materials En-AlPs can serve as sensitive chemosensors for various electron deficient nitroderivatives, with the quenching constant and the detection limit up to 1.5×106 M-1 and 0.3 ppm in water solution. More importantly, the materials can be recycled for many times by simply washed with ethanol, showing potential applications in explosives detection.

Laser desorption with corona discharge ion mobility spectrometry for direct surface detection of explosives.

PubMed

Sabo, M; Malásková, M; Matejčík, S

2014-10-21

We present a new highly sensitive technique for the detection of explosives directly from the surface using laser desorption-corona discharge-ion mobility spectrometry (LD-CD-IMS). We have developed LD based on laser diode modules (LDM) and the technique was tested using three different LDM (445, 532 and 665 nm). The explosives were detected directly from the surface without any further preparation. We discuss the mechanism of the LD and the limitations of this technique such as desorption time, transport time and desorption area. After the evaluation of experimental data, we estimated the potential limits of detection of this method to be 0.6 pg for TNT, 2.8 pg for RDX and 8.4 pg for PETN.

Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Yalcin, Talat; Li, Liang

2009-12-01

Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.

Characterisation of organometallic and coordination compounds by solvent-free matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

PubMed

Wyatt, Mark F; Stein, Bridget K; Brenton, A Gareth

2008-01-01

Insoluble or low solubility organometallic and coordination compounds have been characterised by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry, with solvent-free sample preparation being the key step toward successful analysis.

Oxygen sorption and desorption properties of selected lanthanum manganites and lanthanum ferrite manganites.

PubMed

Nielsen, Jimmi; Skou, Eivind M; Jacobsen, Torben

2015-06-08

Temperature-programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid-oxide fuel cell (SOFC) cathode materials (La(0.85) Sr(0.15)0.95 MnO(3+δ) (LSM) and La(0.60) Sr(0.40) Fe(0.80) Mn(0.20) O(3-δ) (LSFM). The powders were characterized by X-ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second-order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate-determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re-adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling Organic Contaminant Desorption from Municipal Solid Waste Components

NASA Astrophysics Data System (ADS)

Knappe, D. R.; Wu, B.; Barlaz, M. A.

2002-12-01

Approximately 25% of the sites on the National Priority List (NPL) of Superfund are municipal landfills that accepted hazardous waste. Unlined landfills typically result in groundwater contamination, and priority pollutants such as alkylbenzenes are often present. To select cost-effective risk management alternatives, better information on factors controlling the fate of hydrophobic organic contaminants (HOCs) in landfills is required. The objectives of this study were (1) to investigate the effects of HOC aging time, anaerobic sorbent decomposition, and leachate composition on HOC desorption rates, and (2) to simulate HOC desorption rates from polymers and biopolymer composites with suitable diffusion models. Experiments were conducted with individual components of municipal solid waste (MSW) including polyvinyl chloride (PVC), high-density polyethylene (HDPE), newsprint, office paper, and model food and yard waste (rabbit food). Each of the biopolymer composites (office paper, newsprint, rabbit food) was tested in both fresh and anaerobically decomposed form. To determine the effects of aging on alkylbenzene desorption rates, batch desorption tests were performed after sorbents were exposed to toluene for 30 and 250 days in flame-sealed ampules. Desorption tests showed that alkylbenzene desorption rates varied greatly among MSW components (PVC slowest, fresh rabbit food and newsprint fastest). Furthermore, desorption rates decreased as aging time increased. A single-parameter polymer diffusion model successfully described PVC and HDPE desorption data, but it failed to simulate desorption rate data for biopolymer composites. For biopolymer composites, a three-parameter biphasic polymer diffusion model was employed, which successfully simulated both the initial rapid and the subsequent slow desorption of toluene. Toluene desorption rates from MSW mixtures were predicted for typical MSW compositions in the years 1960 and 1997. For the older MSW mixture, which had a low plastics content, the model predicted that 50% of the initially sorbed toluene desorbed over a period of 5.8 days. In contrast, the model predicted that 50% of the initially sorbed toluene desorbed over a period of 4 years for the newer MSW mixture. These results suggest that toluene desorption rates from old MSW mixtures exceed methanogenic toluene degradation rates (toluene half-lives of about 30 to 100 days have been reported for methanogenic systems) and thus imply that biodegradation kinetics control the rate at which sorbed toluene is mineralized in old landfills. For newer MSW mixtures with a larger plastics content, toluene desorption rates are substantially slower; therefore, toluene desorption kinetics likely control the rate at which sorbed toluene can be mineralized in new landfills.

Dynamic Monte Carlo description of thermal desorption processes

NASA Astrophysics Data System (ADS)

Weinketz, Sieghard

1994-07-01

The applicability of the dynamic Monte Carlo method of Fichthorn and Weinberg, in which the time evolution of a system is described in terms of the absolute number of different microscopic possible events and their associated transition rates, is discussed for the case of thermal desorption simulations. It is shown that the definition of the time increment at each successful event leads naturally to the macroscopic differential equation of desorption, in the case of simple first- and second-order processes in which the only possible events are desorption and diffusion. This equivalence is numerically demonstrated for a second-order case. In the sequence, the equivalence of this method with the Monte Carlo method of Sales and Zgrablich for more complex desorption processes, allowing for lateral interactions between adsorbates, is shown, even though the dynamic Monte Carlo method does not bear their limitation of a rapid surface diffusion condition, thus being able to describe a more complex ``kinetics'' of surface reactive processes, and therefore be applied to a wider class of phenomena, such as surface catalysis.

GC-MS determination of parabens, triclosan and methyl triclosan in water by in situ derivatisation and stir-bar sorptive extraction.

PubMed

Casas Ferreira, Ana María; Möder, Monika; Fernández Laespada, María Esther

2011-01-01

Stir-bar sorptive extraction in combination with an in situ derivatisation reaction and thermal desorption-gas chromatography-mass spectrometry was successfully applied to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in water samples. This approach improves both the extraction efficiency and the sensitivity in the GC in a simple way since the derivatisation reaction occurs at the same time as the extraction procedure. The in situ derivatisation reaction was carried out with acetic anhydride under alkaline conditions. Thermal desorption parameters (cryofocusing temperature, desorption flow, desorption time, desorption temperature) were optimised using a Box-Behnken experimental design. All the analytes gave recoveries higher than 79%, except methylparaben (22%). The method afforded detection limits between 0.64 and 4.12 ng/L, with good reproducibility and accuracy values. The feasibility of the method for the determination of analytes in water samples was checked in tap water and untreated and treated wastewater.

Relaxation times measurement in single and multiply excited xenon clusters

NASA Astrophysics Data System (ADS)

Serdobintsev, P. Yu.; Melnikov, A. S.; Pastor, A. A.; Timofeev, N. A.; Khodorkovskiy, M. A.

2018-05-01

Direct measurement of the rates of nonradiative relaxation processes in electronically excited xenon clusters was carried out. The clusters were created in a pulsed supersonic beam and two-photon excited by femtosecond laser pulses with a wavelength of 263 nm. The measurements were performed using the pump-probe method and electron spectroscopy. It is shown that relaxation of light clusters XeN (N < 15) predominantly occurs by desorption of excited xenon atoms with a characteristic time constant of 3 ps. Heavier electronically excited clusters (N > 10) vibrationally relax to the lowest electronically excited state at a rate of about 0.075 eV/ps. Multiply excited clusters are deactivated via energy exchange between excited centers with the ionization of one of them. The production of electrons in this process occurs with a delay of ˜4 ps from the pump pulse, and the process is completed in 10 ps.

Time and temperature dependent adsorption-desorption behaviour of pretilachlor in soil.

PubMed

Kaur, Paawan; Kaur, Pervinder

2018-06-04

Understanding and quantifying the adsorption-desorption behaviour of herbicide in soil is imperative for predicting their fate and transport in the environment. In the present study, the effect of time and temperature on the adsorption-desorption behaviour of pretilachlor in soils was investigated using batch equilibration technique. The adsorption-desorption kinetics of pretilachlor in soils was two step process and was well described by pseudo-second-order kinetic model. Freundlich model accurately predicted the sorption behaviour of pretilachlor. The adsorption-desorption of pretilachlor varied significantly with the concentration, temperature and properties of soil viz. organic matter and clay content. All the studied soils had non-linear slopes (n < 1) and degree of nonlinearity increased with increase in clay, organic matter content and temperature (p < 0.05). Desorption of pretilachlor was hysteretic in studied soils and hysteresis coefficient varied from 0.023 to 0.275. Thermodynamic analysis showed that pretilachlor adsorption onto soils was a feasible, spontaneous and endothermic process which becomes more favourable at high temperature. It could be inferred that the adsorption of pretilachlor on soils was physical in nature. Copyright © 2018 Elsevier Inc. All rights reserved.

Characteristics of SnO2-based 68Ge/68Ga generator and aspects of radiolabelling DOTA-peptides.

PubMed

de Blois, Erik; Sze Chan, Ho; Naidoo, Clive; Prince, Deidre; Krenning, Eric P; Breeman, Wouter A P

2011-02-01

PET scintigraphy with (68)Ga-labelled analogs is of increasing interest in Nuclear Medicine and performed all over the world. Here we report the characteristics of the eluate of SnO(2)-based (68)Ge/(68)Ga generators prepared by iThemba LABS (Somerset West, South Africa). Three purification and concentration techniques of the eluate for labelling DOTA-TATE and concordant SPE purifications were investigated. Characteristics of 4 SnO(2)-based generators (range 0.4-1 GBq (68)Ga in the eluate) and several concentration techniques of the eluate (HCl) were evaluated. The elution profiles of SnO(2)-based (68)Ge/(68)Ga generators were monitored, while [HCl] of the eluens was varied from 0.3-1.0 M. Metal ions and sterility of the eluate were determined by ICP. Fractionated elution and concentration of the (68)Ga eluate were performed using anion and cation exchange. Concentrated (68)Ga eluate, using all three concentration techniques, was used for labelling of DOTA-TATE. (68)Ga-DOTA-TATE-containing solution was purified and RNP increased by SPE, therefore also 11 commercially available SPE columns were investigated. The amount of elutable (68)Ga activity varies when the concentration of the eluens, HCl, was varied, while (68)Ge activity remains virtually constant. SnO(2)-based (68)Ge/(68)Ga generator elutes at 0.6 M HCl >100% of the (68)Ga activity at calibration time and ±75% after 300 days. Eluate at discharge was sterile and Endotoxins were <0.5 EU/mL, RNP was always <0.01%. Metal ions in the eluate were <10 ppm (in total). Highest desorption for anion purification was obtained with the 30 mg Oasis WAX column (>80%). Highest desorption for cation purification was obtained using a solution containing 90% acetone at increasing molarity of HCl, resulted in a (68)Ga desorption of 68±8%. With all (68)Ge/(68)Ga generators and for all 3 purification methods a SA up to 50 MBq/nmol with >95% incorporation (ITLC) and RCP (radiochemical purity) by HPLC ±90% could be achieved. Purification and concentration of the eluate with anion exchange has the benefit of more elutable (68)Ga with 1 M HCl as eluens. The additional washing step of the anion column with NaCl and ethanol, resulted in a lower and less variable [H(+)] in the eluate, and, as a result the pH in the reaction vial is better controlled, more constant, and less addition of buffer is required and concordant smaller reaction volumes. Desorption of (68)Ga-DOTA-TATE of SPE columns varied, highest desorption was obtained with Baker C(18) 100 mg (84%). Purification of (68)Ga-DOTA-TATE by SPE resulted in an RNP of <10(-4)%. Eluate of SnO(2)-based (68)Ge/(68)Ga generator, either by fractionated elution as by ion exchange can be used for labelling DOTA-peptides with (68)Ga at a SA of 50 MBq/nmol at >95% incorporation and a RCP of ±90%. SPE columns are very effective to increase RNP. Copyright © 2010 Elsevier Ltd. All rights reserved.

Nanocomposite PAAm/methyl cellulose/montmorillonite hydrogel: evidence of synergistic effects for the slow release of fertilizers.

PubMed

Bortolin, Adriel; Aouada, Fauze A; Mattoso, Luiz H C; Ribeiro, Caue

2013-08-07

In this work, we synthesized a novel series of hydrogels composed of polyacrylamide (PAAm), methylcellulose (MC), and calcic montmorillonite (MMt) appropriate for the controlled release of fertilizers, where the components presented a synergistic effect, giving very high fertilizer loading in their structure. The synthesized hydrogel was characterized in relation to morphological, hydrophilic, spectroscopic, structural, thermal, and kinetic properties. After those characterizations, the application potential was verified through sorption and desorption studies of a nitrogenated fertilizer, urea (CO(NH2)2). The swelling degree results showed that the clay loading considerably reduces the water absorption capability; however, the hydrolysis process favored the urea adsorption in the hydrogel nanocomposites, increasing the load content according to the increase of the clay mass. The FTIR spectra indicated that there was incorporation of the clay with the polymeric matrix of the hydrogel and that incorporation increased the water absorption speed (indicated by the kinetic constant k). By an X-ray diffraction technique, good nanodispersion (intercalation) and exfoliation of the clay platelets in the hydrogel matrix were observed. Furthermore, the presence of the montmorillonite in the hydrogel caused the system to liberate the nutrient in a more controlled manner than that with the neat hydrogel in different pH ranges. In conclusion, excellent results were obtained for the controlled desorption of urea, highlighting the hydrolyzed hydrogels containing 50% calcic montmorillonite. This system presented the best desorption results, releasing larger amounts of nutrient and almost 200 times slower than pure urea, i.e., without hydrogel. The total values of nutrients present in the system show that this material is potentially viable for application in agriculture as a nutrient carrier vehicle.

Using the reversible inhibition of gastric lipase by Orlistat for investigating simultaneously lipase adsorption and substrate hydrolysis at the lipid-water interface.

PubMed

Bénarouche, Anaïs; Point, Vanessa; Carrière, Frédéric; Cavalier, Jean-François

2014-06-01

The lipolysis reaction carried out by lipases at the water-lipid interface is a complex process including enzyme conformational changes, adsorption/desorption equilibrium and substrate hydrolysis. Mixed monomolecular films of the lipase inhibitor Orlistat and 1,2-dicaprin were used here to investigate the adsorption of dog gastric lipase (DGL) followed by the hydrolysis of 1,2-dicaprin. The combined study of these two essential catalysis steps was made possible thanks to the highest affinity of DGL for Orlistat than 1,2-dicaprin and the fact that the inhibition of DGL by Orlistat is reversible. Upon DGL binding to mixed 1,2-dicaprin/Orlistat monolayers, an increase in surface pressure reflecting lipase adsorption was first recorded. Limited amounts of Orlistat allowed to maintain DGL inactive on 1,2-dicaprin during a period of time that was sufficient to determine DGL adsorption and desorption rate constants. A decrease in surface pressure reflecting 1,2-dicaprin hydrolysis and product desorption was observed after the slow hydrolysis of the covalent DGL-Orlistat complex was complete. The rate of 1,2-dicaprin hydrolysis was recorded using the surface barostat technique. Based on a kinetic model describing the inhibition by Orlistat and the activity of DGL on a mixed 1,2-dicaprin/Orlistat monolayer spread at the air-water interface combined with surface pressure measurements, it was possible to monitor DGL adsorption at the lipid-water interface and substrate hydrolysis in the course of a single experiment. This allowed to assess the kcat/KM* ratio for DGL acting on 1,2-dicaprin monolayer, after showing that mixed monolayers containing a low fraction of Orlistat were similar to pure 1,2-dicaprin monolayers. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Control of dissolved CH4 in a municipal UASB reactor effluent by means of a desorption - Biofiltration arrangement.

PubMed

Huete, A; de Los Cobos-Vasconcelos, D; Gómez-Borraz, T; Morgan-Sagastume, J M; Noyola, A

2018-06-15

The direct anaerobic treatment of municipal wastewater represents an adapted technology to the conditions of developing countries. In order to get an increased acceptance of this technology, a proper control of dissolved methane in the anaerobic effluents should be considered, as methane is a potent greenhouse gas. In this study, a pilot-scale system was operated for 168 days to recover dissolved methane from an effluent of an upflow anaerobic sludge blanket reactor and then oxidize it in a compost biofilter. The system operated at a constant air (0.9 m 3 /h ±0.09) and two air-to anaerobic effluent ratio (1:1 and 1:2). In both conditions (CH 4 concentration of 2.7 ± 0.87 and 4.3% ± 1.14, respectively) the desorption column recovered 99% of the dissolved CH 4 and approximately 30% ± 8.5 of H 2 S, whose desorption was limited due to the high pH (>8) of the effluent. The biofilter removed 70% ± 8 of the average CH 4 load (60 gCH 4 /m 3 h ± 13) and 100% of the H 2 S load at an empty bed retention time of 23 min. The average temperature inside the biofilter was 42 ± 9 °C due to the CH 4 oxidation reaction, indicating that temperature and moisture control is particularly important for CH 4 removal in compost biofilters. The system may achieve a 54% reduction of greenhouse gas emissions from dissolved CH 4 in this particular case. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of sorption processes for the development of low-cost pesticide decontamination techniques.

PubMed

Rojas, Raquel; Vanderlinden, Eva; Morillo, José; Usero, José; El Bakouri, Hicham

2014-08-01

The adsorption/desorption behavior of four pesticides (atrazine, alachlor, endosulfan sulfate and trifluralin) in aqueous solutions onto four adsorbents (sunflower seed shells, rice husk, composted sewage sludge and soil) was investigated. Pesticide determination was carried out using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. Maximum removal efficiency (73.9%) was reached using 1 g of rice husk and 50 mL of pesticide solution (200 μg L(-1)). The pseudo adsorption equilibrium was reached with 0.6 g organic residue, which was used in subsequent experiments. The pseudo-first-order, pseudo-second-order kinetics and the intra-particle diffusion models were used to describe the kinetic data and rate constants were evaluated. The first model was more suitable for the sorption of atrazine and alachlor while the pseudo-second-order best described endosulfan sulfate and trifluralin adsorption, which showed the fastest sorption rates. 4h was considered as the equilibrium time for determining adsorption isotherms. Experimental data were modeled by Langmuir and Freundlich models. In most of the studied cases both models can describe the adsorption process, although the Freundlich model was applicable in all cases. The sorption capacity increased with the hydrophobic character of the pesticides and decreased with their water solubility. Rice husk was revealed as the best adsorbent for three of the four studied pesticides (atrazine, alachlor and endosulfan sulfate), while better results were obtained with composted sewage sludge and sunflower seed shell for the removal of trifluralin. Although desorption percentages were not high (with the exception of alachlor, which reached a desorption rate of 57%), the Kfd values were lower than the Kf values for adsorption and all H values were below 100, indicating that the adsorption was weak. Copyright © 2014 Elsevier B.V. All rights reserved.

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

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

Matsuyama, M.; Kondo, M.; Noda, N.

2015-03-15

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel ismore » limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)« less

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment.

PubMed

Williams, Mike; Kookana, Rai

2010-08-01

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating 12C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with 14C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems. 2010. Published by Elsevier B.V. All rights reserved.

Laboratory Studies of Alkali Components in Tenuous Planetary Atmospheres

NASA Astrophysics Data System (ADS)

Yakshinskiy, B. V.

2004-05-01

We report on studies performed at the Laboratory for Surface Modification of Rutgers University and focused on the origin of alkali vapors (Na, K) in the tenuous atmospheres of the planet Mercury, the Moon, and Jupiter's icy satellite Europa [1, 2]; we also address the question why alkaline-earth metals (Mg, Ca) are less abundant in the atmospheres. A variety of ultrahigh-vacuum surface science techniques are used, including X-ray Photoelectron Spectroscopy (XPS), Low-Energy Ion Scattering (LEIS), Thermal Programmed Desorption (TPD), Electron- and Photon-Stimulated Desorption (ESD and PSD), Surface Ionization (SI). Measurements have been made on different samples, including the model mineral binary oxide SiO2 that simulates lunar silicates, and a lunar sample obtained from NASA. Desorption induced by electronic excitations (mainly PSD) rather than by thermal processes is found to be the dominant source process on the lunar surface. The flux at the lunar surface of ultraviolet photons from the Sun is adequate to insure that PSD of sodium contributes substantially to the Moon's atmosphere. A model based on irradiation-induced charge-transfer is proposed to explain the desorption process. There is a strong temperature-dependence of Na ESD and PSD signals from a lunar sample, under conditions where the Na surface coverage is constant and thermal desorption is negligible [3]. On Mercury solar heating of the surface is high enough that thermal desorption will also be a potential source of atmospheric sodium. Ion bombardment of the lunar sample causes both the sputtering of alkali atoms into vacuum and implantation into the sample bulk. In the future we outline the use a novel method, Nuclear Resonance Profiling (NRP) to study the diffusion of alkalis through model minerals, ices, and lunar samples; these measurements would provide additional information to understand the replenishment of Na at the surface of the Moon, Mercury and Europa. We also describe a new detector that we will use to search for desorption of alkaline-earth atoms. [1] T.E. Madey, R.E. Johnson, T.M. Orlando, Surf. Sci. 500 (2002) 838. [2] B.V. Yakshinskiy, T.E. Madey, Surf. Sci. 528 (2003) 54. [3] B.V. Yakshinskiy, T.E. Madey, Icarus 168 (2004) 53.

Characterization of initial events in bacterial surface colonization by two Pseudomonas species using image analysis.

PubMed

Mueller, R F; Characklis, W G; Jones, W L; Sears, J T

1992-05-01

The processes leading to bacterial colonization on solid-water interfaces are adsorption, desorption, growth, and erosion. These processes have been measured individually in situ in a flowing system in real time using image analysis. Four different substrata (copper, silicon, 316 stainless-steel and glass) and 2 different bacterial species (Pseudomonas aeruginosa and Pseudomonas fluorescens) were used in the experiments. The flow was laminar (Re = 1.4) and the shear stress was kept constant during all experiments at 0.75 N m(-2). The surface roughness varied among the substrata from 0.002 microm (for silicon) to 0.015 microm (for copper). Surface free energies varied from 25.1 dynes cm(-1) for silicon to 31.2 dynes cm(-1) for copper. Cell curface hydrophobicity, reported as hydrocarbon partitioning values, ranged from 0.67 for Ps. fluorescens to 0.97 for Ps. aeruginosa.The adsorption rate coefficient varied by as much as a factor of 10 among the combinations of bacterial strain and substratum material, and was positively correlated with surface free energy, the surface roughness of the substratum, and the hydrophobicity of the cells. The probability of desorption decreased with increasing surface free energy and surface roughness of the substratum. Cell growth was inhibited on copper, but replication of cells overlying an initial cell layer was observed with increased exposure time to the cell-containing bulk water. A mathematical model describing cell accumulation on a substratum is presented.

Desorption modeling of hydrophobic organic chemicals from plastic sheets using experimentally determined diffusion coefficients in plastics.

PubMed

Lee, Hwang; Byun, Da-Eun; Kim, Ju Min; Kwon, Jung-Hwan

2018-01-01

To evaluate rate of migration from plastic debris, desorption of model hydrophobic organic chemicals (HOCs) from polyethylene (PE)/polypropylene (PP) films to water was measured using PE/PP films homogeneously loaded with the HOCs. The HOCs fractions remaining in the PE/PP films were compared with those predicted using a model characterized by the mass transfer Biot number. The experimental data agreed with the model simulation, indicating that HOCs desorption from plastic particles can generally be described by the model. For hexachlorocyclohexanes with lower plastic-water partition coefficients, desorption was dominated by diffusion in the plastic film, whereas desorption of chlorinated benzenes with higher partition coefficients was determined by diffusion in the aqueous boundary layer. Evaluation of the fraction of HOCs remaining in plastic films with respect to film thickness and desorption time showed that the partition coefficient between plastic and water is the most important parameter influencing the desorption half-life. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of equilibration time on Pu desorption from goethite

DOE PAGES

Wong, Jennifer C.; Zavarin, Mavrik; Begg, James D.; ...

2015-01-28

Strongly sorbing ions such as plutonium may become irreversibly bound to mineral surfaces over time implicates near- and far-field transport of Pu. Batch adsorption–desorption data were collected as a function of time and pH to study the surface stability of Pu on goethite. Pu(IV) was adsorbed to goethite over the pH range 4.2 to 6.6 for different periods of time (1, 6, 15, 34 and 116 d). Moreover, following adsorption, Pu was leached from the mineral surface with desferrioxamine B (DFOB), a complexant capable of effectively competing with the goethite surface for Pu. The amount of Pu desorbed from the goethitemore » was found to vary as a function of the adsorption equilibration time, with less Pu removed from the goethite following longer adsorption periods. This effect was most pronounced at low pH. Logarithmic desorption distribution ratios for each adsorption equilibration time were fit to a pH-dependent model. Model slopes decreased between 1 and 116 d adsorption time, indicating that overall Pu(IV) surface stability on goethite surfaces becomes less dependent on pH with greater adsorption equilibration time. The combination of adsorption and desorption kinetic data suggest that non-redox aging processes affect Pu sorption behavior on goethite.« less

Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

PubMed Central

Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M.

2008-01-01

We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

Organic solvent desorption from two tegafur polymorphs.

PubMed

Bobrovs, Raitis; Actiņš, Andris

2013-11-30

Desorption behavior of 8 different solvents from α and β tegafur (5-fluoro-1-(tetrahydro-2-furyl)uracil) has been studied in this work. Solvent desorption from samples stored at 95% and 50% relative solvent vapor pressure was studied in isothermal conditions at 30 °C. The results of this study demonstrated that: solvent desorption rate did not differ significantly for both phases; solvent desorption in all cases occurred faster from samples with the largest particle size; and solvent desorption in most cases occurred in two steps. Structure differences and their surface properties were not of great importance on the solvent desorption rates because the main factor affecting desorption rate was sample particle size and sample morphology. Inspection of the structure packing showed that solvent desorption rate and amount of solvent adsorbed were mainly affected by surface molecule arrangement and ability to form short contacts between solvent molecule electron donor groups and freely accessible tegafur tetrahydrofuran group hydrogens, as well as between solvents molecule proton donor groups and fluorouracil ring carbonyl and fluoro groups. Solvent desorption rates of acetone, acetonitrile, ethyl acetate and tetrahydrofuran multilayers from α and β tegafur were approximately 30 times higher than those of solvent monolayers. Scanning electron micrographs showed that sample storage in solvent vapor atmosphere promotes small tegafur particles recrystallization to larger particles. Copyright © 2013 Elsevier B.V. All rights reserved.

Microfluidic Dynamic Interfacial Tensiometry (μDIT).

PubMed

Brosseau, Quentin; Vrignon, Jérémy; Baret, Jean-Christophe

2014-05-07

We designed, developed and characterized a microfluidic method for the measurement of surfactant adsorption kinetics via interfacial tensiometry on a microfluidic chip. The principle of the measurement is based on the deformability of droplets as a response to hydrodynamic forcing through a series of microfluidic expansions. We focus our analysis on one perfluoro surfactant molecule of practical interest for droplet-based microfluidic applications. We show that although the adsorption kinetics is much faster than the kinetics of the corresponding pendant drop experiment, our droplet-based microfluidic system has a sufficient time resolution to obtain quantitative measurement at the sub-second time-scale on nanoliter droplet volumes, leading to both a gain by a factor of ∼10 in time resolution and a downscaling of the measurement volumes by a factor of ∼1000 compared to standard techniques. Our approach provides new insight into the adsorption of surfactant molecules at liquid-liquid interfaces in a confined environment, relevant to emulsification, encapsulation and foaming, and the ability to measure adsorption and desorption rate constants.

Identification of Bacteria Using Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry

ERIC Educational Resources Information Center

Kedney, Mollie G.; Strunk, Kevin B.; Giaquinto, Lisa M.; Wagner, Jennifer A.; Pollack, Sidney; Patton, Walter A.

2007-01-01

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS or simply MALDI) has become ubiquitous in the identification and analysis of biomacromolecules. As a technique that allows for the molecular weight determination of otherwise nonvolatile molecules, MALDI has had a profound impact in the molecular…

Detection of Volatile Organic Compounds by Self-assembled Monolayer Coated Sensor Array with Concentration-independent Fingerprints

PubMed Central

Chang, Ye; Tang, Ning; Qu, Hemi; Liu, Jing; Zhang, Daihua; Zhang, Hao; Pang, Wei; Duan, Xuexin

2016-01-01

In this paper, we have modeled and analyzed affinities and kinetics of volatile organic compounds (VOCs) adsorption (and desorption) on various surface chemical groups using multiple self-assembled monolayers (SAMs) functionalized film bulk acoustic resonator (FBAR) array. The high-frequency and micro-scale resonator provides improved sensitivity in the detections of VOCs at trace levels. With the study of affinities and kinetics, three concentration-independent intrinsic parameters (monolayer adsorption capacity, adsorption energy constant and desorption rate) of gas-surface interactions are obtained to contribute to a multi-parameter fingerprint library of VOC analytes. Effects of functional group’s properties on gas-surface interactions are also discussed. The proposed sensor array with concentration-independent fingerprint library shows potential as a portable electronic nose (e-nose) system for VOCs discrimination and gas-sensitive materials selections. PMID:27045012

Contour temperature programmed desorption for monitoring multiple chemical reaction products

NASA Astrophysics Data System (ADS)

Chusuei, C. C.; de la Peña, J. V.; Schreifels, J. A.

1999-09-01

A simple method for obtaining a comprehensive overview of major compounds desorbing from the surface during temperature programmed desorption (TPD) experiments is outlined. Standard commercially available equipment is used to perform the experiment. The method is particularly valuable when high molecular mass compounds are being studied. The acquisition of contour temperature programmed desorption (CTPD) spectra, sampling 50-dalton mass ranges at a time in the thermal desorption experiments, is described and demonstrated for the interaction of benzotriazole adsorbed on a Ni(111) surface. Conventional two-dimensional TPD spectra can be extracted from the CTPD by taking vertical slices of the contour.

Top-down proteomic identification of Shiga toxin 2 subtypes from Shiga toxin-producing Escherichia coli by Matrix-Assisted Laser Desorption Ionization-Tandem Time of Flight mass spectrometry

USDA-ARS?s Scientific Manuscript database

We have analyzed 26 Shiga toxin-producing Escherichia coli (STEC) strains for Shiga toxin 2 (Stx2) production using matrix-assisted laser desorption/ionization time-of-flight-time-of-flight tandem mass spectrometry (MALDI-TOF-TOF-MS/MS) and top-down proteomic analysis. STEC strains were induced to ...

Behaviour of pharmaceuticals in spiked lake sediments - effects and interactions with benthic invertebrates.

PubMed

Gilroy, Ève A M; Balakrishnan, Vimal K; Solomon, Keith R; Sverko, Ed; Sibley, Paul K

2012-02-01

The behaviour and effects of atorvastatin (ATO), carbamazepine (CBZ), and 17α-ethinylestradiol (EE2) were investigated in spiked lake sediments, at concentrations up to 56.5 mg kg(-1)dry weight (dw), with the benthic invertebrates Chironomus dilutus and Hyalella azteca. Desorption constants were calculated in the presence and absence of animals, using linear isotherms, yielding K(d) values of 28.2, 189.0 and 125.1 L kg(-1) (ATO), 73.7, 201.7 and 263.2 L kg(-1) (CBZ), and 114.9, 114.2 and 519.2 L kg(-1) (EE2) for C. dilutus, H. azteca, and without animals, respectively. For ATO and CBZ, K(d) values were smaller in the presence of C. dilutus, indicating greater desorption to the overlying water from bioturbation, which is consistent with the predominantly benthic occurrence of C. dilutus compared to H. azteca. In contrast, due to its greater hydrophobicity, bioturbation did not significantly affect desorption of EE2. No significant toxicity was observed, indicating decreased bioavailability of the chemicals sorbed to sediments compared with water-only toxicity assays. Copyright © 2011 Elsevier Ltd. All rights reserved.

Mesoporous aluminium organophosphonates: a reusable chemsensor for the detection of explosives

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

Li, Dongdong, E-mail: lidongdong@jlu.edu.cn; Yu, Xiang

Rapid and sensitive detection of explosives is in high demand for homeland security and public safety. In this work, electron-rich of anthracene functionalized mesoporous aluminium organophosphonates (En-AlPs) were synthesized by a one-pot condensation process. The mesoporous structure and strong blue emission of En-AlPs were confirmed by the N{sub 2} adsorption-desorption isotherms, transmission electron microscopy images and fluorescence spectra. The materials En-AlPs can serve as sensitive chemosensors for various electron deficient nitroderivatives, with the quenching constant and the detection limit up to 1.5×10{sup 6} M{sup −1} and 0.3 ppm in water solution. More importantly, the materials can be recycled for manymore » times by simply washed with ethanol, showing potential applications in explosives detection. - Graphical abstract: Electron-rich of anthracene functionalized mesoporous aluminium organophosphonates can serve as sensitive and recycled chemosensors for nitroderivatives with the quenching constant up to 1.5×10{sup 6} M{sup −1} in water solution. Display Omitted - Highlights: • Anthracene functionalized mesoporous aluminium organophosphonates were synthesized. • The materials serve as sensitive chemosensors for nitroderivatives. • The materials can be recycled for many times by simply washed with ethanol. • The materials show potential applications in explosives detection.« less

Desorption of Hg(II) and Sb(V) on extracellular polymeric substances: effects of pH, EDTA, Ca(II) and temperature shocks.

PubMed

Zhang, Daoyong; Lee, Duu-Jong; Pan, Xiangliang

2013-01-01

Extracellular polymeric substances (EPS) existed ubiquitously in biological systems affect the mobility and availability of heavy metals in the environments. The adsorption-desorption behaviors of Hg(II) and Sb(V) on EPS were investigated. The sorption rates follow Sb(V) > Hg(II), and the desorption rates follow reverse order. Applications of ethylene diamine tetraacetic acid (EDTA), Ca(II) and pH shocks affect desorption rates and desorbed quantities of Hg(II) from EPS-Hg complex. Temperature shock minimally affects the desorption rate of Hg(II). Conversely, the EPS-Sb complex is stable subjected to EDTA, Ca(II), temperature or pH shocks. The excitation-emission matrix (EEM) fluorescence spectroscopy and fast-Fourier (FT-IR) analysis showed that Hg(II) and Sb(V) principally interacted with polysaccharides and protein-like compounds in the EPS, respectively. The EPS-Hg complex presents a time bomb that may release high levels of Hg(II) in short time period under environmental shocks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Two-Dimensional Porous Electrode Model for Capacitive Deionization

DOE PAGES

Hemmatifar, Ali; Stadermann, Michael; Santiago, Juan G.

2015-10-28

Here, ion transport in porous conductive materials is of great importance in a variety of electrochemical systems including batteries and supercapacitors. We here analyze the coupling of flow and charge transport and charge capacitance in capacitive deionization (CDI). In CDI, a pair of porous carbon electrodes is employed to electrostatically retain and remove ionic species from aqueous solutions. We here develop and solve a novel unsteady two-dimensional model for capturing the ion adsorption/desorption dynamics in a flow-between CDI system. We use this model to study the complex, nonlinear coupling between electromigration, diffusion, and advection of ions. We also fabricated amore » laboratory-scale CDI cell which we use to measure the near-equilibrium, cumulative adsorbed salt, and electric charge as a function of applied external voltage. We use these integral measures to validate and calibrate this model. We further present a detailed computational study of the spatiotemporal adsorption/desorption dynamics under constant voltage and constant flow conditions. We show results for low (20 mM KCl) and relatively high (200 mM KCl) inlet ion concentrations and identify effects of ion starvation on desalination. We show that in both cases electromigrative transport eventually becomes negligible and diffusive ion transport reduces the desalination rate.« less

A SIMPLE AND RAPID MATRIX-ASSISTED LASER DESORPTION/IONIZATION TIME OF FLIGHT MASS SPECTROMETRY METHOD TO SCREEN FISH PLASMA SAMPLES FOR ESTROGEN-RESPONSIVE BIOMARKERS

EPA Science Inventory

In this study, we describe and evaluate the performance of a simple and rapid mass spectral method for screening fish plasma for estrogen-responsive biomarkers using matrix assisted laster desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) couopled with a short...

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predictedmore » using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

DOE PAGES

Wang, Chao; Xu, Zhijie; Lai, Kevin; ...

2017-10-24

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predictedmore » using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Recent advances in thermal desorption-gas chromatography-mass spectrometery method to eliminate the matrix effect between air and water samples: application to the accurate determination of Henry's law constant.

PubMed

Kim, Yong-Hyun; Kim, Ki-Hyun

2014-05-16

Accurate values for the Henry's law constants are essential to describe the environmental dynamics of a solute, but substantial errors are recognized in many reported data due to practical difficulties in measuring solubility and/or vapor pressure. Despite such awareness, validation of experimental approaches has scarcely been made. An experimental approach based on thermal desorption-gas chromatography-mass spectrometery (TD-GC-MS) method was developed to concurrently allow the accurate determination of target compounds from the headspace and aqueous samples in closed equilibrated system. The analysis of six aromatics and eight non-aromatic oxygenates was then carried out in a static headspace mode. An estimation of the potential bias and mass balance (i.e., sum of mass measured individually from gas and liquid phases vs. the mass initially added to the system) demonstrates compound-specific phase dependency so that the best results are obtained by aqueous (less soluble aromatics) and headspace analysis (more soluble non-aromatics). Accordingly, we were able to point to the possible sources of biases in previous studies and provide the best estimates for the Henry's constants (Matm(-1)): benzene (0.17), toluene (0.15), p-xylene (0.13), m-xylene (0.13), o-xylene (0.19), styrene (0.27); propionaldehyde (9.26), butyraldehyde (6.19), isovaleraldehyde (2.14), n-valeraldehyde (3.98), methyl ethyl ketone (10.5), methyl isobutyl ketone (3.93), n-butyl acetate (2.41), and isobutyl alcohol (22.2). Copyright © 2014 Elsevier B.V. All rights reserved.

EVALUATION OF SOLID PHASE MICROEXTRACTION FOR THE ANALYSIS OF HYDROPHILIC COMPOUNDS

EPA Science Inventory

Two commercially available solid phase microextractions (SPME) fibers, polyacrylate and carboxem/polydimethylsiloxane (PDMS), were evaluated for their ability to extract hydrophilic compounds from drinking water. Conditions, such as desorption time, desorption temperature, sample...

Formation of a knudsen layer in electronically induced desorption

NASA Astrophysics Data System (ADS)

Sibold, D.; Urbassek, H. M.

1992-10-01

For intense desorption fluxes, particles desorbed by electronic transitions (DIET) from a surface into a vacuum may thermalize in the gas cloud forming above the surface. In immediate vicinity to the surface, however, a non-equilibrium layer (the Knudsen layer) exists which separates the recently desorbed, non-thermal particles from the thermalized gas cloud. We investigate by Monte Carlo computer simulation the time it takes to form a Knudsen layer, and its properties. It is found that a Knudsen layer, and thus also a thermalized gas cloud, is formed after around 200 mean free flight times of the desorbing particles, corresponding to a desorption of 20 monolayers. At the end of the Knudsen layer, the gas density will be higher, and the flow velocity and temperature smaller, than literature values indicate for thermal desorption. These data are of fundamental interest for the modeling of gas-kinetic and gas-dynamic effects in DIET.

Molecule desorption induced by gate-voltage application in MOS structure

NASA Astrophysics Data System (ADS)

Hirota, Nozomu; Hattori, Ken; Daimon, Hiroshi; Hattori, Azusa N.; Tanaka, Hidekazu

2016-04-01

For the first time, we demonstrate desorption from a MOS surface by applying gate voltages (V G). We observed CH4, CO, and CO2 desorption from a MOS (Fe nanofilm/a-SiO2/Si) surface in vacuum only when applying negative V G, suggesting the occurrence of electronic excitation by hot-hole injection. This demonstration is the first step in the application of MOSs to electrically controlled catalysts.

Silver nanostructures in laser desorption/ionization mass spectrometry and mass spectrometry imaging.

PubMed

Sekuła, Justyna; Nizioł, Joanna; Rode, Wojciech; Ruman, Tomasz

2015-09-21

Silver nanoparticles have been successfully applied as a matrix replacement for the laser desorption/ionization time-of-flight mass spectrometry (LDI-ToF-MS). Nanoparticles, producing spectra with highly reduced chemical background in the low m/z region, are perfectly suited for low-molecular weight compound analysis and imaging. Silver nanoparticles (AgNPs) can efficiently absorb ultraviolet laser radiation, transfer energy to the analyte and promote analyte desorption, but also constitute a source of silver ions suitable for analyte cationisation. This review provides an overview of the literature on silver nanomaterials as non-conventional desorption and ionization promoters in LDI-MS and mass spectrometry imaging.

Cesium sorption reversibility and kinetics on illite, montmorillonite, and kaolinite

DOE PAGES

Durrant, Chad B.; Begg, James D.; Kersting, Annie B.; ...

2017-08-17

Understanding sorption and desorption processes is essential to predicting the mobility of radionuclides in the environment. In this study, we investigate adsorption/desorption of cesium in both binary (Cs + one mineral) and ternary (Cs + two minerals) experiments to study component additivity and sorption reversibility over long time periods (500 days). Binary Cs sorption experiments were performed with illite, montmorillonite, and kaolinite in a 5 mM NaCl/0.7 mM NaHCO3 solution (pH 8) and Cs concentration range of 10 –3 to 10 –11 M. The binary sorption experiments were followed by batch desorption experiments. The sorption behavior was modeled with themore » FIT4FD code and the results used to predict desorption behavior. Sorption to montmorillonite and kaolinite was linear over the entire concentration range but sorption to illite was non-linear, indicating the presence of multiple sorption sites. Based on the 14 day batch desorption data, cesium sorption appeared irreversible at high surface loadings in the case of illite but reversible at all concentrations for montmorillonite and kaolinite. Additionally, a novel experimental approach, using a dialysis membrane, was adopted in the ternary experiments, allowing investigation of the effect of a second mineral on Cs desorption from the original mineral. Cs was first sorbed to illite, montmorillonite or kaolinite, then a 3.5–5 kDalton Float-A-Lyzer® dialysis bag with 0.3 g of illite was introduced to each experiment inducing desorption. Nearly complete Cs desorption from kaolinite and montmorillonite was observed over the experiment, consistent with our equilibrium model, indicating complete Cs desorption from these minerals. Results from the long-term ternary experiments show significantly greater Cs desorption compared to the binary desorption experiments. Approximately ~ 45% of Cs desorbed from illite. However, our equilibrium model predicted ~ 65% desorption. Importantly, the data imply that in some cases, slow desorption kinetics rather than permanent fixation may play an important role in apparent irreversible Cs sorption.« less

Determination of stream reaeration coefficients by use of tracers

USGS Publications Warehouse

Kilpatrick, F.A.; Rathbun, R.E.; Yotsukura, N.; Parker, G.W.; DeLong, L.L.

1987-01-01

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes.Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed in which a radioactive tracer gas was injected into a stream--the tracer gas being desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas.This manual describes the slug-injection and constant-rate injection methods of performing gas-tracer desorption measurements. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, methods of injection, sampling and analysis, and computational techniques to compute desorption and reaeration coefficients.

Determination of diphenylether herbicides in water samples by solid-phase microextraction coupled to liquid chromatography.

PubMed

Sheu, Hong-Li; Sung, Yu-Hsiang; Melwanki, Mahaveer B; Huang, Shang-Da

2006-11-01

Solid-phase microextraction (SPME) coupled to LC for the analysis of five diphenylether herbicides (aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen, and lactofen) is described. Various parameters of extraction of analytes onto the fiber (such as type of fiber, extraction time and temperature, pH, impact of salt and organic solute) and desorption from the fiber in the desorption chamber prior to separation (such as type and composition of desorption solvent, desorption mode, soaking time, and flush-out time) were studied and optimized. Four commercially available SPME fibers were studied. PDMS/divinylbenzene (PDMS/DVB, 60 microm) and carbowax/ templated resin (CW/TPR, 50 microm) fibers were selected due to better extraction efficiencies. Repeatability (RSD, < 7%), correlation coefficient (> 0.994), and detection limit (0.33-1.74 and 0.22-1.94 ng/mL, respectively, for PDMS/DVB and CW/TPR) were investigated. Relative recovery (81-104% for PDMS/DVB and 83-100% for CW/TPR fiber) values have also been calculated. The developed method was successfully applied to the analysis of river water and water collected from a vegetable garden.

Kinetics and reversibility of micropollutant sorption in sludge.

PubMed

Barret, Maialen; Carrère, Hélène; Patau, Mathieu; Patureau, Dominique

2011-10-01

The fate of micropollutants throughout wastewater treatment systems is highly dependent on their sorption interactions with sludge matter. In this study, both the sorption and desorption kinetics of polycyclic aromatic hydrocarbons (PAHs) in activated sludge were shown to be very rapid in comparison to biodegradation kinetics. It was concluded that PAH transfer does not limit their biodegradation and that their fate is governed by the sorption/desorption equilibrium state. The effect of contact time between sludge and PAHs was also investigated. It was shown that aging did not influence the sorption/desorption equilibrium although PAH losses during aging suggest that sequestration phenomena had occurred. This implies that for PAH sorption assessment within treatment processes there is no need to include a contact time dimension. As a consequence, thanks to an innovative approach taking into account sorption equilibria and sequestration, this work has demonstrated that studies in the literature which, in main, deal with micropollutant sorption in sewage sludge with only a short contact time can be extrapolated to real systems in which sorption, desorption and aging occur.

Development of a Microfluidic Open Interface with Flow Isolated Desorption Volume for the Direct Coupling of SPME Devices to Mass Spectrometry.

PubMed

Tascon, Marcos; Alam, Md Nazmul; Gómez-Ríos, Germán Augusto; Pawliszyn, Janusz

2018-02-20

Technologies that efficiently integrate the sampling and sample preparation steps with direct introduction to mass spectrometry (MS), providing simple and sensitive analytical workflows as well as capabilities for automation, can generate a great impact in a vast variety of fields, such as in clinical, environmental, and food-science applications. In this study, a novel approach that facilitates direct coupling of Bio-SPME devices to MS using a microfluidic design is presented. This technology, named microfluidic open interface (MOI), which operates under the concept of flow-isolated desorption volume, consists of an open-to-ambient desorption chamber (V ≤ 7 μL) connected to an ionization source. Subsequently, compounds of interest are transported to the ionization source by means of the self-aspiration process intrinsic of these interfaces. Thus, any ionization technology that provides a reliable and constant suction, such as electrospray ionization (ESI), atmospheric-pressure chemical ionization (APCI), or inductively coupled plasma ionization (ICP), can be hyphenated to MOI. Using this setup, the desorption chamber is used to release target compounds from the coating, while the isolation of the flow enables the ionization source to be continuously fed with solvent, all without the necessity of employment of additional valves. As a proof of concept, the design was applied to an ESI-MS/MS system for experimental validation. Furthermore, numerical simulations were undertaken to provide a detailed understanding of the fluid flow pattern inside the interface, then used to optimize the system for better efficiency. The analytical workflow of the developed Bio-SPME-MOI-MS setup consists of the direct immersion of SPME fibers into the matrix to extract/enrich analytes of interest within a short period of time, followed by a rinsing step with water to remove potentially adhering proteins, salts, and/or other interfering compounds. Next, the fiber is inserted into the MOI for desorption of compounds of interest. Finally, the volume contained in the chamber is drained and moved toward the electrospray needle for ionization and direct introduction to MS. Aiming to validate the technology, the fast determination of selected immunosuppressive drugs (e.g., tacrolimus, cyclosporine, sirolimus, and everolimus) from 100 μL of whole blood was assessed. Limits of quantitation in the subppb range were obtained for all studied compounds. Good linearity (r 2 ≥ 0.99) and excellent precision, with (8%) and without (14%) internal standard correction, were attained.

Emerging and Future Applications of Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) Mass Spectrometry in the Clinical Microbiology Laboratory: A Report of the Association for Molecular Pathology.

PubMed

Doern, Christopher D; Butler-Wu, Susan M

2016-11-01

The performance of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MS) for routine bacterial and yeast identification as well as direct-from-blood culture bottle identification has been thoroughly evaluated in the peer-reviewed literature. Microbiologists are now moving beyond these methods to apply MS to other areas of the diagnostic process. This review discusses the emergence of advanced matrix-assisted laser desorption ionization time-of-flight MS applications, including the identification of filamentous fungi and mycobacteria and the current and future state of antimicrobial resistance testing. Copyright © 2016 American Society for Investigative Pathology and the Association for Molecular Pathology. Published by Elsevier Inc. All rights reserved.

Addressing the selectivity issue of cobalt doped zinc oxide thin film iso-butane sensors: Conductance transients and principal component analyses

NASA Astrophysics Data System (ADS)

Ghosh, A.; Majumder, S. B.

2017-07-01

Iso-butane (i-C4H10) is one of the major components of liquefied petroleum gas which is used as fuel in domestic and industrial applications. Developing chemi-resistive selective i-C4H10 thin film sensors remains a major challenge. Two strategies were undertaken to differentiate carbon monoxide, hydrogen, and iso-butane gases from the measured conductance transients of cobalt doped zinc oxide thin films. Following the first strategy, the response and recovery transients of conductances in these gas environments are fitted using the Langmuir adsorption kinetic model to estimate the heat of adsorption, response time constant, and activation energies for adsorption (response) and desorption (recovery). Although these test gases have seemingly different vapor densities, molecular diameters, and reactivities, analyzing the estimated heat of adsorption and activation energies (for both adsorption and desorption), we could not differentiate these gases unequivocally. However, we have found that the lower the vapor density, the faster the response time irrespective of the test gas concentration. As a second strategy, we demonstrated that feature extraction of conductance transients (using fast Fourier transformation) in conjunction with the pattern recognition algorithm (principal component analysis) is more fruitful to address the cross-sensitivity of Co doped ZnO thin film sensors. We have found that although the dispersion among different concentrations of hydrogen and carbon monoxide could not be avoided, each of these three gases forms distinct clusters in the plot of principal component 2 versus 1 and therefore could easily be differentiated.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry and database for identification of Legionella species.

PubMed

He, Ying; Chang, Tsung C; Li, Haijing; Shi, Gongyi; Tang, Yi-Wei

2011-07-01

More than 20 species of Legionella have been identified in relation to human infections. Rapid detection and identification of Legionella isolates is clinically useful to differentiate between infection and contamination and to determine treatment regimens. We explored the use of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) Biotyper system (Bruker Daltonik GmbH, Bremen, Germany) for the identification of Legionella species. The MALDI MS spectra were generated and compared with the Biotyper database, which includes 25 Legionella strains covering 22 species and four Legionella pneumophila serogroups. A total of 83 blind-coded Legionella strains, consisting of 54 reference and 29 clinical strains, were analyzed in the study. Overall, the Biotyper system correctly identified 51 (61.4%) of all strains and isolates to the species level. For species included in the Biotyper database, the method identified 51 (86.4%) strains out of 59 Legionella strains to the correct species level, including 24 (100%) L. pneumophila and 27 (77.1%) non-L. pneumophila strains. The remaining 24 Legionella strains, belonging to species not covered by the Biotyper database, were either identified to the Legionella genus level or had no reliable identification. The Biotyper system produces constant and reproducible MALDI MS spectra for Legionella strains and can be used for rapid and accurate Legionella identification. More Legionella strains, especially the non-L. pneumophila strains, need to be included in the current Biotyper database to cover varieties of Legionella species and to increase identification accuracy.

A Novel Nanocomposite as an Efficient Adsorbent for the Rapid Adsorption of Ni(II) from Aqueous Solution

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A sulfhydryl-lignocellulose/montmorillonite (SLT) nanocomposite was prepared using a chemical intercalation reaction. The SLT nanocomposite was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Transmission Electron Microscopy (TEM), the results demonstrated that an intercalated-exfoliated nanostructure was formed in the SLT nanocomposite. Batch experiments were conducted to optimize parameters such as SLT nanocomposite dosage, the initial concentration of Ni(II), solution pH, temperature, and time. The results indicated that the attractive adsorption capacity reached 1134.08 mg/g with 0.05 g of SLT at an initial concentration of Ni(II) of 700 mg/L, solution pH of 5.5, adsorption temperature of 50 °C, and adsorption time of 40 min, meanwhile, the Ni(II) adsorption capacity significantly decreased with the increase in ionic strength. The pseudo-second order kinetic model could describe the whole adsorption process well, and the isotherm adsorption equilibrium conformed to the Freundlich model. The adsorption mechanism of SLT was also discussed by means of FTIR and Energy-Dispersive X-Ray (EDX). Dramatically, the introduction of sulfhydryl achieves the increased activated functional groups content of SLT nanocomposite, leading to remarkably higher adsorption amount on Ni(II). The desorption capacity of SLT was dependent on parameters such as HNO3 concentration, desorption temperature, and ultrasonic desorption time. The satisfactory desorption capacity and desorption efficiency of 458.21 mg/g and 40.40% were obtained at an HNO3 concentration, desorption temperature, and ultrasonic desorption time of 0.4 mol/L, 40 °C, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of SLT was consistent for four cycles without any appreciable loss and confirmed that the SLT was reusable. Owing to such outstanding features, the novel SLT nanocomposite proved the great potential in adsorption for Ni(II) removal from aqueous solution, and exhibited an extremely significant amount of Ni(II), compared to pristine lignocellulose/montmorillonite and the conventional spent adsorbents. PMID:28937606

Laser-induced desorption of atomic and molecular fragments from a tin dioxide surface modified by a thin organic covering of copper phthalocyanine

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

Komolov, A. S., E-mail: akomolov07@ya.ru; Komolov, S. A.; Lazneva, E. F.

2012-01-15

The systematic features of laser-induced desorption from an SnO{sub 2} surface exposed to 10-ns pulsed neodymium laser radiation are studied at the photon energy 2.34 eV, in the range of pulse energy densities 1 to 50 mJ/cm{sup 2}. As the threshold pulse energy 28 mJ/cm{sup 2} is achieved, molecular oxygen O{sub 2} is detected in the desorption mass spectra from the SnO{sub 2} surface; as the threshold pulse energy 42 mJ/cm{sup 2} is reached, tin Sn, and SnO and (SnO){sub 2} particle desorption is observed. The laser desorption mass spectra from the SnO{sub 2} surface coated with an organic coppermore » phthalocyanine (CuPc) film 50 nm thick are measured. It is shown that laser irradiation causes the fragmentation of CuPc molecules and the desorption of molecular fragments in the laser pulse energy density range 6 to 10 mJ/cm{sup 2}. Along with the desorption of molecular fragments, a weak desorption signal of the substrate components O{sub 2}, Sn, SnO, and (SnO){sub 2} is observed in the same energy range. Desorption energy thresholds of substrate atomic components from the organic film surface are approximately five times lower than thresholds of their desorption from the atomically clean SnO{sub 2} surface, which indicates the diffusion of atomic components of the SnO{sub 2} substrate to the bulk of the deposited organic film.« less

Diel variability of mercury phase and species distributions in the Florida Everglades

USGS Publications Warehouse

Krabbenhoft, D.P.; Hurley, J.P.; Olson, M.L.; Cleckner, L.B.

1998-01-01

Preliminary studies of mercury (Hg) cycling in the Everglades revealed that dissolved gaseous mercury (DGM), total mercury (Hg(T)), and reactive mercury (Hg(R)) show reproducible, diel trends. Peak water-column DGM concentrations were observed on or about noon, with a 3 to 7 fold increase over night-time concentrations. Production of DGM appears to cease during dark periods, with nearly constant water column concentrations that were at or near saturation with respect to the overlying air. A simple mass balance shows that the flux of Hg to the atmosphere from diel DGM production and evasion represents about 10% of the annual input from atmospheric deposition. Production of DGM is likely the result of an indirect photolysis reaction that involves the production of reductive species and/or reduction by electron transfer. Diel variability in Hg(T) and Hg(R) appears to be controlled by two factors: inputs from rainfall and photolytic sorption/desorption processes. A possible mechanism involves photolysis of chromophores on the surface of a solid substrate (e.g., the periphyton mat) giving rise to destabilization of sorbed mercury and net desorption during daylight. At night, the sorption reactions predominate and the water-column Hg(T) decreases. Methylmercury (MeHg) also showed diel trends in concentration but were not clearly linked to the solar cycle or rainfall at the study site.

Development of a second generation biofiltration system

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

Kleinheinz, G.T.; McGinnis, G.D.; Niemi, B.A.

1999-07-01

Biofiltration utilizes microbial processes which are immobilized on a solid support to biodegrade contaminants in air. Biofilters traditionally have been utilized in applications where there is a high volume of air containing low levels of compounds. There are several operational problems biofilters are currently encountering. Some of these problems include systems which are very large, microbial breakdown of the solid support, cycling of compounds onto the biofilters (uneven amounts of compounds in the air), and very short residence times in the biofiltration units. This project was undertaken to determine the feasibility of using physical/chemical methods to adsorb and then desorbmore » analytes to convert a dilute, high volume air stream to a more concentrated low volume air stream. The chemical/physical (adsorption/desorption) system will also serve to provide a relatively consistent air stream to the biofiltration units in order to alleviate the perturbations to the system as a result of uneven analyte concentrations. The ability to concentrate a dilute air stream and provide a constant stream of VOCs to the biofiltration unit will allow for smaller, more efficient, and more economical biofilters. Two years of laboratory studies and initial pilot-scale trials on these coupled systems have shown that they are indeed able to efficiently concentrate dilute streams, and the coupled biofilters are able to remove 90+% of the VOCs from the adsorption/desorption unit.« less

Dynamic desorption of arsenic from polymer-supported hydrated iron(III) oxide in a wastewater treatment plant.

PubMed

Hu, Jian-Long; Yang, Xiao-Song; Liu, Ting; Shao, Li-Nan; Zhang, Wang

2017-11-01

Polymer-supported hydrated iron(III) oxide (PHIO) was successfully applied as adsorbent for arsenic removal in a wastewater treatment plant in Nandan, China. The practical PHIO adsorbent samples (PHIO-P) were collected from the adsorption column of the wastewater treatment plant, and desorption experiments of the adsorbent were carried out. Our results showed that the formation of precipitates on the surface of PHIO-P might block the porous channel of the adsorbent and decrease its arsenic adsorption capacity. In the dynamic arsenic desorption experiment, the arsenic desorption equilibrium was achieved more quickly at decreasing desorption velocity, and higher arsenic desorption efficiency was obtained at increasing NaOH concentration in regenerant. It was found that the PHIO-P adsorbent could be well regenerated at 1.0 M NaOH solution and desorption velocity of 5 BV h -1 . Comparing with the raw adsorbent, the maximum arsenic adsorption capacity of PHIO-P decreased by 41.1% after practical running for 26 months. Additionally, the frequently used waste PHIO adsorbent could be treated as non-hazardous material in the arsenic-containing wastewater treatment process after long-time use.

Detection of the adsorption of water monolayers through the ion oscillation frequency in the magnesium oxide lattice by means of low energy electron diffraction

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

Guevara-Bertsch, M.; Avendaño, E.; Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José

We investigate the variation of the oscillation frequency of the Mg{sup 2+} and O{sup 2−} ions in the magnesium oxide lattice due to the interactions of the surface with water monolayers by means of Low Energy Electron Diffraction. Our key result is a new technique to determine the adsorbate vibrations produced by the water monolayers on the surface lattice as a consequence of their change in the surface Debye temperature and its chemical shift. The latter was systematically investigated for different annealing times and for a constant external thermal perturbation in the range of 110–300 K in order to accomplish adsorptionmore » or desorption of water monolayers in the surface lattice.« less

Using chromatography – desorption method of manufacturing gas mixtures for analytical instruments calibration

NASA Astrophysics Data System (ADS)

Platonov, I. A.; Kolesnichenko, I. N.; Lange, P. K.

2018-05-01

In this paper, the chromatography desorption method of obtaining gas mixtures of known compositions stable for a time sufficient to calibrate analytical instruments is considered. The comparative analysis results of the preparation accuracy of gas mixtures with volatile organic compounds using diffusion, polyabarbotage and chromatography desorption methods are presented. It is shown that the application of chromatography desorption devices allows one to obtain gas mixtures that are stable for 10...60 hours in a dynamic condition. These gas mixtures contain volatile aliphatic and aromatic hydrocarbons with a concentration error of no more than 7%. It is shown that it is expedient to use such gas mixtures for analytical instruments calibration (chromatographs, spectrophotometers, etc.)

USGS Coal Desorption Equipment and a Spreadsheet for Analysis of Lost and Total Gas from Canister Desorption Measurements

USGS Publications Warehouse

Barker, Charles E.; Dallegge, Todd A.; Clark, Arthur C.

2002-01-01

We have updated a simple polyvinyl chloride plastic canister design by adding internal headspace temperature measurement, and redesigned it so it is made with mostly off-the-shelf components for ease of construction. Using self-closing quick connects, this basic canister is mated to a zero-head manometer to make a simple coalbed methane desorption system that is easily transported in small aircraft to remote localities. This equipment is used to gather timed measurements of pressure, volume and temperature data that are corrected to standard pressure and temperature (STP) and graphically analyzed using an Excel(tm)-based spreadsheet. Used together these elements form an effective, practical canister desorption method.

CHARACTERIZATION OF CRYPTOSPORIDIUM PARVUM BY MATRIX-ASSISTED LASER DESORPTION -- IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

EPA Science Inventory

Matrix assisted laser desorption/ionization (MALDI) mass spectrometry was used to investigate whole and freeze thawed Cryptosporidium parvum oocysts. Whole oocysts revealed some mass spectral features. Reproducible patterns of spectral markers and increased sensitivity were obtai...

Bacteriophage cell lysis of Shiga toxin-producing Escherichia coli for top-down proteomic identification of Shiga toxin 1 & 2 using matrix-assisted laser desorption/ionization tandem time-of-light mass spectrometry

USDA-ARS?s Scientific Manuscript database

RATIONALE: Analysis of bacteria by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) often relies upon sample preparation methods that result in cell lysis, e.g. bead-beating. However, Shiga toxin-producing Escherichia coli (STEC) can undergo bacteriophage...

Rapid Identification of Cryptococcus neoformans and Cryptococcus gattii by Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry ▿

PubMed Central

McTaggart, Lisa R.; Lei, Eric; Richardson, Susan E.; Hoang, Linda; Fothergill, Annette; Zhang, Sean X.

2011-01-01

Compared to DNA sequence analysis, matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) correctly identified 100% of Cryptococcus species, distinguishing the notable pathogens Cryptococcus neoformans and C. gattii. Identification was greatly enhanced by supplementing a commercial spectral library with additional entries to account for subspecies variability. PMID:21653762

Isotopic exchange on solid-phase micro extraction fiber in sediment under stagnant conditions: Implications for field application of performance reference compound calibration.

PubMed

Bao, Lian-Jun; Wu, Xiaoqin; Jia, Fang; Zeng, Eddy Y; Gan, Jay

2016-08-01

An overlooked issue for field application of in situ performance reference compound (PRC) calibration methods is the validity of the assumption that both the sorption of a target compound and desorption of its corresponding PRC follow the first-order kinetics with the same rate constants under stagnant conditions. In the present study, disposable polydimethylsiloxane fibers of 2 sizes (7 and 35 µm) impregnated with 8 (13) C-labeled or deuterated PRCs were statically deployed into different marine sediments, from which the kinetics for sorption of the target compounds and desorption of the PRCs were characterized. Nonsymmetrical profiles were observed for exchange of the target analytes and their corresponding PRCs in sediment under stagnant conditions. The hysteretic desorption of PRCs in the kinetic regime may be ascribed to the low chemical potential between the fiber and sediment porewater, which reflects the inability of water molecules to rapidly diffuse through sediment to solvate the PRCs in the aqueous layer around the fiber surface. A moderate correlation (r = 0.77 and r = 0.57, p < 0.05 for both regressions) between the PRC-calibrated equilibrium concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl) ethylene (p,p'-DDE) and polychlorinated biphenyl (PCB)-153 and the lipid normalized levels in worms (Neanthes arenaceodentata) was obtained in co-exposure tests under simulating field conditions, probably resulting from slightly overestimated bioavailability because of the hysteretic desorption of PRCs and toxic effects. Environ Toxicol Chem 2016;35:1978-1985. © 2015 SETAC. © 2015 SETAC.

Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode?

PubMed

Chen, Y-X; Heinen, M; Jusys, Z; Behm, R J

2006-12-05

We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate.

Partially-irreversible sorption of formaldehyde in five polymers

NASA Astrophysics Data System (ADS)

Ye, Wei; Cox, Steven S.; Zhao, Xiaomin; Frazier, Charles E.; Little, John C.

2014-12-01

Due to its environmental ubiquity and concern over its potential toxicity, the mass-transfer characteristics of formaldehyde are of critical importance to indoor air quality research. Previous studies have suggested that formaldehyde mass transfer in polymer is partially irreversible. In this study, mechanisms that could cause the observed irreversibility were investigated. Polycarbonate and four other polymeric matrices were selected and subjected to formaldehyde sorption/desorption cycles. Mass transfer of formaldehyde was partially irreversible in all cases, and three potential mechanisms were evaluated. First, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis was used to investigate possible formaldehyde polymerization on polymer surfaces. ATR-FTIR showed no detectable paraformaldehyde or formaldehyde on the film surfaces that had been exposed to formaldehyde and air. ATR-FTIR did detect aliphatic acids suggesting oxidation had occurred on film surfaces as a result of exposure to formaldehyde. However, additional study suggested that air is not the primary cause for irreversibility. Second, statistical physics theory was tested as a possible explanation. According to this theory, reversible and irreversible sorption could be taking place simultaneously. The irreversible fraction should be constant during sorption and the fraction could be determined by performing a complete sorption/desorption test. The sorption/desorption data was consistent with this theory. Third, chemisorption was considered as another possible cause for irreversibility. Extraction/fluorimetry testing of post-sorption and post-desorption polymer films showed measurable quantities of formaldehyde suggesting that some of the chemisorbed formaldehyde was reversible at the higher extraction temperature. Further quantitative study on chemical reaction products is needed.

Electron- and photon-stimulated desorption of atomic hydrogen from radiation-modified alkali halide surfaces

NASA Astrophysics Data System (ADS)

Hudson, L. T.; Tolk, N. H.; Bao, C.; Nordlander, P.; Russell, D. P.; Xu, J.

2000-10-01

The desorption yields of excited hydrogen atoms from the surfaces of KCl, KBr, NaCl, NaF, and LiF have been measured as a function of incident photon and electron energy and flux, time of irradiation, dosing pressure of H2 and sample temperature. As these surfaces are exposed to H2 gas during electron or photon bombardment, the fluorescence from excited hydrogen atoms ejected from the surface is monitored. The desorption yields are found to be contingent upon surface damage induced by the incident particle radiation, leading to dissociative adsorption at surface sites containing an excess of alkali metal. A desorption mechanism is presented in which incident electrons or photons induce a valence excitation to a neutral, antibonding state of the surface alkali hydride molecule complex, leading to the desorption of hydrogen atoms possessing several eV of kinetic energy.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

Nanomaterials as Assisted Matrix of Laser Desorption/Ionization Time-of-Flight Mass Spectrometry for the Analysis of Small Molecules.

PubMed

Lu, Minghua; Yang, Xueqing; Yang, Yixin; Qin, Peige; Wu, Xiuru; Cai, Zongwei

2017-04-21

Matrix-assisted laser desorption/ionization (MALDI), a soft ionization method, coupling with time-of-flight mass spectrometry (TOF MS) has become an indispensible tool for analyzing macromolecules, such as peptides, proteins, nucleic acids and polymers. However, the application of MALDI for the analysis of small molecules (<700 Da) has become the great challenge because of the interference from the conventional matrix in low mass region. To overcome this drawback, more attention has been paid to explore interference-free methods in the past decade. The technique of applying nanomaterials as matrix of laser desorption/ionization (LDI), also called nanomaterial-assisted laser desorption/ionization (nanomaterial-assisted LDI), has attracted considerable attention in the analysis of low-molecular weight compounds in TOF MS. This review mainly summarized the applications of different types of nanomaterials including carbon-based, metal-based and metal-organic frameworks as assisted matrices for LDI in the analysis of small biological molecules, environmental pollutants and other low-molecular weight compounds.

Nanomaterials as Assisted Matrix of Laser Desorption/Ionization Time-of-Flight Mass Spectrometry for the Analysis of Small Molecules

PubMed Central

Lu, Minghua; Yang, Xueqing; Yang, Yixin; Qin, Peige; Wu, Xiuru; Cai, Zongwei

2017-01-01

Matrix-assisted laser desorption/ionization (MALDI), a soft ionization method, coupling with time-of-flight mass spectrometry (TOF MS) has become an indispensible tool for analyzing macromolecules, such as peptides, proteins, nucleic acids and polymers. However, the application of MALDI for the analysis of small molecules (<700 Da) has become the great challenge because of the interference from the conventional matrix in low mass region. To overcome this drawback, more attention has been paid to explore interference-free methods in the past decade. The technique of applying nanomaterials as matrix of laser desorption/ionization (LDI), also called nanomaterial-assisted laser desorption/ionization (nanomaterial-assisted LDI), has attracted considerable attention in the analysis of low-molecular weight compounds in TOF MS. This review mainly summarized the applications of different types of nanomaterials including carbon-based, metal-based and metal-organic frameworks as assisted matrices for LDI in the analysis of small biological molecules, environmental pollutants and other low-molecular weight compounds. PMID:28430138

Non-thermal ion desorption from an acetonitrile (CH3CN) astrophysical ice analogue studied by electron stimulated ion desorption.

PubMed

Ribeiro, F de A; Almeida, G C; Garcia-Basabe, Y; Wolff, W; Boechat-Roberty, H M; Rocco, M L M

2015-11-07

The incidence of high-energy radiation onto icy surfaces constitutes an important route for leading new neutral or ionized molecular species back to the gas phase in interstellar and circumstellar environments, especially where thermal desorption is negligible. In order to simulate such processes, an acetonitrile ice (CH3CN) frozen at 120 K is bombarded by high energy electrons, and the desorbing positive ions are analyzed by time-of-flight mass spectrometry (TOF-MS). Several fragment and cluster ions were identified, including the Hn=1-3(+), CHn=0-3(+)/NHn=0-1(+); C2Hn=0-3(+)/CHn=0-3N(+), C2Hn=0-6N(+) ion series and the ion clusters (CH3CN)n=1-2(+) and (CH3CN)n=1-2H(+). The energy dependence on the positive ion desorption yield indicates that ion desorption is initiated by Coulomb explosion following Auger electronic decay. The results presented here suggest that non-thermal desorption processes, such as desorption induced by electronic transitions (DIET) may be responsible for delivering neutral and ionic fragments from simple nitrile-bearing ices to the gas-phase, contributing to the production of more complex molecules. The derived desorption yields per electron impact may contribute to chemical evolution models in different cold astrophysical objects, especially where the abundance of CH3CN is expected to be high.

The effect of ozone on nicotine desorption from model surfaces:evidence for heterogeneous chemistry

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

Destaillats, Hugo; Singer, Brett C.; Lee, Sharon K.

Assessment of secondhand tobacco smoke exposure using nicotine as a tracer or biomarker is affected by sorption of the alkaloid to indoor surfaces and by its long-term re-emission into the gas phase. However, surface chemical interactions of nicotine have not been sufficiently characterized. Here, the reaction of ozone with nicotine sorbed to Teflon and cotton surfaces was investigated in an environmental chamber by monitoring nicotine desorption over a week following equilibration in dry or humid air (65-70 % RH). The Teflon and cotton surfaces had N{sub 2}-BET surface areas of 0.19 and 1.17 m{sup 2} g{sup -1}, and water massmore » uptakes (at 70 % RH) of 0 and 7.1 % respectively. Compared with dry air baseline levels in the absence of O{sub 3}, gas phase nicotine concentrations decrease, by 2 orders of magnitude for Teflon after 50 h at 20-45 ppb O{sub 3}, and by a factor of 10 for cotton after 100 h with 13-15 ppb O{sub 3}. The ratios of pseudo first-order rate constants for surface reaction (r) to long-term desorption (k) were r/k = 3.5 and 2.0 for Teflon and cotton surfaces, respectively. These results show that surface oxidation was competitive with desorption. Hence, oxidative losses could significantly reduce long-term re-emissions of nicotine from indoor surfaces. Formaldehyde, N-methylformamide, nicotinaldehyde and cotinine were identified as oxidation products, indicating that the pyrrolidinic N was the site of electrophilic attack by O{sub 3}. The presence of water vapor had no effect on the nicotine-O{sub 3} reaction on Teflon surfaces. By contrast, nicotine desorption from cotton in humid air was unaffected by the presence of ozone. These observations are consistent with complete inhibition of ozone-nicotine surface reactions in an aqueous surface film present in cotton but not in Teflon surfaces.« less

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

USGS Publications Warehouse

Gao, S.; Goldberg, S.; Herbel, M.J.; Chalmers, A.T.; Fujii, R.; Tanji, K.K.

2006-01-01

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching in natural environments. ?? 2006 Elsevier B.V. All rights reserved.

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

The first part of this paper (Part 1) presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work has the ability to account for both chemical absorption and desorption of CO2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry’s constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO 2) capture. In this study, to generate data for WWC model validation, CO 2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO 2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO 2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N 2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO 2 reaction rate constants after using the N 2O/CO 2 analogy method. Finally, the calibrated model can be used to predict the CO 2 mass transfer in a WWC for a wider range of operating conditions.« less

Application of the Nernst-Planck approach to lead ion exchange in Ca-loaded Pelvetia canaliculata.

PubMed

Costa, Joana F de Sá S; Vilar, Vítor J P; Botelho, Cidália M S; da Silva, Eduardo A B; Boaventura, Rui A R

2010-07-01

Ca-loaded Pelvetia canaliculata biomass was used to remove Pb(2+) in aqueous solution from batch and continuous systems. The physicochemical characterization of algae Pelvetia particles by potentiometric titration and FTIR analysis has shown a gel structure with two major binding groups - carboxylic (2.8 mmol g(-1)) and hydroxyl (0.8 mmol g(-1)), with an affinity constant distribution for hydrogen ions well described by a Quasi-Gaussian distribution. Equilibrium adsorption (pH 3 and 5) and desorption (eluents: HNO(3) and CaCl(2)) experiments were performed, showing that the biosorption mechanism was attributed to ion exchange among calcium, lead and hydrogen ions with stoichiometry 1:1 (Ca:Pb) and 1:2 (Ca:H and Pb:H). The uptake capacity of lead ions decreased with pH, suggesting that there is a competition between H(+) and Pb(2+) for the same binding sites. A mass action law for the ternary mixture was able to predict the equilibrium data, with the selectivity constants alpha(Ca)(H)=9+/-1 and alpha(Ca)(Pb)=44+/-5, revealing a higher affinity of the biomass towards lead ions. Adsorption (initial solution pH 4.5 and 2.5) and desorption (0.3M HNO(3)) kinetics were performed in batch and continuous systems. A mass transfer model using the Nernst-Planck approximation for the ionic flux of each counter-ion was used for the prediction of the ions profiles in batch systems and packed bed columns. The intraparticle effective diffusion constants were determined as 3.73x10(-7)cm(2)s(-1) for H(+), 7.56x10(-8)cm(2)s(-1) for Pb(2+) and 6.37x10(-8)cm(2)s(-1) for Ca(2+). Copyright 2010 Elsevier Ltd. All rights reserved.

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

DOE PAGES

Wang, Chao; Xu, Zhijie; Lai, Kevin; ...

2017-10-24

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO 2) capture. In this study, to generate data for WWC model validation, CO 2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO 2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO 2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N 2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO 2 reaction rate constants after using the N 2O/CO 2 analogy method. Finally, the calibrated model can be used to predict the CO 2 mass transfer in a WWC for a wider range of operating conditions.« less

Time-resolved spectroscopy at surfaces and adsorbate dynamics:insights from a model-system approach

NASA Astrophysics Data System (ADS)

Boström, Emil; Mikkelsen, Anders; Verdozzi, Claudio

We introduce a finite-system, model description of the initial stages of femtosecond laser induced desorption at surfaces. Using the exact many-body time evolution and also results from a novel time-dependent DFT description for electron-nuclear systems, we analyse the competition between several surface-response mechanisms and electronic correlations in the transient and longer time dynamics under the influence of dipole-coupled fields. Our model allows us to explore how coherent multiple-pulse protocols impact desorption in a variety of prototypical experiments.

Analysis of Phospholipid Mixtures from Biological Tissues by Matrix-Assisted Laser Desorption and Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS): A Laboratory Experiment

ERIC Educational Resources Information Center

Eibisch, Mandy; Fuchs, Beate; Schiller, Jurgen; Sub, Rosmarie; Teuber, Kristin

2011-01-01

Matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) is increasingly used to investigate the phospholipid (PL) compositions of tissues and body fluids, often without previous separation of the total mixture into the individual PL classes. Therefore, the questions of whether all PL classes are detectable…

Solid-phase microextraction coupled to liquid chromatography for the analysis of phenolic compounds in water.

PubMed

González-Toledo, E; Prat, M D; Alpendurada, M F

2001-07-20

Solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) has been applied to the analysis of priority pollutant phenolic compounds in water samples. Two types of polar fibers [50 microm Carbowax-templated resin (CW-TPR) and 60 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB)] were evaluated. The effects of equilibration time and ionic strength of samples on the adsorption step were studied. The parameters affecting the desorption process, such as desorption mode, solvent composition and desorption time, were optimized. The developed method was used to determine the phenols in spiked river water samples collected in the Douro River, Portugal. Detection limits of 1-10 microg l(-1) were achieved under the optimized conditions.

Critical factors determining the quantification capability of matrix-assisted laser desorption/ionization– time-of-flight mass spectrometry

PubMed Central

Wang, Chia-Chen; Lai, Yin-Hung; Ou, Yu-Meng; Chang, Huan-Tsung; Wang, Yi-Sheng

2016-01-01

Quantitative analysis with mass spectrometry (MS) is important but challenging. Matrix-assisted laser desorption/ionization (MALDI) coupled with time-of-flight (TOF) MS offers superior sensitivity, resolution and speed, but such techniques have numerous disadvantages that hinder quantitative analyses. This review summarizes essential obstacles to analyte quantification with MALDI-TOF MS, including the complex ionization mechanism of MALDI, sensitive characteristics of the applied electric fields and the mass-dependent detection efficiency of ion detectors. General quantitative ionization and desorption interpretations of ion production are described. Important instrument parameters and available methods of MALDI-TOF MS used for quantitative analysis are also reviewed. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644968

Laser-induced surface-plasmon desorption of dye molecules from aluminum films

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

Lee, I.; Callcott, T.A.; Arakawa, E.T.

1992-03-01

Rhodamine 8 molecules were desorbed without fragmentation from the surface of an Al film by surface-plasmon-induced desorption. Surface plasmons were excited In the Al film by the second harmonic of a Nd:YAG laser in an attenuated-to-tal-reflection (ATR) geometry. The desorbed neutrals were Ionized by a XeCl excimer laser and detected by a time-of-flight mass spectrometer. The desorption yields of both Al and rhodamine B showed a dependence with incidence angle which peaked at the plasmon resonance angle. The thresholds for desorption of Al and rhodamine B occur at the same laser fluence. Two models are proposed to explain these observations.more » 31 refs., 4 figs.« less

The desorptivity model of bulk soil-water evaporation

NASA Technical Reports Server (NTRS)

Clapp, R. B.

1983-01-01

Available models of bulk evaporation from a bare-surfaced soil are difficult to apply to field conditions where evaporation is complicated by two main factors: rate-limiting climatic conditions and redistribution of soil moisture following infiltration. Both factors are included in the "desorptivity model', wherein the evaporation rate during the second stage (the soil-limiting stage) of evaporation is related to the desorptivity parameter, A. Analytical approximations for A are presented. The approximations are independent of the surface soil moisture. However, calculations using the approximations indicate that both soil texture and soil moisture content at depth significantly affect A. Because the moisture content at depth decreases in time during redistribution, it follows that the A parameter also changes with time. Consequently, a method to calculate a representative value of A was developed. When applied to field data, the desorptivity model estimated cumulative evaporation well. The model is easy to calculate, but its usefulness is limited because it requires an independent estimate of the time of transition between the first and second stages of evaporation. The model shows that bulk evaporation after the transition to the second stage is largely independent of climatic conditions.

2D particle-in-cell simulation of the entire process of surface flashover on insulator in vacuum

NASA Astrophysics Data System (ADS)

Wang, Hongguang; Zhang, Jianwei; Li, Yongdong; Lin, Shu; Zhong, Pengfeng; Liu, Chunliang

2018-04-01

With the introduction of an external circuit model and a gas desorption model, the surface flashover on the plane insulator-vacuum interface perpendicular to parallel electrodes is simulated by a Particle-In-Cell method. It can be seen from simulations that when the secondary electron emission avalanche (SEEA) occurs, the current sharply increases because of the influence of the insulator surface charge on the cathode field emission. With the introduction of the gas desorption model, the current keeps on increasing after SEEA, and then the feedback of the external circuit causes the voltage between the two electrodes to decrease. The cathode emission current decreases, while the anode current keeps growing. With the definition that flashover occurs when the diode voltage drops by more than 20%, we obtained the simulated flashover voltage which agrees with the experimental value with the use of the field enhancement factor β = 145 and the gas molecule desorption coefficient γ=0.25 . From the simulation results, we can also see that the time delay of flashover decreases exponentially with voltage. In addition, from the gas desorption model, the gas density on the insulator surface is found to be proportional to the square of the gas desorption rate and linear with time.

LASER DESORPTION IONIZATION OF ULTRAFINE AEROSOL PARTICLES. (R823980)

EPA Science Inventory

On-line analysis of ultrafine aerosol particle in the 12 to 150 nm size range is performed by
laser desorption/ionization. Particles are size selected with a differential mobility analyzer and then
sent into a linear time-of-flight mass spectrometer where they are ablated w...

Plume Image Profiling of UV Laser Desorbed Biomolecules

NASA Astrophysics Data System (ADS)

Merrigan, T. L.; Hunniford, C. A.; Timson, D. J.; Catney, M.; McCullough, R. W.

2008-12-01

An experimental system, based upon the techniques of UV and IR laser desorption with time of flight mass spectrometry, has been constructed to enable the production and characterization of neutral biomolecular targets. The feasibility of the laser desorption technique for the purpose of radiation interaction experiments is investigated here. Fluorescent dye tagging and laser induced fluorescence imaging has been used to help characterize the laser produced plumes of biomolecules revealing their spatial density profiles and temporal evolution. Peak target thicknesses of 2×1012 molecules cm-2 were obtained 30 μs after laser desorption.

Density matrix approach to the hot-electron stimulated photodesorption

NASA Astrophysics Data System (ADS)

Kühn, Oliver; May, Volkhard

1996-07-01

The dissipative dynamics of the laser-induced nonthermal desorption of small molecules from a metal surface is investigated here. Based on the density matrix formalism a multi-state model is introduced which explicitly takes into account the continuum of electronic states in the metal. Various relaxation mechanisms for the electronic degrees of freedom are shown to govern the desorption dynamics and hence the desorption probability. Particular attention is paid to the modeling of the time dependence of the electron energy distribution in the metal which reflects different excitation conditions.

Dynamic Moisture Sorption and Desorption in Fumed Silica-filled Silicone Foam

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

Trautschold, Olivia Carol

Characterizing dynamic moisture sorption and desorption in fumed silica-filled silicone foam is necessary for determining material compatibilities and life predictions, particularly in sealed environments that may be exposed to a range of environmental conditions. Thermogravimetric analysis (TGA) and near infrared spectroscopy (NIR) were performed on S5470 fumed silica-filled silicone foam to determine the weight percent of moisture at saturation. Additionally, TGA was used to determine the time, temperature, and relative humidity levels required for sorption and desorption of physisorbed moisture in S5470.

Proceedings (1st) of the Topical Meeting on the Microphysics of Surfaces, Beams, and Adsorbates Held in Santa Fe, New Mexico on 4-6 February 1985.

DTIC Science & Technology

1985-12-18

by other molecules within the area of irradiation were desorbed with methods. Therefore, the laser thermal desorption techrique a single pulse . This...of 30 ns irradiated on W surfaces covered with D face temperature raised by a laser pulse . The problem asso- atoms. D, desorption time-of-flight was...surface region which cm- I.2411a The desorption yield (Y) dependence on the laser was not irradiated by the laser pulses . The diffusion coeffi

Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry.

PubMed

Feng, Dan; Xia, Yan

2018-07-19

Covalent organic framework (COF) was explored as a novel matrix with a high desorption/ionization efficiency for direct detection of small molecules by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). By using COF as an LDI MS matrix, we could detect not only biological micro molecules such as amino acids and fatty acids, but also emerging environmental pollutants like bisphenol S (BPS) and pyrene. With COF as the matrix, higher desorption/ionization efficiency, and less background interference were achieved than the conventional organic matrices. Good salt tolerance (as high as 500 mM NaCl) and repeatability allowed the detection limit of amino acids was 90 fmol. In addition, COF matrix performed well for amino acids analysis in the honey sample. The ionization mechanism was also discussed. These results demonstrate that COF is a powerful matrix for small molecules analysis in real samples by MS. Copyright © 2018 Elsevier B.V. All rights reserved.

Bacterial desorption from food container and food processing surfaces.

PubMed

McEldowney, S; Fletcher, M

1988-03-01

The desorption ofStaphylococcus aureus, Acinetobacter calcoaceticus, and a coryneform from the surfaces of materials used for manufacturing food containers (glass, tin plate, and polypropylene) or postprocess canning factory conveyor belts (stainless steel and nylon) was investigated. The effect of time, pH, temperature, and adsorbed organic layers on desorption was studied.S. aureus did not detach from the substrata at any pH investigated (between pH 5 and 9).A. calcoaceticus and the coryneform in some cases detached, depending upon pH and substratum composition. The degree of bacterial detachment from the substrata was not related to bacterial respiration at experimental pH values. Bacterial desorption was not affected by temperature (4-30°C) nor by an adsorbed layer of peptone and yeast extract on the substrata. The results indicate that bacterial desorption, hence bacterial removal during cleaning or their transfer via liquids flowing over colonized surfaces, is likely to vary with the surface composition and the bacterial species colonizing the surfaces.

Effect of experimental variables onto Co(2+) and Sr(2+) sorption behavior in red mud-water suspensions.

PubMed

Milenković, Aleksandra S; Smičiklas, Ivana D; Šljivić-Ivanović, Marija Z; Živković, Ljiljana S; Vukelić, Nikola S

2016-07-02

The prospects of rinsed red mud (alumina production residue) utilization for liquid radioactive waste treatment have been investigated, with Co(2+) and Sr(2+) as model cations of radioactive elements. To evaluate the sorption effectiveness and corresponding binding mechanisms, the process was analyzed in batch conditions, by varying experimental conditions (pH, Co(2+) and Sr(2+) concentrations in single solutions and binary mixtures, contact time, and the concentration of competing cations and ligands common in liquid radioactive waste). Comparison of the Co(2+) and Sr(2+) sorption pH edges with the red mud isoelectric point has revealed that Co(2+) removal took place at both positive and negative red mud surface, while Sr(2+) sorption abruptly increased when the surface became negatively charged. The increase of initial cation content and pH resulted in increased equilibrium times and sorption capacity and decreased rate constants. From single metal solutions and various binary mixtures, Co(2+) was sorbed more efficiently and selectively than Sr(2+). While Sr(2+) sorption was reduced by coexisting cations in the order Al(3+) ≥ Ca(2+) >Na(+) ≥Cs(+), removal of Co(2+) was affected by Al(3+) species and complexing agents (EDTA and citrate). Desorption of Co(2+) was negligible in Ca(2+) and Sr(2+) containing media and in solutions with initial pH 4-7. Sr(2+) desorption was generally more pronounced, especially at low pH and in the presence of Co(2+). Collected macroscopic data signify that Co(2+) sorption by red mud minerals occurred via strong chemical bonds, while Sr(2+) was retained mainly by weaker ion-exchange or electrostatic interactions. Results indicate that the rinsed red mud represent an efficient, low-cost sorbent for Co(2+) and Sr(2+) immobilization.

Investigation into the feasibility of black carbon for remediation of nonylphenol polluted sediment through desorption kinetics after different order spiking.

PubMed

Cheng, Guanghuan; Sun, Mingyang; Yao, Lingdan; Wang, Lixiao; Sorial, George A; Xu, Xinhua; Lou, Liping

2015-11-01

The binding order of sorbent, sediment and organic compounds, as well as binding time is important factors determining the potential success of sorbent amendment, which should be considered when the practicability of sorbents was assessed. But until now, relevant research was rare. In this study, desorption in three practical conditions were simulated, by three mixing spiking orders among nonylphenol (NP), rice straw black carbon (RC) and sediment (the order of mixing spiking is (RC+Sediment)+NP, (Sediment+NP)+RC and (RC+NP)+Sediment, for situation I, II and III, respectively), to discuss the feasibility of using RC to remedy NP pollution. Results demonstrated that amendment of RC into sediment decreased desorption fractions of NP, and increased the resistant desorption fraction (Fr), implying strong affinity of NP to RC and efficient sequestration by RC. No significant differences were observed for desorption among the three fresh situations, meaning NP may be adsorbed on RC exterior surface sites and inter-phase diffusion is faster than desorption. However, Fr for three aged situations was in the order: situation I0.5, suggesting RC is an effective sorbent for remedying NP pollution in the aquatic environment. Overall, we proposed a practical and analytical method for properly assessing the validity of a sorbent. Copyright © 2015. Published by Elsevier Ltd.

Assessment of bioavailability of soil-sorbed atrazine.

PubMed

Park, Jeong-Hun; Feng, Yucheng; Ji, Pingsheng; Voice, Thomas C; Boyd, Stephen A

2003-06-01

Bioavailability of pesticides sorbed to soils is an important determinant of their environmental fate and impact. Mineralization of sorbed atrazine was studied in soil and clay slurries, and a desorption-biodegradation-mineralization (DBM) model was developed to quantitatively evaluate the bioavailability of sorbed atrazine. Three atrazine-degrading bacteria that utilized atrazine as a sole N source (Pseudomonas sp. strain ADP, Agrobacterium radiobacter strain J14a, and Ralstonia sp. strain M91-3) were used in the bioavailability assays. Assays involved establishing sorption equilibrium in sterile soil slurries, inoculating the system with organisms, and measuring the CO(2) production over time. Sorption and desorption isotherm analyses were performed to evaluate distribution coefficients and desorption parameters, which consisted of three desorption site fractions and desorption rate coefficients. Atrazine sorption isotherms were linear for mineral and organic soils but displayed some nonlinearity for K-saturated montmorillonite. The desorption profiles were well described by the three-site desorption model. In many instances, the mineralization of atrazine was accurately predicted by the DBM model, which accounts for the extents and rates of sorption/desorption processes and assumes biodegradation of liquid-phase, but not sorbed, atrazine. However, for the Houghton muck soil, which manifested the highest sorbed atrazine concentrations, enhanced mineralization rates, i.e., greater than those expected on the basis of aqueous-phase atrazine concentration, were observed. Even the assumption of instantaneous desorption could not account for the elevated rates. A plausible explanation for enhanced bioavailability is that bacteria access the localized regions where atrazine is sorbed and that the concentrations found support higher mineralization rates than predicted on the basis of aqueous-phase concentrations. Characteristics of high sorbed-phase concentration, chemotaxis, and attachment of cells to soil particles seem to contribute to the bioavailability of soil-sorbed atrazine.

Assessment of Bioavailability of Soil-Sorbed Atrazine

PubMed Central

Park, Jeong-Hun; Feng, Yucheng; Ji, Pingsheng; Voice, Thomas C.; Boyd, Stephen A.

2003-01-01

Bioavailability of pesticides sorbed to soils is an important determinant of their environmental fate and impact. Mineralization of sorbed atrazine was studied in soil and clay slurries, and a desorption-biodegradation-mineralization (DBM) model was developed to quantitatively evaluate the bioavailability of sorbed atrazine. Three atrazine-degrading bacteria that utilized atrazine as a sole N source (Pseudomonas sp. strain ADP, Agrobacterium radiobacter strain J14a, and Ralstonia sp. strain M91-3) were used in the bioavailability assays. Assays involved establishing sorption equilibrium in sterile soil slurries, inoculating the system with organisms, and measuring the CO2 production over time. Sorption and desorption isotherm analyses were performed to evaluate distribution coefficients and desorption parameters, which consisted of three desorption site fractions and desorption rate coefficients. Atrazine sorption isotherms were linear for mineral and organic soils but displayed some nonlinearity for K-saturated montmorillonite. The desorption profiles were well described by the three-site desorption model. In many instances, the mineralization of atrazine was accurately predicted by the DBM model, which accounts for the extents and rates of sorption/desorption processes and assumes biodegradation of liquid-phase, but not sorbed, atrazine. However, for the Houghton muck soil, which manifested the highest sorbed atrazine concentrations, enhanced mineralization rates, i.e., greater than those expected on the basis of aqueous-phase atrazine concentration, were observed. Even the assumption of instantaneous desorption could not account for the elevated rates. A plausible explanation for enhanced bioavailability is that bacteria access the localized regions where atrazine is sorbed and that the concentrations found support higher mineralization rates than predicted on the basis of aqueous-phase concentrations. Characteristics of high sorbed-phase concentration, chemotaxis, and attachment of cells to soil particles seem to contribute to the bioavailability of soil-sorbed atrazine. PMID:12788728

Performance and cost analysis of matrix-assisted laser desorption ionization-time of flight mass spectrometry for routine identification of yeast.

PubMed

Dhiman, Neelam; Hall, Leslie; Wohlfiel, Sherri L; Buckwalter, Seanne P; Wengenack, Nancy L

2011-04-01

Matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry was compared to phenotypic testing for yeast identification. MALDI-TOF mass spectrometry yielded 96.3% and 84.5% accurate species level identifications (spectral scores, ≥ 1.8) for 138 common and 103 archived strains of yeast. MALDI-TOF mass spectrometry is accurate, rapid (5.1 min of hands-on time/identification), and cost-effective ($0.50/sample) for yeast identification in the clinical laboratory.

Changes in metal availability, desorption kinetics and speciation in contaminated soils during repeated phytoextraction with the Zn/Cd hyperaccumulator Sedum plumbizincicola.

PubMed

Li, Zhu; Jia, Mingyun; Wu, Longhua; Christie, Peter; Luo, Yongming

2016-02-01

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorption-desorption equilibrium and diffusion of tetracycline in poultry litter and municipal biosolids soil amendments.

PubMed

D'Angelo, E

2017-12-01

Tetracycline (TET) is commonly used to treat bacterial diseases in humans and chickens (Gallus gallus domesticus), is largely excreted, and is found at elevated concentrations in treated sewage sludge (biosolids) and poultry litter (excrement plus bedding materials). Routine application of these nutrient-and carbon-enriched materials to soils improves fertility and other characteristics, but the presence of antibiotics (and other pharmaceuticals) in amendments raises questions about potential adverse effects on biota and development of antibiotic resistance in the environment. Hazard risks are largely dictated by sorption-desorption and diffusion behavior in amendments, so these processes were evaluated from sorption-desorption equilibrium isotherm and diffusion cell experiments with four types amendments (biosolids, poultry manure, wood chip litter, and rice hull litter) at three temperatures (8 °C, 20 °C and 32 °C). Linear sorption-desorption equilibrium distribution constants (Kd) in native amendments ranged between 124-2418 L kg -1 . TET sorption was significantly increased after treatment with alum, and there was a strong exponential relationship between Kd and the concentration of bound Al 3+ in amendments (R 2  = 0.94), which indicated that amendments contained functional groups capable of chelating Al 3+ and forming metal bridges with TET. Effective diffusion coefficients of TET in amendments ranged between 0.1 and 5.2 × 10 -6  cm 2  s -1 , which were positively related to temperature and inversely related to Kd by a multiple regression model (R 2  = 0.86). Treatment of organic amendments with alum greatly increased Kd, would decrease D s , and so would greatly reduce hazard risks of applying these organic amendments with this antibiotic to soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

2015-06-01

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

PubMed Central

Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

2015-01-01

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary. PMID:26047466

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons.

PubMed

Mitropoulos, A C; Stefanopoulos, K L; Favvas, E P; Vansant, E; Hankins, N P

2015-06-05

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of 'ink-bottle' pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

Role of organic matter on boron adsorption-desorption hysteresis of soils

USDA-ARS?s Scientific Manuscript database

In this study we evaluated the boron (B) adsorption/desorption reaction in six soils and examined the extent to which organic matter content, as well as incubation time affected B release. Six soils varying in initial pH, clay content, and were selected for the study. Adsorption experiments were c...

Laser-desorption tandem time-of-flight mass spectrometry with continuous liquid introduction

NASA Astrophysics Data System (ADS)

Williams, Evan R.; Jones, Glenn C., Jr.; Fang, LiLing; Nagata, Takeshi; Zare, Richard N.

1992-05-01

A new method to combine aqueous sample introduction with matrix assisted laser desorption mass spectrometry (MS) for interfacing liquid-chromatographic techniques, such as capillary electrophoresis, to MS is described. Aqueous sample solution is introduced directly into the ion source of a time-of-. flight (TOF) mass spectrometer through a fused silica capillary; evaporative cooling results in ice formation at the end of the capillary. The ice can be made to extrude continuously by using localized resistive heating. With direct laser desorption, molecular ions from proteins as large as bovine insulin (5734 Da) can be produced. Two-step desorption/photoionization with a variety of wavelengths is demonstrated, and has the advantages of improved resolution and shot-to-shot reproducibility. Ion structural information is obtained using surface-induced dissociation with an in-line collision device in the reflectron mirror of the TOF instrument. Product ion resolution of ~70 is obtained at m/z77. Extensive fragmentation can be produced with dissociation efficiencies between 7-15% obtained for molecular ions of small organic molecules. Efficiencies approaching 30% are obtained for larger peptide ions.

Removal of sudan dyes from water with C18-functional ultrafine magnetic silica nanoparticles.

PubMed

Jiang, Chunzhu; Sun, Ying; Yu, Xi; Zhang, Lei; Sun, Xiumin; Gao, Yan; Zhang, Hanqi; Song, Daqian

2012-01-30

In this study, the new C(18)-functionalized ultrafine magnetic silica nanoparticles (C(18)-UMS NPs) were successfully synthesized and applied for extraction of sudan dyes in water samples based on the magnetic solid-phase extraction (MSPE). The extraction and concentration were carried out in one step by blending C(18)-UMS NPs and water samples. The sudan dyes adsorbed C(18)-UMS NPs were isolated from the matrix easily with an external magnetic field. After desorption the quantitation of sudan dyes was done by ultra fast liquid chromatography (UFLC). Satisfactory extraction recovery can be obtained with only 50 mg C(18)-UMS NPs. The effects of experimental parameters, including the amount of the nanoparticles, extraction time, pH value, desorption solvent, volume of desorption solvent and desorption time were investigated. The limits of detection for sudan I, II, III and IV were 0.066, 0.070, 0.12 and 0.12 ng mL(-1), respectively. Recoveries obtained by analyzing the six spiked water samples were between 68% and 103%. Copyright © 2011 Elsevier B.V. All rights reserved.

Matrix-assisted laser desorption ionization-time of flight mass spectrometry for direct bacterial identification from positive blood culture pellets.

PubMed

Prod'hom, Guy; Bizzini, Alain; Durussel, Christian; Bille, Jacques; Greub, Gilbert

2010-04-01

An ammonium chloride erythrocyte-lysing procedure was used to prepare a bacterial pellet from positive blood cultures for direct matrix-assisted laser desorption-ionization time of flight (MALDI-TOF) mass spectrometry analysis. Identification was obtained for 78.7% of the pellets tested. Moreover, 99% of the MALDI-TOF identifications were congruent at the species level when considering valid scores. This fast and accurate method is promising.

[Application of Stir Bar Sorptive Extraction and Gas Chromatograph Mass Spectrometer to the Phthalic Acid Esters Analysis in Seawater].

PubMed

Gao, Chen-chen; Li, Feng-min; Lu, Lun; Sun, Yue

2015-10-01

For the determination of trace amounts of phthalic acid esters (PAEs) in complex seawater matrix, a stir bar sorptive extraction gas chromatography mass spectrometry (SBSE-GC-MS) method was established. Dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), dibutyl phthalate (2-ethylhexyl) phthalate (DEHP) and dioctyl phthalate (DOP) were selected as study objects. The effects of extraction time, amount of methanol, amount of sodium chloride, desorption time and desorption solvent were optimized. The method of SBSE-GC-MS was validated through recoveries and relative standard deviation. The optimal extraction time was 2 h. The optimal methanol content was 10%. The optimal sodium chloride content was 5% . The optimal desorption time was 50 min. The optimal desorption solvent was the mixture of methanol to acetonitrile (4:1, volume: volume). The linear relationship between the peak area and the concentration of PAEs was relevant. The correlation coefficients were greater than 0.997. The detection limits were between 0.25 and 174.42 ng x L(-1). The recoveries of different concentrations were between 56.97% and 124.22% . The relative standard deviations were between 0.41% and 14.39%. On the basis of the method, several estuaries water sample of Jiaozhou Bay were detected. DEP was detected in all samples, and the concentration of BBP, DEHP and DOP were much higher than the rest.

Reaction-Mediated Desorption of Macromolecules: Novel Phenomenon Enabling Simultaneous Reaction and Separation.

PubMed

Isakari, Yu; Kishi, Yuhi; Yoshimoto, Noriko; Yamamoto, Shuichi; Podgornik, Aleš

2018-02-02

Combining chemical reaction with separation offers several advantages. In this work possibility to induce spontaneous desorption of adsorbed macromolecules, once being PEGylated, through adjustment of the reagent composition is investigated. Bovine serum albumin (BSA) and activated oligonucleotide, 9T, are used as the test molecules and 20 kDa linear activated PEG is used for their PEGylation. BSA solid-phase PEGylation is performed on Q Sepharose HP. Distribution coefficient of BSA and PEG-BSA as a function of NaCl is determined using linear gradient elution (LGE) experiments and Yamamoto model. According to the distribution coefficient the selectivity between BSA and PEG - BSA of around 15 is adjusted by using NaCl. Spontaneous desorption of PEG - BSA is detected with no presence of BSA. However, due to a rather low selectivity, also desorption of BSA occurred at high elution volume. A similar procedure is applied for activated 9T oligonucleotide, this time using monolithic CIM QA disk monolithic column for adsorption. Selectivity of over 2000 is obtained by proper adjustment of PEG reagent composition. High selectivity enables spontaneous desorption of PEG-9T without any desorption of activated 9T. Both experiments demonstrates that reaction-mediated desorption of macromolecules is possible when the reaction conditions are properly tuned. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of stream reaeration coefficients by use of tracers

USGS Publications Warehouse

Kilpatrick, F.A.; Rathbun, R.E.; Yotsukura, Nobuhiro; Parker, G.W.; DeLong, L.L.

1989-01-01

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes. Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed whereby a radioactive tracer gas was injected into a stream-the principle being that the tracer gas would be desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas. This manual describes the slug-injection and constant-rate-injection methods of measuring gas-tracer desorption. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, on methods of injection, sampling, and analysis, and on techniques for computing desorption and reaeration coefficients.

Binding of the water of primary hydration to the sodium and cesium salts of deoxyribonucleic acid and potassium hyaluronate

NASA Astrophysics Data System (ADS)

Whitson, K. B.; Lukan, A. M.; Marlowe, R. L.; Lee, S. A.; Anthony, L.; Rupprecht, A.

1998-08-01

Differential scanning calorimetry (DSC) has been used to evaluate the average enthalpy of desorption of the water of primary hydration bound to wet-spun films of potassium hyaluronate (KHA) and CsDNA. The enthalpies were measured to be 0.24+/-0.08 eV/H2O molecule for KHA and 0.32+/-0.10 eV/H2O molecule for CsDNA. A Kissinger analysis was used to extract the net activation energy (0.61+/-0.04 eV) for the desorption of this water from KHA by analyzing DSC data acquired at different heating rates. The average effective force constants at 295 K of this water bound to KHA (63+/-3 μdyn/Å) and NaDNA (17+/-4 μdyn/Å) are determined from Rayleigh scattering of Mossbauer radiation data [G. Albanese, A. Deriu, F. Cavatorta, and A. Rupprecht, Hyperfine Interact. 95, 97 (1995)] via a harmonic approximation.

Biosorption of copper by marine algae Gelidium and algal composite material in a packed bed column.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Loureiro, José M; Boaventura, Rui A R

2008-09-01

Marine algae Gelidium and algal composite material were investigated for the continuous removal of Cu(II) from aqueous solution in a packed bed column. The biosorption behaviour was studied during one sorption-desorption cycle of Cu(II) in the flow through column fed with 50 and 25 mg l(-1) of Cu(II) in aqueous solution, at pH 5.3, leading to a maximum uptake capacity of approximately 13 and 3 mg g(-1), respectively, for algae Gelidium and composite material. The breakthrough time decreases as the inlet copper concentration increases, for the same flow rate. The pH of the effluent decreases over the breakthrough time of copper ions, which indicates that ion exchange is one of the mechanisms involved in the biosorption process. Temperature has little influence on the metal uptake capacity and the increase of the ionic strength reduces the sorption capacity, decreasing the breakthrough time. Desorption using 0.1M HNO(3) solution was 100% effective. After two consecutive sorption-desorption cycles no changes in the uptake capacity of the composite material were observed. A mass transfer model including film and intraparticle resistances, and the equilibrium relationship, for adsorption and desorption, was successfully applied for the simulation of the biosorption column performance.

Thermal desorption comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry for vapour phase mainstream tobacco smoke analysis.

PubMed

Savareear, Benjamin; Brokl, Michał; Wright, Chris; Focant, Jean-Francois

2017-11-24

A thermal desorption comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (TD-GC×GC-TOFMS) method has been developed for the analysis of mainstream tobacco smoke (MTS) vapour phase (VP). The selection process of the sample introduction approach involved comparing the results obtained from three different approaches: a) use of gas sampling bag followed by SPME (Tedlar ® -SPME), b) gas sampling bag followed by TD (Tedlar ® -TD), and c) sampling directly on TD sorbents (Direct-TD). Six different SPME fibers and six different TD sorbent beds were evaluated for the extraction capacities in terms of total number of peaks and related intensities or peak areas. The best results were obtained for the Direct-TD approach using Tenax TA/Carbograph1TD/Carboxen1003 sorbent tubes. The optimisation of TD tube desorption parameters was carried out using a face-centered central composite experimental design and resulted in the use of the Tenax TA/Carbograph 1TD/Carboxen 1003 sorbent with a 7.5min desorption time, a 60mL/min tube desorption flow, and a 250°C tube desorption temperature. The optimised method was applied to the separation of MTS-VP constituents, with 665 analytes detected. The method precision ranged from 1% to 15% for over 99% of identified peak areas and from 0% to 3% and 0% to 1% for both first ( 1 t R ) and second ( 2 t R ) dimension retention times, respectively. The method was applied to the analyses of two cigarette types differing in their filter construction. Principal component analysis (PCA) allowed a clear differentiation of the studied cigarette types (PC1 describing 94% of the explained variance). Supervised Fisher ratio analysis permitted the identification of compounds responsible for the chemical differences between the two sample types. A set of 91 most relevant compounds was selected by applying a Fisher ratio cut-off approach and most of them were selectively removed by one of the cigarette filter types. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of glyphosate transport through suspended particulate matter

NASA Astrophysics Data System (ADS)

Amiot, Audrey; Landry, David; Jadas-Hécart, Alain; La Jeunesse, Isabelle; Sourice, Stéphane; Ballouche, Aziz

2014-05-01

The results have been produced in a project aiming to improve the water quality of the Layon localy supported by stakeholders involved in the implementation of the Water Framework Directive as the SAGE-Layon Aubance. The study site is a small vineyard catchment (2.2 ha) of the Loire Valley. The slopes of the study site are between 8 and 40% resulting in strong erosive episodes during rainy event. The main objective is to understand the transfer of pesticide residues to stream. Preliminary results have shown glyphosate can be found with high concentrations during runoff. However this study was realized only in the dissolved phase. The objective is now to understand the glyphosate transport driven by SPM. The methodology developed has been (i) characterization and production of the erodible water fraction from soils aggregates; (ii) achievement of the adsorption of glyphosate on these erodible materials to compare this results with adsorption on soil sieved to 2 mm, (iii) achievement of the desorption of glyphosate on these erodible materials. Measurements have been performed on soil samples distinguishing weed or grassed soils. Soils are sieved to 2 mm or between 2 and 5 mm (to produce the erodible water fraction). Both fractions are then used to glyphosate sorption and desorption. The erodible fraction was produce with a wet sieving machine (eijkelkampt Method Kemper and Rosenau, 1986), using sieve porosity of 250 microns. The fraction obtained at 250 microns is considered to be the erodible water fraction and is used to study the adsorption and desorption of glyphosate. Kinetics has been first carried out then the isotherm to obtain the value of Kd. A ratio soil/solution of 1/5 was used. Successive desorption's method was chosen with a stirring time of 20 min, centrifugation at 6000 g and the supernatant in each desorption of 20 min is analyzed. This step is repeated 25 times. The main results of the study are: (i) adsorption of glyphosate is rapid and almost complete (95% in 2 min). (ii) Kd obtained on the erodible fraction are two times higher than on 2 mm sieved soils. (iii) Desorption showed that glyphosate is desorbed from the erodible fraction at 40% after 25 desorptions. The aim of this study was to show the potential transport of glyphosate through suspended particulate matter. The adsorption on the erodible fraction argued to a significant transport potential of glyphosate on this fraction. The desorption of glyphosate from the erodible water fraction have revealed that the adsorption of glyphosate is reversible but it is much slower. These results demonstrate that glyphosate may be stored on the erodible fraction and be transported by these fractions. Keywords: Adsorption, Desorption, Glyphosate, Suspended Solids, Erosion.

Detection of Nonvolatile Inorganic Oxidizer-Based Explosives from Wipe Collections by Infrared Thermal Desorption-Direct Analysis in Real Time Mass Spectrometry.

PubMed

Forbes, Thomas P; Sisco, Edward; Staymates, Matthew

2018-05-07

Infrared thermal desorption (IRTD) was coupled with direct analysis in real time mass spectrometry (DART-MS) for the detection of both inorganic and organic explosives from wipe collected samples. This platform generated discrete and rapid heating rates that allowed volatile and semivolatile organic explosives to thermally desorb at relatively lower temperatures, while still achieving elevated temperatures required to desorb nonvolatile inorganic oxidizer-based explosives. IRTD-DART-MS demonstrated the thermal desorption and detection of refractory potassium chlorate and potassium perchlorate oxidizers, compounds difficult to desorb with traditional moderate-temperature resistance-based thermal desorbers. Nanogram to sub-nanogram sensitivities were established for analysis of a range of organic and inorganic oxidizer-based explosive compounds, with further enhancement limited by the thermal properties of the most common commercial wipe materials. Detailed investigations and high-speed visualization revealed conduction from the heated glass-mica base plate as the dominant process for heating of the wipe and analyte materials, resulting in thermal desorption through boiling, aerosolization, and vaporization of samples. The thermal desorption and ionization characteristics of the IRTD-DART technique resulted in optimal sensitivity for the formation of nitrate adducts with both organic and inorganic species. The IRTD-DART-MS coupling and IRTD in general offer promising explosive detection capabilities to the defense, security, and law enforcement arenas.

Comparison of a disposable sorptive sampler with thermal desorption in a gas chromatographic inlet, or in a dedicated thermal desorber, to conventional stir bar sorptive extraction-thermal desorption for the determination of micropollutants in water.

PubMed

Wooding, Madelien; Rohwer, Egmont R; Naudé, Yvette

2017-09-01

The presence of micropollutants in the aquatic environment is a worldwide environmental concern. The diversity of micropollutants and the low concentration levels at which they may occur in the aquatic environment have greatly complicated the analysis and detection of these chemicals. Two sorptive extraction samplers and two thermal desorption methods for the detection of micropollutants in water were compared. A low-cost, disposable, in-house made sorptive extraction sampler was compared to SBSE using a commercial Twister sorptive sampler. Both samplers consisted of polydimethylsiloxane (PDMS) as a sorptive medium to concentrate micropollutants. Direct thermal desorption of the disposable samplers in the inlet of a GC was compared to conventional thermal desorption using a commercial thermal desorber system (TDS). Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was used for compound separation and identification. Ten micropollutants, representing a range of heterogeneous compounds, were selected to evaluate the performance of the methods. The in-house constructed sampler, with its associated benefits of low-cost and disposability, gave results comparable to commercial SBSE. Direct thermal desorption of the disposable sampler in the inlet of a GC eliminated the need for expensive consumable cryogenics and total analysis time was greatly reduced as a lengthy desorption temperature programme was not required. Limits of detection for the methods ranged from 0.0010 ng L -1 to 0.19 ng L -1 . For most compounds, the mean (n = 3) recoveries ranged from 85% to 129% and the % relative standard deviation (% RSD) ranged from 1% to 58% with the majority of the analytes having a %RSD of less than 30%. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of Culture Media on Detection of Carbapenem Hydrolysis by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

PubMed

Ramos, Ana Carolina; Carvalhaes, Cecília Godoy; Cordeiro-Moura, Jhonatha Rodrigo; Rockstroh, Anna Carolina; Machado, Antonia Maria Oliveira; Gales, Ana Cristina

2016-07-01

In this study, we evaluated the influence of distinct bacterial growth media on detection of carbapenemase hydrolysis by matrix-assisted laser desorption ionization-time of flight mass spectrometry. False-negative results were observed for OXA-25-, OXA-26-, and OXA-72-producing Acinetobacter baumannii isolates grown on MacConkey agar medium. The other culture media showed 100% sensitivity and 100% specificity for detecting carbapenemase. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Identification of Non-diphtheriae Corynebacterium by Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

PubMed Central

Alatoom, Adnan A.; Cazanave, Charles J.; Cunningham, Scott A.; Ihde, Sherry M.

2012-01-01

We evaluated the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry for identification of 92 clinical isolates of Corynebacterium species in comparison to identification using rpoB or 16S rRNA gene sequencing. Eighty isolates (87%) yielded a score of ≥1.700, and all of these were correctly identified to the species level with the exception of Corynebacterium aurimucosum being misidentified as the closely related Corynebacterium minutissimum. PMID:22075579

Use of Infrared Spectrometry to Determine the Effect of Trichloroethylene Resident Time on Desorption Rates from Flint Clay

DTIC Science & Technology

1994-08-01

processing industry as an extraction agent to decaffeinate coffee (1:3-5). The Air Force has been using TCE to degrease aircraft, aircraft parts, cleaning...contribution of surface charge to the overall absorption process . Another distinction between the two studies is that one used soil with a small amount...had to be taken to keep from adding liquid nitrogen to the detectors at critical times in the desorption process . 58 When the intensity readings

Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry for Caspofungin Susceptibility Testing of Candida and Aspergillus Species

PubMed Central

De Carolis, Elena; Vella, Antonietta; Florio, Ada R.; Posteraro, Patrizia; Perlin, David S.; Posteraro, Brunella

2012-01-01

Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) was evaluated for testing susceptibility to caspofungin of wild-type and fks mutant isolates of Candida and Aspergillus. Complete essential agreement was observed with the CLSI reference method, with categorical agreement for 94.1% of the Candida isolates tested. Thus, MALDI-TOF MS is a reliable and accurate method to detect fungal isolates with reduced caspofungin susceptibility. PMID:22535984

Use of matrix-assisted laser desorption ionization-time of flight mass spectrometry for caspofungin susceptibility testing of Candida and Aspergillus species.

PubMed

De Carolis, Elena; Vella, Antonietta; Florio, Ada R; Posteraro, Patrizia; Perlin, David S; Sanguinetti, Maurizio; Posteraro, Brunella

2012-07-01

Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was evaluated for testing susceptibility to caspofungin of wild-type and fks mutant isolates of Candida and Aspergillus. Complete essential agreement was observed with the CLSI reference method, with categorical agreement for 94.1% of the Candida isolates tested. Thus, MALDI-TOF MS is a reliable and accurate method to detect fungal isolates with reduced caspofungin susceptibility.

Carbon isotopic fractionation of CH4 and CO2 during canister desorption of coal

USGS Publications Warehouse

Strapoc, D.; Schimmelmann, A.; Mastalerz, Maria

2006-01-01

Canister desorption of coal gas from freshly sampled coal is commonly used for exploratory assessment of the coalbed methane (CBM) potential of a basin or prospect, as well as for the sampling of gas for isotopic determination of the gas origin. Compositional and ??13C isotopic time-series of desorbing CBM and carbon dioxide (CO2) over 3-4 months demonstrate considerable compositional and isotopic shifts over time. Non-stationary chemical and isotopic characteristics are due to differences in diffusivity and adsorbance behavior of gas molecules and must be taken into account when attempting to reproducibly sample coal gases. Off-line gas processing on a vacuum line and on-line GC/MS analyses were performed on coal gas samples from the Springfield and Seelyville Coal Members of the Pennsylvanian age that were cored in the SE Illinois Basin in SW Indiana, USA. The coals cover a narrow range of maturity from 0.54% to 0.64% vitrinite reflectance. Methane initially desorbed faster than CO2, resulting in a 50% increase of the CO 2 content in bulk desorbing gas on the 50th day relative to the first day of desorption. After 50 days of desorption, about 90% of all coal gas was desorbed. Over the same time period, ??13C values of incrementally sampled coal gas increased by 2??? and 9???, for CH 4 and CO2, respectively, testifying to the greater retention of 13CH4 and 13CO2 relative to 12CH4 and 12CO2. An isotopic mass balance of the individual, sequentially desorbed and sampled gas amounts yielded weighted mean ??13CCH4 and ??13CCO2 values for characterizing the cumulatively desorbed gas. The overall mean ??13C values were equivalent to ??13C values of gases that desorbed at a time when half of the potentially available gas had been desorbed from coal, corresponding in this study to a time between day 5 and day 12 of canister desorption at 15-18??C. The total expected gas volume and the ???50% midpoint can thus be approximated for a desorbing coal gas sample, based on a dynamic prediction after the first five days of canister desorption. ?? 2005 Elsevier Ltd. All rights reserved.

Desorption of zinc by extracellularly produced metabolites of Trichoderma harzianum, Trichoderma reesei and Coriolus versicolor.

PubMed

Adams, P; Lynch, J M; De Leij, F A A M

2007-12-01

To determine the role of fungal metabolites in the desorption of metals. Desorption of Zn from charcoal by three different fungi was compared against metal desorption with reverse osmosis water, a 0.1% Tween 80 solution and a 0.1 mol l(-1) CaCl(2) solution. All three fungal filtrates desorbed three times more Zn than either 0.1% Tween 80 or 0.1 mol l(-1) CaCl(2). Metal chelator production in Trichoderma harzianum and Coriolus versicolor was constitutively expressed while chelator production in Trichoderma reesei was induced by Zn. The presence of Zn inhibited the production of metal chelators by C. versicolor. Only C. versicolor was found to produce oxalic acid (a strong metal chelator). All fungi caused a marked decrease in pH, although this was not enough to explain the increased desorption of the metals by the different fungal filtrates. Metal chelation via organic acids and proteins are the main mechanisms by which the fungal filtrates increase zinc desorption. The results of this study explain why plants inoculated with T. harzianum T22 take up more metal from soil, than noninoculated plants while metabolites produced by fungi could be used for metal leaching from contaminated soils.

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

PubMed

Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

2017-09-19

Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

Identification of carbohydrates by matrix-free material-enhanced laser desorption/ionisation mass spectrometry.

PubMed

Hashir, Muhammad Ahsan; Stecher, Guenther; Bakry, Rania; Kasemsook, Saowapak; Blassnig, Bernhard; Feuerstein, Isabel; Abel, Gudrun; Popp, Michael; Bobleter, Ortwin; Bonn, Guenther K

2007-01-01

Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is a sensitive mass spectrometric technique which utilises acidic materials as matrices for laser energy absorption, desorption and ionisation of analytes. These matrix materials produce background signals particularly in the low-mass range and make the detection and identification of small molecules difficult and nearly impossible. To overcome this problem this paper introduces matrix-free material-enhanced laser desorption/ionisation mass spectrometry (mf-MELDI-MS) for the screening and analysis of small molecules such as carbohydrates. For this purpose, 4,4'-azo-dianiline was immobilised on silica gel enabling the absorption of laser energy sufficient for successful desorption and ionisation of low molecular weight compounds. The particle and pore sizes, the solvent system for suspension and the sample preparation procedures have been optimised. The newly synthesised MELDI material delivered excellent spectra with regard to signal-to-noise ratio and detection sensitivity. Finally, wheat straw degradation products and Salix alba L. plant extracts were analysed proving the high performance and excellent behaviour of the introduced material. Copyright (c) 2007 John Wiley & Sons, Ltd.

A mass spectrometric system for analyzing thermal desorption spectra of ion-implanted argon and cesium in tungsten. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Wood, G. M., Jr.

1974-01-01

A mass spectrometric system for determining the characteristics of materials used in instrumental development and aerospace applications was developed. The desorption spectra of cesium that was ion-implanted into polycrystalline tungsten and the effects on the spectra of bombardment of the tungsten by low energy (70 eV) electrons were investigated. Work function changes were measured by the retarding potential diode method. Flash desorption characteristics were observed and gas-reaction mechanisms of the surface of heated metal filaments were studied. Desorption spectra were measured by linearly increasing the sample temperature at a selected rate, the temperature cycling being generated from a ramp-driven dc power supply, with the mass spectrometer tuned to a mass number of interest. Results of the study indicate an anomolous desorption mechanism following an electron bombardment of the sample surface. The enhanced spectra are a function of the post-bombardment time and energy and are suggestive of an increased concentration of cesium atoms, up to 10 or more angstroms below the surface.

Decomposition of multilayer benzene and n-hexane films on vanadium.

PubMed

Souda, Ryutaro

2015-09-21

Reactions of multilayer hydrocarbon films with a polycrystalline V substrate have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. Most of the benzene molecules were dissociated on V, as evidenced by the strong depression in the thermal desorption yields of physisorbed species at 150 K. The reaction products dehydrogenated gradually after the multilayer film disappeared from the surface. Large amount of oxygen was needed to passivate the benzene decomposition on V. These behaviors indicate that the subsurface sites of V play a role in multilayer benzene decomposition. Decomposition of the n-hexane multilayer films is manifested by the desorption of methane at 105 K and gradual hydrogen desorption starting at this temperature, indicating that C-C bond scission precedes C-H bond cleavage. The n-hexane dissociation temperature is considerably lower than the thermal desorption temperature of the physisorbed species (140 K). The n-hexane multilayer morphology changes at the decomposition temperature, suggesting that a liquid-like phase formed after crystallization plays a role in the low-temperature decomposition of n-hexane.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: a new possibility for the identification and typing of anaerobic bacteria.

PubMed

Nagy, Elizabeth

2014-01-01

Anaerobic bacteria predominate in the normal flora of humans and are important, often life-threatening pathogens in mixed infections originating from the indigenous microbiota. The isolation and identification of anaerobes by phenotypic and DNA-based molecular methods at a species level is time-consuming and laborious. Following the successful adaptation of the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the routine laboratory identification of bacteria, the extensive development of a database has been initiated to use this method for the identification of anaerobic bacteria. Not only frequently isolated anaerobic species, but also newly recognized and taxonomically rearranged genera and species can be identified using direct smear samples or whole-cell protein extraction, and even phylogenetically closely related species can be identified correctly by means of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Typing of anaerobic bacteria on a subspecies level, determination of antibiotic resistance and direct identification of blood culture isolates will revolutionize anaerobe bacteriology in the near future.

Kinetic and equilibrium studies on the removal of Cd2+ ions from water using polyacrylamide grafted rice (Oryza sativa) husk and (Tectona grandis) saw dust.

PubMed

Sharma, Neeta; Kaur, Kulwinder; Kaur, Sumanjit

2009-04-30

The increase in the use of heavy metals has resulted in an increased flux of metallic substances into the aquatic environment which poses a danger to human health. The present work relates to the removal of cadmium ions by treatment with polyacrylamide grafted rice (Oryza sativa) husk/saguan (Tectona grandis) saw dust. The drinking water guideline value recommended by WHO for cadmium is 0.005 ppm.The adsorbent has been prepared by treatment of rice husk/saw dust with acrylamide. Removal has been studied at various pH values for different times of contact and adsorbate concentrations and is found to be pH-dependent, maximum removal occurs at pH 9 and at a contact time of 180 min for both the adsorbents. The results were found to be consistent with both the Langmuir and Freundlich isotherm models. The value of n (rate constant) determined at pH 9 has been found to be 1 (within experimental limits). This is further substantiated by applying the Lagergren model. The intra-particle diffusion constants were determined by the Morris-Weber model. Continuous flow column studies have also been undertaken and the breakthrough characteristics were determined. Desorption has been affected with 0.5M HCl. The results suggest that both polyacrylamide grafted rice husk/saw dust can be used as efficient and cost effective adsorbents for cadmium ion removal.

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

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

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

DOE PAGES

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.; ...

2017-04-17

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Adsorption/Desorption Transition of Recombinant Human Neurotrophin 4: Physicochemical Characterization.

PubMed

Dąbkowska, Maria; Adamczak, Małgorzata; Barbasz, Jakub; Cieśla, Michał; Machaliński, Bogusław

2017-09-26

Bulk physicochemical properties of neurotrophin 4 (NT-4) in electrolyte solutions and its adsorption/desorption on/from mica surfaces have been studied using dynamic light scattering (DLS), microelectrophoresis, a solution depletion technique (enzyme-linked immunosorbent assay, ELISA), and AFM imaging. Our study presents a determination of the diffusion coefficient, hydrodynamic diameters, electrophoretic mobility, and isoelectric point of the NT-4 under various ionic strength and pH conditions. The size of the NT-4 homodimer for an ionic strength of 0.015 M was substantially independent of pH and equal to 5.1 nm. It has been found that the number of electrokinetic charges per NT-4 molecule was equal to zero for all studied ionic strengths at pH 8.1, which was identified as the isoelectric point (iep). The protein adsorption/desorption on/from mica surfaces was examined as a function of ionic strength and pH. The kinetics of neurotrophin adsorption/desorption were evaluated at pH 3.5, 7.4, and 11 by direct AFM imaging and the ELISA technique. A monotonic increase in the maximum coverage of adsorbed NT-4 molecules with ionic strength (up to 5.5 mg/m 2 ) was observed at pH 3.5. These results were interpreted in terms of the theoretical model postulating an irreversible adsorption of the protein governed by the random sequential adsorption (RSA). Our measurements revealed a significant role of ionic strength, pH, and electrolyte composition in the lateral electrostatic interactions among differently charged NT-4 molecules. The transition between adsorption/desorption processes is found for the region of high pH and low surface concentration of adsorbed neurotrophin molecules at constant ionic strength. Additionally, results presented in this work show that the adsorption behavior of neurotrophin molecules may be governed by intrasolvent electrostatic interactions yielding an aggregation process. Understanding polyvalent neurotrophin interactions may have an impact on the reversibility/irreversibility of adsorption, and hence they might be useful for obtaining well-ordered protein layers, targeting the future development of drug delivery systems for treating neurodegenerative diseases.

Adsorption of Pb2+ on Thiol-functionalized Mesoporous Silica, SH-MCM-48

NASA Astrophysics Data System (ADS)

Taba, P.; Mustafa, R. D. P.; Ramang, L. M.; Kasim, A. H.

2018-03-01

Modification of mesoporous silica, MCM-48, by using 3- mercaptopropyltrimethoxysilane has been successfully conducted. MCM-48 and SH-MCM-48 were characterized using XRD and FTIR. SH-MCM-48 was used as an adsorbent of Pb2+ ions from solution. A number of Pb2+ ions adsorbed were studied as the function of time, pH, and concentration. The concentration of the ions after adsorption was determined by an Atomic Absorption Spectrophotometer. The removal of the adsorbed ions from the SH-MCM-48 was also studied using several desorbing agents. The result showed that the optimum time was 20 minutes and optimum pH was 4. The adsorption of Pb(II) ion followed the pseudo-second-order with the rate constant of 0,2632 g•mg-1•min-1. Adsorption of Pb(II) ion fitted the Langmuir isotherm with the adsorption capacity of 0,1088 mmol/g. The best desorbing agent to remove the adsorbed ion from SH-MCM-48 was 0.3 M HCl solution with the desorption percentage of 58.6%.

Phosphorus Adsorption and Desorption Properties of Minnesota Basalt Lunar Simulant and Lunar Glass Simulant

NASA Technical Reports Server (NTRS)

Sutter, Brad; Hossner, Lloyd R.; Ming, Douglas W.

1996-01-01

Phosphorus (P) adsorption and desorption characteristics of Minnesota Basalt Lunar Simulant (MBLS) and Lunar Glass Simulant (LGS) were evaluated. Results of P interactions with lunar simulants indicated that mineral and glass components adsorbed between 50 and 70% of the applied P and that between 85 and 100% of the applied P was desorbed. The Extended Freundlich equation best described the adsorption data (r(sup 2) = 0.92), whereas the Raven/Hossner equation best described the desorption data ((r(sup 2) = 0.97). Kinetic desorption results indicated that MBLS and LGS released most of their P within 15 h. The expanded Elovich equation fit the data best at shorter times while t/Q(sub DT) equation had a better fit at longer times. These results indicate that P does not strongly adsorb to the two simulants and that any P that was adsorbed was readily desorbed in the presence of anion exchange resin. This work suggests that multiple small applications of P (10-20 mg P/kg) should be added to the simulants to ensure adequate solution P for plant uptake and efficient use of P fertilizer.

Ionic Adsorption and Desorption of CNT Nanoropes

PubMed Central

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-01-01

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment. PMID:28335306

Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO 2(111)

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

Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

2016-03-24

Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO 2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on themore » surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

[Life support of the Mars exploration crew. Control of a zeolite system for carbon dioxide removal from space cabin air within a closed air regeneration cycle].

PubMed

Chekov, Iu F

2009-01-01

The author describes a zeolite system for carbon dioxide removal integrated into a closed air regeneration cycle aboard spacecraft. The continuous operation of a double-adsorbent regeneration system with pCO2-dependable productivity is maintained through programmable setting of adsorption (desorption) semicycle time. The optimal system regulation curve is presented within the space of statistical performance family obtained in quasi-steady operating modes with controlled parameters of the recurrent adsorption-desorption cycle. The automatically changing system productivity ensures continuous intake of concentrated CO2. Control of the adsorption-desorption process is based on calculation of the differential adsorption (desorption) heat from gradient of adsorbent and test inert substance temperatures. The adaptive algorithm of digital control is implemented through the standard spacecraft interface with the board computer system and programmable microprocessor-based controllers.

Ionic Adsorption and Desorption of CNT Nanoropes.

PubMed

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-09-28

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

Adsorption of octylamine on titanium dioxide

NASA Astrophysics Data System (ADS)

Siwińska, Daria; Kołodziejczak-Radzimska, Agnieszka; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

2009-05-01

Processes of adsorption and desorption of a model active substance (octylamine) on the surface of unmodified titanium dioxide (E 171) have been performed. The effects of concentration of octylamine and time of the process on the character of adsorption have been studied and the efficiency of the adsorption/desorption has been determined. The samples obtained have been studied by X-ray diffraction. The nitrogen adsorption/desorption isotherms, particle size distribution and absorption capacities of water, dibutyl phthalate and paraffin oil have been determined. The efficiency of octylamine adsorption on the surface of the titanium dioxide has been found positively correlated with the concentration of octylamine in the initial solution. The desorption of octylamine has decreased with increasing concentration of this compound adsorbed. For octylamine in low concentrations the physical adsorption has been found to dominate, which is desirable when using TiO 2 in the production of pharmaceuticals.

Development of Carbotrap B-packed needle trap device for determination of volatile organic compounds in air.

PubMed

Poormohammadi, Ali; Bahrami, Abdulrahman; Farhadian, Maryam; Ghorbani Shahna, Farshid; Ghiasvand, Alireza

2017-12-08

Carbotrap B as a highly pure surface sorbent with excellent adsorption/desorption properties was packed into a stainless steel needle to develop a new needle trap device (NTD). The performance of the prepared NTD was investigated for sampling, pre-concentration and injection of benzene, toluene, ethyl benzene, o-xylene, and p-xylene (BTEX) into the column of gas chromatography-mass spectrometry (GC-MS) device. Response surface methodology (RSM) with central composite design (CCD) was also employed in two separate consecutive steps to optimize the sampling and device parameters. First, the sampling parameters such as sampling temperature and relative humidity were optimized. Afterwards, the RSM was used for optimizing the desorption parameters including desorption temperature and time. The results indicated that the peak area responses of the analytes of interest decreased with increasing sampling temperature and relative humidity. The optimum values of desorption temperature were in the range 265-273°C, and desorption time were in the range 3.4-3.8min. The limits of detection (LODs) and limits of quantitation (LOQs) of the studied analytes were found over the range of 0.03-0.04ng/mL, and 0.1-0.13ng/mL, respectively. These results demonstrated that the NTD packed with Carbotrap B offers a high sensitive procedure for sampling and analysis of BTEX in concentration range of 0.03-25ng/mL in air. Copyright © 2017 Elsevier B.V. All rights reserved.

Basic poly(propylene glycols) as reference compounds for internal mass calibration in positive-ion matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gross, Jürgen H

2017-12-01

Basic poly(propylene glycols), commercially available under the trade name Jeffamine, are evaluated for their potential use as internal mass calibrants in matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry. Due to their basic amino endgroups Jeffamines are expected to deliver [M+H] + ions in higher yields than neutral poly(propylene glycols) or poly(ethylene glycols). Aiming at accurate mass measurements and molecular formula determinations by matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry, four Jeffamines (M-600, M-2005, D-400, D-230) were thus compared. As a result, Jeffamine M-2005 is introduced as a new mass calibrant for positive-ion matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry in the range of m/z 200-1200 and the reference mass list is provided. While Jeffamine M-2005 is compatible with α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxybenzoic acid, and 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile matrix, its use in combination with 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile provides best results due to low laser fluence requirements. Applications to PEG 300, PEG 600, the ionic liquid trihexyl(tetradecyl)-phosphonium tris(pentafluoroethyl)-trifluorophosphate, and [60]fullerene demonstrate mass accuracies of 2-5 ppm.

Composite glycerol/graphite/aromatic acid matrices for thin-layer chromatography/matrix-assisted laser desorption/ionization mass spectrometry of heterocyclic compounds.

PubMed

Esparza, Cesar; Borisov, R S; Varlamov, A V; Zaikin, V G

2016-10-28

New composite matrices have been suggested for the analysis of mixtures of different synthetic organic compounds (N-containing heterocycles and erectile dysfunction drugs) by thin layer chromatography/matrix-assisted laser desorption ionization time-of-flight mass spectrometry (TLC/MALDI-TOF). Different mixtures of classical MALDI matrices and graphite particles dispersed in glycerol were used for the registration of MALDI mass spectra directly from TLC plates after analytes separation. In most of cases, the mass spectra possessed [M+H] + ions; however, for some analytes only [M+Na] + and [M+K] + ions were observed. These ions have been used to generate visualized TLC chromatograms. The described approach increases the desorption/ionization efficiencies of analytes separated by TLC, prevent spot blurring, simplifies and decrease time for sample preparation. Copyright © 2016 Elsevier B.V. All rights reserved.

A combined radio- and stable-isotopic study of a California coastal aquifer system

USGS Publications Warehouse

Swarzenski, Peter W.; Baskaran, Mark; Rosenbauer, Robert J.; Edwards, Brian D.; Land, Michael

2013-01-01

Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ18O), dissolved inorganic carbon (δ13CDIC), and radioactive isotopes (3H, 222Rn and 223,224,226,228Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl− concentrations attained seawater-like values and in conjunction with isotopically heavier δ18O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ13CDIC in the absence of SO42− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234U/238U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer characteristics, such as geochemical cycling, rock/water interactions, and subsurface transport and mixing.

Hydrogen loss during N-15 nuclear reaction analysis of high strength steel

NASA Astrophysics Data System (ADS)

Larochelle, J. S.; Désilets-Benoit, A.; Borduas, G.; Laliberté-Riverin, S.; Roorda, S.; Brochu, M.

2017-10-01

High strength steel samples were analysed by N-15 nuclear reaction analysis in order to detect hydrogen that may have been introduced by electroplating process. The NRA signal decreased during exposure of the ion beam and residual gas analysis showed that the gas was desorbed by the beam interaction. The variable hydrogen signal could be well described as the sum of a constant concentration and a fraction susceptible to second order desorption. A mechanically polished bevel allowed measurements to be extended to a depth of 0.2 mm.

Performance of Matrix-Assisted Laser Desorption Ionization−Time of Flight Mass Spectrometry for Identification of Aspergillus, Scedosporium, and Fusarium spp. in the Australian Clinical Setting

PubMed Central

Sleiman, Sue; Halliday, Catriona L.; Chapman, Belinda; Brown, Mitchell; Nitschke, Joanne; Lau, Anna F.

2016-01-01

We developed an Australian database for the identification of Aspergillus, Scedosporium, and Fusarium species (n = 28) by matrix-assisted laser desorption ionization−time of flight mass spectrometry (MALDI-TOF MS). In a challenge against 117 isolates, species identification significantly improved when the in-house-built database was combined with the Bruker Filamentous Fungi Library compared with that for the Bruker library alone (Aspergillus, 93% versus 69%; Fusarium, 84% versus 42%; and Scedosporium, 94% versus 18%, respectively). PMID:27252460

An in-house assay is superior to Sepsityper for direct matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry identification of yeast species in blood cultures.

PubMed

Bidart, Marie; Bonnet, Isabelle; Hennebique, Aurélie; Kherraf, Zine Eddine; Pelloux, Hervé; Berger, François; Cornet, Muriel; Bailly, Sébastien; Maubon, Danièle

2015-05-01

We developed an in-house assay for the direct identification, by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry, of yeasts in blood culture. Sixty-one representative strains from 12 species were analyzed in spiked blood cultures. Our assay accurately identified 95 of 107 (88.8%) positive blood cultures and outperformed the commercial Sepsityper kit (81.7% identification). Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Comparison of Heat Inactivation and Cell Disruption Protocols for Identification of Mycobacteria from Solid Culture Media by Use of Vitek Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

PubMed Central

Machen, Alexandra; Kobayashi, Miwako; Connelly, Mary Robin

2013-01-01

Two novel protocols for inactivation and extraction were developed and used to identify 107 Mycobacterium clinical isolates, including Mycobacterium tuberculosis complex, from solid cultures using Vitek matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry. The protocol using heat inactivation with sonication and cell disruption with glass beads resulted in 82.2% and 88.8% species and genus level identifications, respectively. PMID:24068013

Current status of matrix-assisted laser desorption ionisation-time of flight mass spectrometry in the clinical microbiology laboratory.

PubMed

Kok, Jen; Chen, Sharon C A; Dwyer, Dominic E; Iredell, Jonathan R

2013-01-01

The integration of matrix-assisted laser desorption ionisation-time of flight mass spectrometry (MALDI-TOF MS) into many clinical microbiology laboratories has revolutionised routine pathogen identification. MALDI-TOF MS complements and has good potential to replace existing phenotypic identification methods. Results are available in a more clinically relevant timeframe, particularly in bacteraemic septic shock. Novel applications include strain typing and the detection of antimicrobial resistance, but these are not widely used. This review discusses the technical aspects, current applications, and limitations of MALDI-TOF MS.

Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry for Use with Positive Blood Cultures: Methodology, Performance, and Optimization.

PubMed

Faron, Matthew L; Buchan, Blake W; Ledeboer, Nathan A

2017-12-01

Early initiation of effective antibiotics for septic patients is essential for patient survival. Matrix-assisted desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has revolutionized clinical microbiology for isolate identification and has the possibility to impact how blood culture testing is performed. This review discusses the various uses of MALDI-TOF MS for the identification and susceptibility testing of positive blood cultures, the performance of these methods, and the outcomes involved with its implementation. Copyright © 2017 American Society for Microbiology.

Commercial silicate phosphate sequestration and desorption leads to a gradual decline of aquatic systems.

PubMed

Svatos, Karl B W

2018-02-01

Laboratory desorption behaviour, function and elemental composition of commercially marketed silicate minerals used to sequester phosphorus pollution as well as Zeolite, Smectite, and Kaolinite were determined to see whether their use by environmental scientists and water managers in eutrophic waterways has the potential to contribute to longer-term environmental impacts. As expected, lower phosphorus concentrations were observed, following treatment. However, data relating to desorption, environmental fate and bioavailability of phospho-silicate complexes (especially those containing rare earth elements) appear to be underrepresented in product testing and trial publications. Analysis of desorption of phosphate (P) was > 5 μg[P]/L for all three non-commercial samples and 0 > μg[P]/L > 5 for all commercial silicates for a range of concentrations from 0 to 300 μg[P]/L. Based on a review of bioaccumulation data specific to the endangered Cherax tenuimanus (Hairy Marron) and other endemic species, this is significant considering anything > 20 μg[La]/L is potentially lethal to the hairy marron, other crustaceans and even other phyla. Where prokaryotic and eukaryotic effects are underreported, this represents a significant challenge. Especially where product protocols recommend continual reapplication, this is significant because both the forward and reverse reactions are equally important. The users of silicate minerals in water columns should accept the dynamic nature of the process and pay equal attention to both adsorption and desorption because desorption behaviour is an inherent trait. Even if broader desorption experimentation is difficult, expensive and time-consuming, it is a critical consideration nonetheless.

Surface-assisted laser desorption ionization mass spectrometry techniques for application in forensics.

PubMed

Guinan, Taryn; Kirkbride, Paul; Pigou, Paul E; Ronci, Maurizio; Kobus, Hilton; Voelcker, Nicolas H

2015-01-01

Matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is an excellent analytical technique for the rapid and sensitive analysis of macromolecules (>700 Da), such as peptides, proteins, nucleic acids, and synthetic polymers. However, the detection of smaller organic molecules with masses below 700 Da using MALDI-MS is challenging due to the appearance of matrix adducts and matrix fragment peaks in the same spectral range. Recently, nanostructured substrates have been developed that facilitate matrix-free laser desorption ionization (LDI), contributing to an emerging analytical paradigm referred to as surface-assisted laser desorption ionization (SALDI) MS. Since SALDI enables the detection of small organic molecules, it is rapidly growing in popularity, including in the field of forensics. At the same time, SALDI also holds significant potential as a high throughput analytical tool in roadside, work place and athlete drug testing. In this review, we discuss recent advances in SALDI techniques such as desorption ionization on porous silicon (DIOS), nano-initiator mass spectrometry (NIMS) and nano assisted laser desorption ionization (NALDI™) and compare their strengths and weaknesses with particular focus on forensic applications. These include the detection of illicit drug molecules and their metabolites in biological matrices and small molecule detection from forensic samples including banknotes and fingerprints. Finally, the review highlights recent advances in mass spectrometry imaging (MSI) using SALDI techniques. © 2014 Wiley Periodicals, Inc.

Identification of Scirpus triqueter root exudates and the effects of organic acids on desorption and bioavailability of pyrene and lead in co-contaminated wetland soils.

PubMed

Hou, Yunyun; Liu, Xiaoyan; Zhang, Xinying; Chen, Xiao; Tao, Kaiyun; Chen, Xueping; Liang, Xia; He, Chiquan

2015-11-01

Root exudates (REs) of Scirpus triqueter were extracted from the rhizosphere soil in this study. The components in the REs were identified by GC-MS. Many organic acids, such as hexadecanoic acid, pentadecanoic acid, vanillic acid, octadecanoic acid, citric acid, succinic acid, glutaric acid, and so on, were found. Batch simulated experiments were conducted to evaluate the impacts of different organic acids, such as citric acid, artificial root exudates (ARE), succinic acid, and glutaric acid in REs of S. triqueter on desorption of pyrene (PYR) and lead (Pb) in co-contaminated wetland soils. The desorption amount of PYR and Pb increased with the rise in concentrations of organic acids in the range of 0-50 g·L(-1), within shaking time of 2-24 h. The desorption effects of PYR and Pb in soils with various organic acids treatments decreased in the following order: citric acid > ARE > succinic acid > glutaric acid. The desorption rate of PYR and Pb was higher in co-contaminated soil than in single pollution soil. The impacts of organic acids in REs of S. triqueter on bioavailability of PYR and Pb suggested that organic acids enhanced the bioavailability of PYR and Pb in wetland soil, and the bioavailability effects of organic acids generally followed the same order as that of desorption effects.

Optimization of the secondary drying step in freeze drying using TDLAS technology.

PubMed

Schneid, Stefan C; Gieseler, Henning; Kessler, William J; Luthra, Suman A; Pikal, Michael J

2011-03-01

The secondary drying phase in freeze drying is mostly developed on a trial-and-error basis due to the lack of appropriate noninvasive process analyzers. This study describes for the first time the application of Tunable Diode Laser Absorption Spectroscopy, a spectroscopic and noninvasive sensor for monitoring secondary drying in laboratory-scale freeze drying with the overall purpose of targeting intermediate moisture contents in the product. Bovine serum albumin/sucrose mixtures were used as a model system to imitate high concentrated antibody formulations. First, the rate of water desorption during secondary drying at constant product temperatures (-22 °C, -10 °C, and 0 °C) was investigated for three different shelf temperatures. Residual moisture contents of sampled vials were determined by Karl Fischer titration. An equilibration step was implemented to ensure homogeneous distribution of moisture (within 1%) in all vials. The residual moisture revealed a linear relationship to the water desorption rate for different temperatures, allowing the evaluation of an anchor point from noninvasive flow rate measurements without removal of samples from the freeze dryer. The accuracy of mass flow integration from this anchor point was found to be about 0.5%. In a second step, the concept was successfully tested in a confirmation experiment. Here, good agreement was found for the initial moisture content (anchor point) and the subsequent monitoring and targeting of intermediate moisture contents. The present approach for monitoring secondary drying indicated great potential to find wider application in sterile operations on production scale in pharmaceutical freeze drying. © 2011 American Association of Pharmaceutical Scientists

[Special application of matrix-assisted laser desorption ionization time-of-flight mass spectrometry in clinical microbiological diagnostics].

PubMed

Nagy, Erzsébet; Abrók, Marianna; Bartha, Noémi; Bereczki, László; Juhász, Emese; Kardos, Gábor; Kristóf, Katalin; Miszti, Cecilia; Urbán, Edit

2014-09-21

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry as a new possibility for rapid identification of bacteria and fungi revolutionized the clinical microbiological diagnostics. It has an extreme importance in the routine microbiological laboratories, as identification of the pathogenic species rapidly will influence antibiotic selection before the final determination of antibiotic resistance of the isolate. The classical methods for identification of bacteria or fungi, based on biochemical tests, are influenced by many environmental factors. The matrix-assisted laser desorption ionization time-of-flight mass spectrometry is a rapid method which is able to identify a great variety of the isolated bacteria and fungi based on the composition of conserved ribosomal proteins. Recently several other applications of the method have also been investigated such as direct identification of pathogens from the positive blood cultures. There are possibilities to identify bacteria from the urine samples in urinary tract infection or from other sterile body fluids. Using selective enrichment broth Salmonella sp from the stool samples can be identified more rapidly, too. The extended spectrum beta-lactamase or carbapenemase production of the isolated bacteria can be also detected by this method helping the antibiotic selection in some cases. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry based methods are suitable to investigate changes in deoxyribonucleic acid or ribonucleic acid, to carry out rapid antibiotic resistance determination or other proteomic analysis. The aim of this paper is to give an overview about present possibilities of using this technique in the clinical microbiological routine procedures.

On the Interaction between Superabsorbent Hydrogels and Cementitious Materials

NASA Astrophysics Data System (ADS)

Farzanian, Khashayar

Autogenous shrinkage induced cracking is a major concern in high performance concretes (HPC), which are produced with low water to cement ratios. Internal curing to maintain high relative humidity in HPC with the use of an internal water reservoir has proven effective in mitigating autogenous shrinkage in HPC. Superabsorbent polymers (SAP) or hydrogels have received increasing attention as an internal curing agent in recent years. A key advantage of SAP is its versatility in size distribution and absorption/desorption characteristics, which allow it to be adapted to specific mix designs. Understanding the behavior of superabsorbent hydrogels in cementitious materials is critical for accurate design of internal curing. The primary goal of this study is to fundamentally understand the interaction between superabsorbent hydrogels and cementitious materials. In the first step, the effect of chemical and mechanical conditions on the absorption of hydrogels is investigated. In the second step, the desorption of hydrogels in contact with porous cementitious materials is examined to aid in understanding the mechanisms of water release from superabsorbent hydrogels (SAP) into cementitious materials. The dependence of hydrogel desorption on the microstructure of cementitious materials and relative humidity is studied. It is shown that the capillary forces developed at the interface between the hydrogel and cementitious materials increased the desorption of the hydrogels. The size of hydrogels is shown to influence desorption, beyond the known size dependence of bulk diffusion, through debonding from the cementitious matrix, thereby decreasing the effect of the Laplace pressure on desorption. In the third step, the desorption of hydrogels synthesized with varied chemical compositions in cementitious materials are investigated. The absorption, chemical structure and mechanical response of hydrogels swollen in a cement mixture are studied. The effect of the capillary forces on the desorption of hydrogels is investigated in relation to the chemical composition of the hydrogels. In the second set of experiments of this part, the behavior of the hydrogels in a hydrating cement paste is monitored by tracking the size and morphology evolution of hydrogels interacting with the cement paste matrix. It is shown that the changes on the surface characteristics of hydrogels as a result of interactions with the pore solution and cement particles can affect the desorption rate of hydrogels in contact with a porous cementitious material. Scanning electron microscopic (SEM) examination demonstrates two different desorption modes with distinct morphologies of hydrogels depending on the chemical composition of hydrogels. The effect of the interfacial bonding between the hydrogels and the cementitious matrix and its relation to the desorption is illustrated. The desorption of hydrogels with different chemical compositions in blended cement mixture containing different supplementary cementitious materials (SCMs) such as slag, fly ash, silica fume and two types of glass powders, are examined. The absorption/desorption kinetics of hydrogels in different hydrating blended cement mixtures are monitored by freeze drying the samples at different times. The surface characteristics of different hydrogels after interaction with pore solution, cement particles and SCMs particles are examined and their relation to interfacial bonding is illustrated. It is shown that different SCMs can cause distinct changes on interfacial bonding. The understanding of hydrogel behavior in cementitious materials helps with accurate mixture design for internal curing. The kinetics of desorption is crucial for the purpose of internal curing. The understanding of release mechanisms and the change in the hydrogel morphology is important for the self-healing and self-sealing applications. Two major contributions of this research are (1) to show the effect of capillary forces developed at the interface between cementitious matrix and hydrogel which can increase the rate of desorption dramatically and (2) to illustrate the chemo-physical interaction between cement pore solution and hydrating particles with hydrogels which can affect the interfacial bonding between hydrogel and cement. These two main contributions will be useful to understand the absorption and desorption behavior of hydrogel in cementitious materials. Two main strengths of experimental procedures of this research are (1) use of in-house synthesis of hydrogels that permits establishing a link between the chemical composition of hydrogels and their behavior in cementitious materials and (2) use of freeze drying for the first time to monitor the behavior of hydrogels interacting with a hydrating cementitious matrix.

Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 2. Transport of TCE

USGS Publications Warehouse

Sahoo, D.; Smith, J.A.; Imbrigiotta, T.E.; Mclellan, H.M.

1998-01-01

Field studies were conducted under an induced gradient in a trichloroethene (TCE)-contaminated aquifer at Picatinny Arsenal, NJ, to study (a) the rate-limited desorption of TCE from aquifer sediments to water and (b) the effect of a surfactant (Triton X-100) on the desorption and transport of TCE. Clean water was injected into the contaminated aquifer for 206 day. Triton X-100 was added for a 36-day period (days 36-71 from the start of clean water injection). The effect of Triton X-100 on the desorption and transport of TCE in the field was examined by observing the concentrations of these two solutes in four monitoring wells 3-9 m from the injection wells. These data show a small but discernible increase in the TCE concentration in two of the wells corresponding approximately to the time when surfactant reaches the wells; in the other two monitoring wells, the increase in TCE concentration is negligible. A solute transport model that assumes local sorption equilibrium and used a laboratory-derived distribution coefficient could not adequately describe TCE desorption and transport observed in the aquifer. Two model formulations that accounted for rate-limited sorption - two-site and multisite models - fit the data well. TCE concentrations after surfactant injection were underpredicted by the models unless mass transfer rate was increased to account for the effect of surfactant on the rate of TCE desorption. The concentration data from the two wells and the model analysis suggest that the rate of TCE desorption is increased (by approximately 30%) as a result of Triton X-100 injection.Field studies were conducted under an induced gradient in a trichloroethene (TCE)-contaminated aquifer at Picatinny Arsenal, NJ, to study (a) the rate-limited desorption of TCE from aquifer sediments to water and (b) the effect of a surfactant (Triton X-100) on the desorption and transport of TCE. Clean water was injected into the contaminated aquifer for 206 day. Triton X-100 was added for a 36-day period (days 36-71 from the start of clean water injection). The effect of Triton X-100 on the desorption and transport of TCE in the field was examined by observing the concentrations of these two solutes in four monitoring wells 3-9 m from the injection wells. These data show a small but discernible increase in the TCE concentration in two of the wells corresponding approximately to the time when surfactant reaches the wells; in the other two monitoring wells, the increase in TCE concentration is negligible. A solute transport model that assumes local sorption equilibrium and used a laboratory-derived distribution coefficient could not adequately describe TCE desorption and transport observed in the aquifer. Two model formulations that accounted for rate-limited sorption - two-site and multisite models - fit the data well. TCE concentrations after surfactant injection were underpredicted by the models unless mass transfer rate was increased to account for the effect of surfactant on the rate of TCE desorption. The concentration data from the two wells and the model analysis suggest that the rate of TCE desorption is increased (by approximately 30%) as a result of Triton X-100 injection.

Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis

NASA Astrophysics Data System (ADS)

Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.; Holzinger, Rupert; Rosenørn, Thomas; Sperlich, Peter; Julien, Maxime; Remaud, Gerald S.; Bilde, Merete; Röckmann, Thomas; Johnson, Matthew S.

2017-05-01

Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from -6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39-800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was raised from 100 to 250 °C. At temperatures above 250 °C, the O : C ratio of thermally desorbed material, presumably from oligomeric precursors, was constant. The observation of a number of components that occurred across the full range of desorption temperatures suggests that they are generated by thermal decomposition of oligomers. The isotopic composition of SOA was more or less independent of desorption temperature above 100 °C. TC analysis showed that SOA was enriched in 13C by 0.6-1.2 ‰ relative to the initial α-pinene. According to mass balance, gas-phase products will be depleted relative to the initial α-pinene. Accordingly, organic material on the back filters, which contain adsorbed gas-phase compounds, is depleted in 13C in TC by 0.7 ‰ relative to the initial α-pinene, and by 1.3 ‰ compared to SOA collected on the front filter. The observed difference in 13C between the gas and particle phases may arise from isotope-dependent changes in the branching ratios in the α-pinene + O3 reaction. Alternatively, some gas-phase products involve carbon atoms from highly enriched and depleted sites, as shown in the PSIA analysis, giving a non-kinetic origin to the observed fractionations. In either case, the present study suggests that the site-specific distribution of 13C in the source material itself governs the abundance of 13C in SOA.

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Trends in polychlorinated biphenyl concentrations in Hudson River water five years after elimination of point sources

USGS Publications Warehouse

Schroeder, R.A.; Barnes, C.R.

1983-01-01

Industrial discharge of polychlorinated biphenyls (PCBs) to the Hudson River from 1950 to the mid-1970 's has resulted in serious degradation of the water. Contaminated river-bottom sediments continue to contribute PCBs to the river water. Concentrations in the sediment range from several hundred micrograms per gram near the outfall to less than 10 micrograms per gram in the lower estuary. PCBs are supplied by bottom sediments to the overlying water by two mechanisms--desorption and resuspension. Because desorption is a relatively constant process, concentrations of PCBs decrease as water discharge increases. At high flow, however, scouring by turbulence causes resuspension of PCB-laden sediment. Transport rates indicate that most PCBs enter the water from the most contaminated sediments, which are within 20 kilometers of the outfall. Mean daily transport from the upper river (except during high discharges) has decreased from 10 kilograms in 1976 to 5 kilograms in the late 1970 's and to 1 kilogram in 1981. This decrease probably results from the burial of highly contaminated sediments by cleaner sediments originating upstream. (USGS)

Towards High-Resolution Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry Coupled to Shear Force Microscopy

NASA Astrophysics Data System (ADS)

Nguyen, Son N.; Sontag, Ryan L.; Carson, James P.; Corley, Richard A.; Ansong, Charles; Laskin, Julia

2018-02-01

Constant mode ambient mass spectrometry imaging (MSI) of tissue sections with high lateral resolution of better than 10 μm was performed by combining shear force microscopy with nanospray desorption electrospray ionization (nano-DESI). Shear force microscopy enabled precise control of the distance between the sample and nano-DESI probe during MSI experiments and provided information on sample topography. Proof-of-concept experiments were performed using lung and brain tissue sections representing spongy and dense tissues, respectively. Topography images obtained using shear force microscopy were comparable to the results obtained using contact profilometry over the same region of the tissue section. Variations in tissue height were found to be dependent on the tissue type and were in the range of 0-5 μm for lung tissue and 0-3 μm for brain tissue sections. Ion images of phospholipids obtained in this study are in good agreement with literature data. Normalization of nano-DESI MSI images to the signal of the internal standard added to the extraction solvent allowed us to construct high-resolution ion images free of matrix effects.

Adsorption, desorption, and removal of polymeric nanomedicine on and from cellulose surfaces: effect of size.

PubMed

Zhang, Ming; Akbulut, Mustafa

2011-10-18

The increased production and commercial use of nanoparticulate drug delivery systems combined with a lack of regulation to govern their disposal may result in their introduction to soils and ultimately into groundwater systems. To better understand how such particles interact with environmentally significant interfaces, we study the adsorption, desorption, and removal behavior of poly(ethylene glycol)-based nanoparticulate drug delivery systems on and from cellulose, which is the most common organic compound on Earth. It is shown that such an adsorption process is only partially reversible, and most of the adsorbate particles do not desorb from the cellulose surface even upon rinsing with a large amount of water. The rate constant of adsorption decreases with increasing particle size. Furthermore, hydrodynamic forces acting parallel to the surfaces are found to be of great importance in the context of particle dynamics near the cellulose surface, and ultimately responsible for the removal of some fraction of particles via rolling or sliding. As the particle size increases, the removal rates of the particles increase for a given hydrodynamical condition. © 2011 American Chemical Society

Differential Scanning Calorimetric Study and Potential Model of the Binding of the Primary Water of Hydration to K-Hyaluronate

NASA Astrophysics Data System (ADS)

Whitson, K. B.; Marlowe, R. L.; Lukan, A. M.; Lee, S. A.; Anthony, L.; Rupprecht, A.

1997-11-01

DSC was performed on samples of K-hyaluronate (KHA) through a temperature range of 25-180^oC. A transition peak was observed which is due to the desorption of the primary water of hydration. The maximum position of the peak was observed to change with different scan rates. The average energy of activation, E_A, and enthalpy for desorption of the primary water of hydration was determined to be 0.62 and 0.17 eV per water molecule, respectively. Analysis of Mossbauer data(G. Albanese et al., Hyperfine Int.,) 95, 97 (1995) allowed us to determine the effective force constant, k_eff, of the water bound to KHA to be approximately 19.4 eV/nm^2. The parameters E_A, ΔH,and k_eff allow us to construct a potential model for the primary water of hydration of KHA. Comparison of these parameters with the same parameters for HA and DNA with different counterions reveal that the energy of activation is similar, as well as the enthalpy change.

Global modelling of plasma-wall interaction in reversed field pinches

NASA Astrophysics Data System (ADS)

Bagatin, M.; Costa, S.; Ortolani, S.

1989-04-01

The impurity production and deuterium recycling mechanisms in ETA—BETA II and RFX are firstly discussed by means of a simple model applicable to a stationary plasma interacting with the wall. This gives the time constant and the saturation values of the impurity concentration as a function of the boundary temperature and density. If the latter is sufficiently high, the impurity buildup in the main plasma becomes to some extent stabilized by the shielding effect of the edge. A self-consistent global model of the time evolution of an RFP plasma interacting with the wall is then described. The bulk and edge parameters are derived by solving the energy and particle balance equations incorporating some of the basic plasma-surface processes, such as sputtering, backscattering and desorption. The application of the model to ETA-BETA II confirms the impurity concentrations of the light and metal impurities as well as the time evolution of the average electron density found experimentally under different conditions. The model is then applied to RFX, a larger RFP experiment under construction, whose wall will be protected by a full graphite armour. The time evolution of the discharge shows that carbon sputtering could increase Zeff to ~ 4, but without affecting significantly the plasma performance.

Application of principal component analysis for the optimisation of lead(II) biosorption.

PubMed

Wajda, Łukasz; Duda-Chodak, Aleksandra; Tarko, Tomasz; Kamiński, Paweł

2017-10-03

Current study was focused on optimising lead(II) biosorption carried out by living cells of Arthrospira platensis using Principal Component Analysis. Various experimental conditions were considered: initial metal concentration (50 and 100 mg/l), solution pH (4.0, 4.5, 5.0, 5.5) and contact time (10, 20, 30, 40, 50 and 60 min) at constant rotary speed 200 rpm. It was found that when the biomass was separated from experimental solutions by the filtration, almost 50% of initial metal dose was removed by the filter paper. Moreover, pH was the most important parameter influencing examined processes. The Principal Component Analysis indicated that the most optimum conditions for lead(II) biosorption were metal initial concentration 100 mg/l, pH 4.5 and time 60 min. According to the analysis of the first component it might be stated that the lead(II) uptake increases in time. In overall, it was found to be useful for analysing data obtained in biosorption experiments and eliminating insignificant experimental conditions. Experimental data fitted Langmuir and Dubinin-Radushkevich models indicating that physical and chemical absorption take place at the same time. Further studies are necessary to verify how sorption-desorption cycles affect A. platensis cells.

The laser desorption/laser ionization mass spectra of some anti-inflammatory drugs

NASA Astrophysics Data System (ADS)

Milnes, John; Rogers, Kevin; Jones, Sian; Gormally, John

1994-03-01

The IR laser desorption/ultraviolet laser ionization time-of-flight mass spectra are reported for the anti-inflammatory drugs indomethacin, acemetacin, ibuprofen, flurbiprofen, diflunisal and mefenamic acid. It is found that the six compounds can be readily ionized by two photon absorption at a fixed wavelength of 266 nm. Mass spectra have been obtained under conditions of high ionizing irradiance and the observed fragmentation behaviour is discussed.

Effects of human management on black carbon sorption/desorption during a water transfer project: Recognizing impacts and identifying mitigation possibilities.

PubMed

Hao, Rong; Zhang, Jinliang; Wang, Peichao; Hu, Ronggui; Song, Yantun; Wu, Yupeng; Qiu, Guohong

2018-05-15

Water resources management is an important public concern. In this study, we examined the extent of sorption/desorption of trace pollutants to soil black carbon (BC) in the water level fluctuation zone (WLFZ) of the middle route of the South to North Water Transfer Project in China. In addition, we investigated the main management measures affecting these processes during the project. The results showed that the pseudo second-order model adequately describes the sorption/desorption of phenanthrene on the soil BC in the WLFZ. Water level fluctuation may indirectly influenced BC sorption/desorption by altering water chemistry. Water level residence time had negative effects on BC sorption in short-term experiments (days to months), but the impact gradually diminished with increased residence time. The results suggested that long-term field monitoring of water chemistry is urgent. During the initial period of water transfer, delaying the water supplies as drinking water source or directly irrigating crops could mitigate the adverse impacts. Future research should focus on the water-soluble products of BC degradation. The findings of this study should be useful in improving sustainable management of water resources for water transfer projects. Copyright © 2018 Elsevier Ltd. All rights reserved.

Determination of proflavine in rat whole blood without sample pretreatment by laser desorption postionization mass spectrometry.

PubMed

Chen, Jiaxin; Hu, Yongjun; Lu, Qiao; Wang, Pengchao; Zhan, Huaqi

2017-04-01

A novel pretreatment-free method involving laser desorption postionization (LDPI) coupled with time-of-flight mass spectrometry (MS) was developed for the monitoring of proflavine level in rat whole blood. It comprises a protocol for dosing via intravenous administration and collection of whole blood, followed by direct LDPI-MS analysis without any sample pretreatment. An intense ion signal at m/z 209 was observed from whole blood without any interference signals, except some background signals below m/z 100. The calibration curve was established with use of 9-phenylacridine as the internal standard for proflavine determination from the plotting of the peak ratios of proflavine to the internal standard, with a correlation coefficient (R 2 ) greater than 0.99. The limit of detection was estimated to be 0.48 pmol/mm 2 and the quantification range was 0.5-16.5 μg/mL for proflavine. In addition, only a minimal matrix effect was observed, as expected from considerations of the desorption and ionization mechanism. Interday and intraday accuracy and precision were calculated to be within 13% and 82-114%, respectively. Estimated concentrations of proflavine residue in whole blood were also successfully obtained at selected time points after dosing. The proposed method is simple, low cost, and sensitive, and should be seen as a complementary method for monitoring drug levels in blood. Graphical Abstract Monitoring proflavine levels in rat whole blood at different time points using laser desorption postionization mass spectrometry (LDPI-MS).

Magnetized graphene layers synthesized on the carbon nanofibers as novel adsorbent for the extraction of polycyclic aromatic hydrocarbons from environmental water samples.

PubMed

Rezvani-Eivari, Mostafa; Amiri, Amirhassan; Baghayeri, Mehdi; Ghaemi, Ferial

2016-09-23

The application of magnetized graphene (G) layers synthesized on the carbon nanofibers (CNFs) (m-G/CNF) was investigated as novel adsorbent for the magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in water samples followed by gas chromatography-flame ionization detector (GC-FID). Six important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 5min for extraction time, 20mg for sorbent amount, dichloromethane as desorption solvent, 1mL for desorption solvent volume, 5min for desorption time and 15% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. The calibration curves were linear over the concentration ranges from 0.012 to 100ngmL(-1) with correlation coefficients (r) between 0.9950 and 0.9967 for all the analytes. The limits of detection (LODs, S/N=3) of the proposed method for the studied PAHs were 0.004-0.03ngmL(-1). The relative standard deviations (RSDs) for five replicates at two concentration levels (0.1 and 50ngmL(-1)) of PAHs were ranged from 3.4 to 5.7%. Appropriate relative recovery values, in the range of 95.5-99.9%, were also obtained for the real water sample analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

PubMed

Yu, Honglian; Merib, Josias; Anderson, Jared L

2016-03-18

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Dynamics of the sorption of copper(II) and silver(I) by materials based on sulfoethylchitosan with various degrees of crosslinking

NASA Astrophysics Data System (ADS)

Petrova, Yu. S.; Pestov, A. V.; Alifkhanova, L. M. k.; Neudachina, L. K.

2017-04-01

Optimum conditions of the dynamic concentration of copper(II) and silver(I) ions simultaneously present in a solution with N-(2-sulfoethyl)chitosan with a degree of modification equal to 0.5 and different degrees of crosslinking by glutaraldehyde are determined. The values of coefficients of selectivity K Ag/Cu are determined under dynamic conditions. It is shown that the selectivity of the sorption of silver(I) increases (compared to copper(II)) as the degree of crosslinking of sorbents based on N-(2-sulfoethyl)chitosan is raised. Mathematical treatment of the obtained dynamic curves is performed according to the Thomas, Adams-Bohart, and Yoon and Nelson models. As a result, the values of dynamic capacity of sorbents, the rate constant of the reaction, and the release time of 50% of the sorbate are determined. The quantitative desorption of copper and silver from the surface of sorbents is achieved by using 1 mol/dm3 solution of nitric acid.

Effect of Water Vapor and Surface Morphology on the Low Temperature Response of Metal Oxide Semiconductor Gas Sensors

PubMed Central

Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Eickhoff, Martin

2015-01-01

In this work the low temperature response of metal oxide semiconductor gas sensors is analyzed. Important characteristics of this low-temperature response are a pronounced selectivity to acid- and base-forming gases and a large disparity of response and recovery time constants which often leads to an integrator-type of gas response. We show that this kind of sensor performance is related to the trend of semiconductor gas sensors to adsorb water vapor in multi-layer form and that this ability is sensitively influenced by the surface morphology. In particular we show that surface roughness in the nanometer range enhances desorption of water from multi-layer adsorbates, enabling them to respond more swiftly to changes in the ambient humidity. Further experiments reveal that reactive gases, such as NO2 and NH3, which are easily absorbed in the water adsorbate layers, are more easily exchanged across the liquid/air interface when the humidity in the ambient air is high. PMID:28793583

Cadmium biosorption rate in protonated Sargassum biomass

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

Yang, J.; Volesky, B.

1999-03-01

Biosorption of the heavy metal ion Cd{sup 2+} by protonated nonliving brown alga Sargassum fluitans biomass was accompanied by the release of hydrogen protons from the biomass. The uptake of cadmium and the release of proton matched each other throughout the biosorption process. The end-point titration methodology was used to maintain the constant pH 4.0 for developing the dynamic sorption rate. The sorption isotherm could be well represented by the Langmuir sorption model. A mass transfer model assuming the intraparticle diffusion in a one-dimensional thin plate as a controlling step was developed to describe the overall biosorption rate of cadmiummore » ions in flat seaweed biomass particles. The overall biosorption mathematical model equations were solved numerically yielding the effective diffusion coefficient D{sub e} about 3.5 {times} 10{sup {minus}6} cm{sup 2}/s. This value matches that obtained for the desorption process and is approximately half of that of the molecular diffusion coefficient for cadmium ions in aqueous solution.« less

Performance of Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry for Identification of Aspergillus, Scedosporium, and Fusarium spp. in the Australian Clinical Setting.

PubMed

Sleiman, Sue; Halliday, Catriona L; Chapman, Belinda; Brown, Mitchell; Nitschke, Joanne; Lau, Anna F; Chen, Sharon C-A

2016-08-01

We developed an Australian database for the identification of Aspergillus, Scedosporium, and Fusarium species (n = 28) by matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS). In a challenge against 117 isolates, species identification significantly improved when the in-house-built database was combined with the Bruker Filamentous Fungi Library compared with that for the Bruker library alone (Aspergillus, 93% versus 69%; Fusarium, 84% versus 42%; and Scedosporium, 94% versus 18%, respectively). Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Formic Acid-Based Direct, On-Plate Testing of Yeast and Corynebacterium Species by Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

PubMed Central

Theel, Elitza S.; Schmitt, Bryan H.; Hall, Leslie; Cunningham, Scott A.; Walchak, Robert C.; Patel, Robin

2012-01-01

An on-plate testing method using formic acid was evaluated on the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry system using 90 yeast and 78 Corynebacterium species isolates, and 95.6 and 81.1% of yeast and 96.1 and 92.3% of Corynebacterium isolates were correctly identified to the genus and species levels, respectively. The on-plate method using formic acid yielded identification percentages similar to those for the conventional but more laborious tube-based extraction. PMID:22760034

Analysis of fatty acids by graphite plate laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Park, K H; Kim, H J

2001-01-01

Fatty acids obtained from triglycerides (trioelin, tripalmitin), foods (milk, corn oil), and phospholipids (phosphotidylcholine, phosphotidylserine, phosphatidic acid) upon alkaline hydrolysis were observed directly without derivatization by graphite plate laser desorption/ionization time-of-flight mass spectrometry (GPLDI-TOFMS). Mass-to-charge ratios predicted for sodium adducts of expected fatty acids (e.g. palmitic, oleic, linoleic and arachidonic acids) were observed without interference. Although at present no quantitation is possible, the graphite plate method enables a simple and rapid qualitative analysis of fatty acids. Copyright 2001 John Wiley & Sons, Ltd.

Formic acid-based direct, on-plate testing of yeast and Corynebacterium species by Bruker Biotyper matrix-assisted laser desorption ionization-time of flight mass spectrometry.

PubMed

Theel, Elitza S; Schmitt, Bryan H; Hall, Leslie; Cunningham, Scott A; Walchak, Robert C; Patel, Robin; Wengenack, Nancy L

2012-09-01

An on-plate testing method using formic acid was evaluated on the Bruker Biotyper matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry system using 90 yeast and 78 Corynebacterium species isolates, and 95.6 and 81.1% of yeast and 96.1 and 92.3% of Corynebacterium isolates were correctly identified to the genus and species levels, respectively. The on-plate method using formic acid yielded identification percentages similar to those for the conventional but more laborious tube-based extraction.

Mass spectrometry imaging for visualizing organic analytes in food.

PubMed

Handberg, Eric; Chingin, Konstantin; Wang, Nannan; Dai, Ximo; Chen, Huanwen

2015-01-01

The demand for rapid chemical imaging of food products steadily increases. Mass spectrometry (MS) is featured by excellent molecular specificity of analysis and is, therefore, a very attractive method for chemical profiling. MS for food imaging has increased significantly over the past decade, aided by the emergence of various ambient ionization techniques that allow direct and rapid analysis in ambient environment. In this article, the current status of food imaging with MSI is reviewed. The described approaches include matrix-assisted laser desorption/ionization (MALDI), but emphasize desorption atmospheric pressure photoionization (DAPPI), electrospray-assisted laser desorption/ionization (ELDI), probe electrospray ionization (PESI), surface desorption atmospheric pressure chemical ionization (SDAPCI), and laser ablation flowing atmospheric pressure afterglow (LA-FAPA). The methods are compared with regard to spatial resolution; analysis speed and time; limit of detection; and technical aspects. The performance of each method is illustrated with the description of a related application. Specific requirements in food imaging are discussed. © 2014 Wiley Periodicals, Inc.

Effect of metal surfaces on matrix-assisted laser desorption/ionization analyte peak intensities.

PubMed

Kancharla, Vidhyullatha; Bashir, Sajid; Liu, Jingbo L; Ramirez, Oscar M; Derrick, Peter J; Beran, Kyle A

2017-10-01

Different metal surfaces in the form of transmission electron microscope grids were examined as support surfaces in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a view towards enhancement of peptide signal intensity. The observed enhancement between 5-fold and 20-fold relative to the normal stainless steel slide was investigated by applying the thermal desorption model for matrix-assisted laser desorption/ionization. A simple model evaluates the impact that the thermal properties of the metals have on the ion yield of the analyte. It was observed that there was not a direct, or strong, correlation between the thermal properties of the metals and the corresponding ion yield of the peptides. The effects of both fixed and variable laser irradiances versus ion yield were also examined for the respective metals studied. In all cases the use of transmission electron microscope grids required much lower laser irradiances in order to generate similar peak intensities as those observed with a stainless steel surface.

Simplified behaviors from increased heterogeneity: I. 2-D uranium transport experiments at the decimeter scale.

PubMed

Miller, Andrew W; Rodriguez, Derrick R; Honeyman, Bruce D

2013-05-01

Intermediate scale tank studies were conducted to examine the effects of physical heterogeneity of aquifer material on uranium desorption and subsequent transport in order to bridge the scaling gap between bench and field scale systems. Uranium contaminated sediment from a former uranium mill field site was packed into two 2-D tanks with internal dimensions of 2.44×1.22×0.076 m (tank 1) and 2.44×0.61×0.076 m (tank 2). Tank 1 was packed in a physically homogenous manner, and tank 2 was packed with long lenses of high and low conductivities resulting in different flow fields within the tanks. Chemical gradients within the flow domain were altered by temporal changes in influent water chemistry. The uranium source was desorption from the sediment. Despite the physical differences in the flow fields, there were minimal differences in global uranium leaching behavior between the two tanks. The dominant uranium species in both tanks over time and space was Ca2UO2(CO3)3(0). However, the uranium/alkalinity relationships varied as a function of time in tank 1 and were independent of time in tank 2. After planned stop-flow events, small, short-lived rebounds were observed in tank 1 while no rebound of uranium concentrations was observed in tank 2. Despite appearing to be in local equilibrium with respect to uranium desorption, a previously derived surface complexation model was insufficient to describe uranium partitioning within the flow domain. This is the first in a pair of papers; the companion paper presents an intermediate scale 3-D tank experiment and inter-tank comparisons. For these systems, physical heterogeneity at or above the decimeter scale does not affect global scale uranium desorption and transport. Instead, uranium fluxes are controlled by chemistry dependent desorption patterns induced by changing the influent ionic composition. Published by Elsevier B.V.

Simplified behaviors from increased heterogeneity: I. 2-D uranium transport experiments at the decimeter scale

NASA Astrophysics Data System (ADS)

Miller, Andrew W.; Rodriguez, Derrick R.; Honeyman, Bruce D.

2013-05-01

Intermediate scale tank studies were conducted to examine the effects of physical heterogeneity of aquifer material on uranium desorption and subsequent transport in order to bridge the scaling gap between bench and field scale systems. Uranium contaminated sediment from a former uranium mill field site was packed into two 2-D tanks with internal dimensions of 2.44 × 1.22 × 0.076 m (tank 1) and 2.44 × 0.61 × 0.076 m (tank 2). Tank 1 was packed in a physically homogenous manner, and tank 2 was packed with long lenses of high and low conductivities resulting in different flow fields within the tanks. Chemical gradients within the flow domain were altered by temporal changes in influent water chemistry. The uranium source was desorption from the sediment. Despite the physical differences in the flow fields, there were minimal differences in global uranium leaching behavior between the two tanks. The dominant uranium species in both tanks over time and space was Ca2UO2(CO3)30. However, the uranium/alkalinity relationships varied as a function of time in tank 1 and were independent of time in tank 2. After planned stop-flow events, small, short-lived rebounds were observed in tank 1 while no rebound of uranium concentrations was observed in tank 2. Despite appearing to be in local equilibrium with respect to uranium desorption, a previously derived surface complexation model was insufficient to describe uranium partitioning within the flow domain. This is the first in a pair of papers; the companion paper presents an intermediate scale 3-D tank experiment and inter-tank comparisons. For these systems, physical heterogeneity at or above the decimeter scale does not affect global scale uranium desorption and transport. Instead, uranium fluxes are controlled by chemistry dependent desorption patterns induced by changing the influent ionic composition.

Uptake of dyes by a promising locally available agricultural solid waste: coir pith.

PubMed

Namasivayam, C; Radhika, R; Suba, S

2001-01-01

The adsorption of rhodamine-B and acid violet by coir pith carbon was carried out by varying the parameters such as agitation time, dye concentration, adsorbent dose and pH. The adsorption followed both Langmuir and Freundlich isotherms. The adsorption capacity was found to be 2.56 mg and 8.06 mg dye per g of the adsorbent for rhodamine-B and acid violet, respectively. Adsorption of dyes followed first order rate kinetics. Acidic pH was favorable for the adsorption of acid violet and alkaline pH was favorable to rhodamine-B. Desorption studies showed that alkaline pH was favorable for the desorption of acid violet and acidic pH was favorable for the desorption of rhodamine-B.

Buckling vs. particle desorption in a particle-covered drop subject to compressive surface stresses: a simulation study.

PubMed

Gu, Chuan; Botto, Lorenzo

2018-01-31

Predicting the behaviour of particle-covered fluid interfaces under compression has implications in several fields. The surface-tension driven adhesion of particles to drops and bubbles is exploited for example to enhance the stability of foams and emulsion and develop new generation materials. When a particle-covered fluid interface is compressed, one can observe either smooth buckling or particle desorption from the interface. The microscopic mechanisms leading to the buckling-to-desorption transition are not fully understood. In this paper we simulate a spherical drop covered by a monolayer of spherical particles. The particle-covered interface is subject to time-dependent compressive surface stresses that mimic the slow deflation of the drop. The buckling-to-desorption transition depends in a non-trivial way on three non-dimensional parameters: the ratio Π s /γ of particle-induced surface pressure and bare surface tension, the ratio a/R of particle and drop radii, and the parameter f characterising the strength of adhesion of each particle to the interface. Based on the insights from the simulations, we propose a configuration diagram describing the effect of these controlling parameters. We find that particle desorption is highly correlated with a mechanical instability that produces small-scale undulations of the monolayer of the order of the particle size that grow when the surface pressure is sufficiently large. We argue that the large local curvature associated with these small undulations can produce large normal forces, enhancing the probability of desorption.

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Matrix Assisted and/or Laser Desorption Ionization Quadrupole Ion Trap Time-of-Flight Mass Spectrometry of WO3 Clusters Formation in Gas Phase. Nanodiamonds, Fullerene, and Graphene Oxide Matrices

NASA Astrophysics Data System (ADS)

Ausekar, Mayuri Vilas; Mawale, Ravi Madhukar; Pazdera, Pavel; Havel, Josef

2018-03-01

The formation of W x O y +●/-● clusters in the gas phase was studied by laser desorption ionization (LDI) and matrix assisted laser desorption ionization (MALDI) of solid WO3. LDI produced (WO3) n + ●/- ● ( n = 1-7) clusters. In MALDI, when using nano-diamonds (NDs), graphene oxide (GO), or fullerene (C60) matrices, higher mass clusters were generated. In addition to (WO3) n -● clusters, oxygen-rich or -deficient species were found in both LDI and MALDI (with the total number of clusters exceeding one hundred ≈ 137). This is the first time that such matrices have been used for the generation of(WO3) n + ●/-● clusters in the gas phase, while new high mass clusters (WO3) n -● ( n = 12-19) were also detected. [Figure not available: see fulltext.

In vitro and in vivo biological activities of anthocyanins from Nitraria tangutorun Bobr. fruits.

PubMed

Ma, Tao; Hu, Na; Ding, Chenxi; Zhang, Qiulong; Li, Wencong; Suo, Yourui; Wang, Honglun; Bai, Bo; Ding, Chenxu

2016-03-01

Anthocyanins are the main compounds in Nitraria tangutorun Bobr. The enrichment and purification of anthocyanins on macroporous resins were investigated. Regarding anthocyanin purification, static adsorption and desorption were studied. The optimal experimental conditions were the following: resin type: X-5; static adsorption time: 6h; desorption solution: ethanol-water-HCl (80:19:1, V/V/V; pH 1); desorption time: 40min. Furthermore, the in vitro and in vivo biological activities of the anthocyanins were evaluated. The anthocyanins showed ideal scavenging effects on free radicals in vitro, especially on 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl free radical (OH). In the animal experiment, blood lipid metabolism of hyperlipidemia rats was regulated by anthocyanin contents. The superoxide dismutase (SOD) activity and the total antioxidant capacity (TAC) of hyperlipidemia rats were also improved by anthocyanins. These results showed that anthocyanins from N. tangutorun Bobr. fruits had potential biological activities in vivo as well as in vitro. Copyright © 2015. Published by Elsevier Ltd.

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D

2017-06-01

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (k a ) and desorption (k d ) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated k a and k d values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermal stability of single-side hydrogenated graphene

NASA Astrophysics Data System (ADS)

Openov, L. A.; Podlivaev, A. I.

2012-11-01

The temperature dependence of the time of hydrogen desorption from single-side hydrogenated graphene is calculated using molecular dynamics simulation. The activation energy ( E a = 0.75 ± 0.10 eV) and the frequency factor ( A = (2.5 ± 1.0) × 1015 s-1) of the desorption are found. This quasi-two-dimensional carbon-hydrogen system is shown to have a relatively low thermal stability, which makes it difficult to use it in practice.

Evidence that Polycyclic Aromatic Hydrocarbons in Two Carbonaceous Chondrites Predate Parent-Body Formation

NASA Technical Reports Server (NTRS)

Plows, F. L.; Elsila, J. E.; Zare, R. N.; Buseck, P. R.

2003-01-01

Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated using spatially resolved microprobe laser-desorption laser-ionization mass spectrometry. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating prior to or contemporary with the formation of the parent body, consistent with proposed interstellar formation mechanisms.

Metolachlor Sorption and Degradation in Soil Amended with Fresh and Aged Biochars.

PubMed

Trigo, Carmen; Spokas, Kurt A; Hall, Kathleen E; Cox, Lucia; Koskinen, William C

2016-04-27

Addition of organic amendments such as biochar to soils can influence pesticide sorption-desorption processes and, in turn, the amount of pesticide readily availability for transport and biodegradation. Sorption-desorption processes are affected by both the physical and chemical properties of soils and pesticides, as well as soil-pesticide contact time, or aging. Changes in sorption-desorption of metolachlor with aging in soil amended with three macadamia nut shell biochars aged 0 (BCmac-fr), 1 year (BCmac-1yr), and 2 years (BCmac-2yr) and two wood biochars aged 0 (BCwood-fr) and 5 years (BCwood-5yr) were determined. Apparent sorption coefficient (Kd-app) values increased with incubation time to a greater extent in amended soil as compared to unamended soils; Kd-app increased by 1.2-fold for the unamended soil, 2.0-fold for BCwood-fr, 1.4-fold for BCwood-5yr, 2.4-fold for BCmac-fr, 2.5-fold for BCmac-1yr, and 1.9-fold for BCmac-4yr. The increase in calculated Kd-app value was the result of a 15% decrease in the metolachlor solution concentration extractable with CaCl2 solution with incubation time in soil as compared to a 50% decrease in amended soil with very little change in the sorbed concentration. Differences could possibly be due to diffusion to less accessible or stronger binding sites with time, a faster rate of degradation (in solution and on labile sites) than desorption, or a combination of the two in the amended soils. These data show that transport models would overpredict the depth of movement of metolachlor in soil if effects of aging or biochar amendments are not considered.

Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride tanks: Thermodynamic and design considerations towards integrated systems

NASA Astrophysics Data System (ADS)

Yiotis, Andreas G.; Kainourgiakis, Michael E.; Kosmidis, Lefteris I.; Charalambopoulou, Georgia C.; Stubos, Athanassios K.

2014-12-01

We study the thermal coupling potential between a high temperature metal hydride (MH) tank and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources. Based on principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical expressions for both the thermal power produced during SOFC operation and the corresponding thermal power required for H2 desorption, as a function of the operating temperature, efficiency and fuel utilization ratio in the SOFC, and the MH enthalpy of desorption in the tank. Based on these calculations, we propose an integrated SOFC/MH design where heat is transferred primarily by radiation to the tank in order to maintain steady-state desorption conditions. We develop a mathematical model for this particular design that accounts for heat/mass transfer and desorption kinetics in the tank, and solve for the dynamics of the system assuming MgH2 as a storage material. Our results focus primarily on tank operating conditions, such as pressure, temperature and H2 saturation profiles vs operation time.

Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

PubMed

Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

2015-12-01

Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air.

Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

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

Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignmentmore » throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.« less

Desorption kinetics of methanol, ethanol, and water from graphene.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water, the first and second layers are not resolved. At low water coverages (<1 monolayer (ML)) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10-100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the nonalignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

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

Smith, R. Scott; Kay, Bruce D.

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer TPD spectra have the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An inversion analysis of the monolayer benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 1017 ±more » 1 s-1. The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 1016 ± 1 ML s-1.« less

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

USGS Publications Warehouse

Fuller, C.C.; Davis, J.A.

1987-01-01

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation. ?? 1987.

Simulating the volatilization of solvents in unsaturated soils during laboratory and field infiltration experiments

USGS Publications Warehouse

Cho, H. Jean; Jaffe, Peter R.; Smith, James A.

1993-01-01

This paper describes laboratory and field experiments which were conducted to study the dynamics of trichloroethylene (TCE) as it volatilized from contaminated groundwater and diffused in the presence of infiltrating water through the unsaturated soil zone to the land surface. The field experiments were conducted at the Picatinny Arsenal, which is part of the United States Geological Survey Toxic Substances Hydrology Program. In both laboratory and field settings the gas and water phase concentrations of TCE were not in equilibrium during infiltration. Gas-water mass transfer rate constants were calibrated to the experimental data using a model in which the water phase was treated as two phases: a mobile water phase and an immobile water phase. The mass transfer limitations of a volatile organic compound between the gas and liquid phases were described explicitly in the model. In the laboratory experiment the porous medium was nonsorbing, and water infiltration rates ranged from 0.076 to 0.28 cm h−1. In the field experiment the water infiltration rate was 0.34 cm h−1, and sorption onto the soil matrix was significant. The laboratory-calibrated gas-water mass transfer rate constant is 3.3×10−4 h−1 for an infiltration rate of 0.076 cm h−1 and 1.4×10−3 h−1 for an infiltration rate of 0.28 cm h−1. The overall mass transfer rate coefficients, incorporating the contribution of mass transfer between mobile and immobile water phases and the variation of interfacial area with moisture content, range from 3×10−4 h−1 to 1×10−2 h−1. A power law model relates the gas-water mass transfer rate constant to the infiltration rate and the fraction of the water phase which is mobile. It was found that the results from the laboratory experiments could not be extrapolated to the field. In order to simulate the field experiment the very slow desorption of TCE from the soil matrix was incorporated into the mathematical model. When desorption from the soil matrix was added to the model, the calibrated gas-water mass transfer rate constant is 2 orders of magnitude lower than that predicted using the power law model developed for the nonsorbing laboratory soil.

Hydrogen Storage Performances of REMg11Ni (RE = Sm, Y) Alloys Prepared by Mechanical Milling

NASA Astrophysics Data System (ADS)

Zhang, Yanghuan; Cui, Songsong; Yuan, Zeming; Gao, Jinliang; Dong, Xiaoping; Qi, Yan; Guo, Shihai

2018-01-01

This study adopted mechanical milling to prepare Mg-based REMg11Ni (RE = Sm, Y) hydrogen storage alloys. The alloy structures were examined by X-ray diffraction and transmission electron microscopy. The isothermal hydrogenation thermodynamics and kinetics were determined by an automatic Sievert apparatus. The non-isothermal dehydrogenation performance of the alloys was tested by differential scanning calorimetry and thermogravimetry at different heating rates. The results showed a nanocrystalline and amorphous tendency for the alloys. The YMg11Ni alloy exhibited a larger hydrogen absorption capacity, faster hydriding rate, and lower temperature of onset hydrogen desorption than the SmMg11Ni alloy. The hydrogen desorption temperatures of the REMg11Ni (RE = Sm, Y) alloys were 557.6 K and 549.8 K (284.6 °C and 276.8 °C), respectively. The hydrogen desorption property of the RE = Y alloy was found superior to the RE = Sm alloy based on the time required to absorb 3 wt pct H2, i.e., the time needed by the RE = Y alloy was reduced to 1106, 456, 363, and 180 s, respectively, corresponding to the hydrogen desorption temperatures of 593 K, 613 K, 633 K, and 653 K (320 °C, 340 °C, 360 °C, and 380 °C), compared to 1488, 574, 390, and 192 s for the RE = Sm alloy under identical conditions. The dehydrogenation activation energies were 100.31 and 98.01 kJ/mol for the REMg11Ni (RE = Sm, Y) alloys, respectively, which agreed with those of the RE = Y alloy showing a superior hydrogen desorption property.

Bicarbonate Impact on U(VI) Bioreduction in a Shallow Alluvial Aquifer

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

Long, Philip E.; Williams, Kenneth H.; Davis, James A.

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggestedmore » the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, that the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.« less

Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

NASA Astrophysics Data System (ADS)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S. F.; Gupta, Manish; Chandler, Darrell P.; Murray, Chris; Peacock, Aaron D.; Giloteaux, Ludovic; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

2015-02-01

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ∼3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

Wellsite, laboratory, and mathematical techniques for determining sorbed gas content of coals and gas shales utilizing well cuttings

USGS Publications Warehouse

Newell, K.D.

2007-01-01

Drill cuttings can be used for desorption analyses but with more uncertainty than desorption analyses done with cores. Drill cuttings are not recommended to take the place of core, but in some circumstances, desorption work with cuttings can provide a timely and economic supplement to that of cores. The mixed lithologic nature of drill cuttings is primarily the source of uncertainty in their analysis for gas content, for it is unclear how to apportion the gas generated from both the coal and the dark-colored shale that is mixed in usually with the coal. In the Western Interior Basin Coal Basin in eastern Kansas (Pennsylvanian-age coals), dark-colored shales with normal (??? 100 API units) gamma-ray levels seem to give off minimal amounts of gas on the order of less than five standard cubic feet per ton (scf/ton). In some cuttings analyses this rule of thumb for gas content of the shale is adequate for inferring the gas content of coals, but shales with high-gamma-ray values (>150 API units) may yield several times this amount of gas. The uncertainty in desorption analysis of drill cuttings can be depicted graphically on a diagram identified as a "lithologic component sensitivity analysis diagram." Comparison of cuttings desorption results from nearby wells on this diagram, can sometimes yield an unique solution for the gas content of both a dark shale and coal mixed in a cuttings sample. A mathematical solution, based on equating the dry, ash-free gas-contents of the admixed coal and dark-colored shale, also yields results that are correlative to data from nearby cores. ?? 2007 International Association for Mathematical Geology.

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

NASA Technical Reports Server (NTRS)

Yu, Anthony W.; Li, Steven X.; Fahey, Molly E.; Grubisic, Andrej; Farcy, Benjamin J.; Uckert, Kyle; Li, Xiang; Getty, Stephanie

2017-01-01

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 µm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Desorption Kinetics of Benzene and Cyclohexane from a Graphene Surface.

PubMed

Smith, R Scott; Kay, Bruce D

2018-01-18

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature-programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer and submonolayer TPD spectra for coverages greater than ∼0.1 ML have nearly the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An "inversion" procedure in which the prefactor is varied to find the value that best reproduces the entire set of experimental desorption spectra was used to analyze the benzene data. The inversion analysis of the benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 10 17±1 s -1 . The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 10 16±1 ML s -1 .

A novel approach to bar adsorptive microextraction: Cork as extractor phase for determination of benzophenone, triclocarban and parabens in aqueous samples.

PubMed

Dias, Adriana Neves; da Silva, Ana Cristine; Simão, Vanessa; Merib, Josias; Carasek, Eduardo

2015-08-12

This study describes the use of cork as a new coating for bar adsorptive microextraction (BAμE) and its application in determining benzophenone, triclocarban and parabens in aqueous samples by HPLC-DAD. In this study bars with 7.5 and 15 mm of length were used. The extraction and liquid desorption steps for BAμE were optimized employing multivariate and univariate procedures. The desorption time and solvent used for liquid desorption were optimized by univariate and multivariate studies, respectively. For the extraction step the sample pH was optimized by univariate experiments while the parameters extraction time and ionic strength were evaluated using the Doehlert design. The optimum extraction conditions were sample pH 5.5, NaCl concentration 25% and extraction time 90 min. Liquid desorption was carried out for 30 min with 250 μL (bar length of 15 mm) or 100 μL (bar length of 7.5 mm) of ACN:MeOH (50:50, v/v). The quantification limits varied between 1.6 and 20 μg L(-1) (bar length of 15 mm) and 0.64 and 8 μg L(-1) (bar length of 7.5 mm). The linear correlation coefficients were higher than 0.98 for both bars. The method with 7.5 mm bar length showed recovery values between 65 and 123%. The bar-to-bar reproducibility and the repeatability were lower than 13% (n = 2) and 14% (n = 3), respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Detection of Serum Lysophosphatidic Acids Using Affinity Binding and Surface Enhanced Laser Desorption/Ionization (SELDI) Time of Flight Mass Spectrometry

DTIC Science & Technology

2005-04-01

AD Award Number: DAIMD17-03-1-0222 TITLE: Detection of Serum Lysophosphatidic Acids Using Affinity Binding and Surface Enhanced Laser Desorption...Annual (1 Apr 04 - 31 Mar 05) 4. TITLE AND SUBTITLE 5. FUNDING NUMBERS Detection of Serum Lysophosphatidic Acids Using Affinity DAMD17-03-1-0222...of multiple forms of lysophosphatidic acid (LPA). LPA increases proliferation, prevents apoptosis and anoikis, increases invasiveness, decreases

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

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

Ovchinnikova, Olga S; Nikiforov, Maxim; Bradshaw, James A

2011-01-01

Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2more » array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.« less

Determination of phenolic priority pollutants utilizing permeation sampling method

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

Zhang, Guozheng.

1990-01-01

A passive permeation sampling method for the determination of phenolic priority pollutants in water was developed. Phenols in an aqueous solution permeate a polymeric membrane and are collected on a solid adsorbent in a sampling device. Both solvent and thermal desorption techniques were employed to recovery phenolic pollutants collected. In the solvent desorption, phenolic compounds collected on the XAD-7 resin, and then desorbed by acetonitrile. In the thermal desorption, phenolic compounds collected on Tenax-TA were recovered thermally, Separation and quantification is achieved by a SPB-5 capillary column gas chromatography using a flame ionization detector. There are linear relationships between themore » amount of phenolic compounds collected and the products of the exposure times and concentrations over the range from 5 ppb to 20 ppm with precisions no worse than 13%. The permeation rates of the phenolic pollutants depend upon the exposure temperature, solution pH and membrane area. Samples collected can be stored for up to two weeks without loss. This method provides a simple, convenient and inexpensive way for monitoring the time-weighted-average concentration without the use of a pumping system. An automated sampler which combines the permeation and the thermal desorption techniques together was also developed for water sample obtained from grab sampling. The on-line setup provides a high degree of automation. Detection limits at 10 ppb can be achieved using this sampler.« less

Direct and comprehensive analysis of dyes based on integrated molecular and structural information via laser desorption laser postionization mass spectrometry.

PubMed

Liu, Rong; Yin, Zhibin; Leng, Yixin; Hang, Wei; Huang, Benli

2018-01-01

Laser desorption laser postionization time-of-flight mass spectrometry (LDPI-TOFMS) was employed for direct analysis and determination of typical basic dyes. It was also used for the analysis and comprehensive understanding of complex materials such as blue ballpoint pen inks. Simultaneous emergences of fragmental and molecular information largely simplify and facilitate unambiguous identification of dyes via variable energy of 266nm postionization laser. More specifically, by optimizing postionization laser energy with the same energy of desorption laser, the structurally significant results show definite differences in the fragmentation patterns, which offer opportunities for discrimination of isomeric species with identical molecular weight. Moreover, relatively high spectra resolution can be acquired without the expense of sensitivity. In contrast to laser desorption/ionization mass spectrometry (LDI-MS), LDPI-MS simultaneously offers valuable molecular information about dyes in traces, solvents and additives about inks, thereby offering direct determination and comprehensive understanding of blue ballpoint inks and giving a high level of confidence to discriminate the complicated evidentiary samples. In addition, direct analysis of the inks not only allows the avoidance of the tedious sample preparation processes, significantly shortening the overall analysis time and improving throughput, but allows minimized sample consumption which is important for rare and precious samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Species identification of clinical isolates of anaerobic bacteria: a comparison of two matrix-assisted laser desorption ionization-time of flight mass spectrometry systems.

PubMed

Justesen, Ulrik Stenz; Holm, Anette; Knudsen, Elisa; Andersen, Line Bisgaard; Jensen, Thøger Gorm; Kemp, Michael; Skov, Marianne Nielsine; Gahrn-Hansen, Bente; Møller, Jens Kjølseth

2011-12-01

We compared two matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) systems (Shimadzu/SARAMIS and Bruker) on a collection of consecutive clinically important anaerobic bacteria (n = 290). The Bruker system had more correct identifications to the species level (67.2% versus 49.0%), but also more incorrect identifications (7.9% versus 1.4%). The system databases need to be optimized to increase identification levels. However, MALDI-TOF MS in its present version seems to be a fast and inexpensive method for identification of most clinically important anaerobic bacteria.

Identification of Aeromonas isolates by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

PubMed

Lamy, Brigitte; Kodjo, Angeli; Laurent, Frédéric

2011-09-01

We evaluated the accuracy of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for identifying aeromonads with an extraction procedure. Genus-level accuracy was 100%. Compared to rpoB gene sequencing, species-level accuracy was 90.6% (29/32) for type and reference strains and 91.4% for a collection of 139 clinical and environmental isolates, making this system one of the most accurate and rapid methods for phenotypic identification. The reliability of this technique was very promising, although some improvements in database composition, taxonomy, and discriminatory power are needed. Copyright © 2011 Elsevier Inc. All rights reserved.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometric analysis of degradation products after treatment of methylene blue aqueous solution with three-dimensionally integrated microsolution plasma

NASA Astrophysics Data System (ADS)

Shirafuji, Tatsuru; Nomura, Ayano; Hayashi, Yui; Tanaka, Kenji; Goto, Motonobu

2016-01-01

Methylene blue can be degraded in three-dimensionally integrated microsolution plasma. The degradation products have been analyzed by matrix-assisted laser desorption ionization time-of-flight (MALDI TOF) mass spectrometry to understand the degradation mechanisms. The results of MALDI TOF mass spectrometry have shown that sulfoxide is formed at the first stage of the oxidation. Then, partial oxidation proceeds on the methyl groups left on the sulfoxide. The sulfoxide is subsequently separated to two benzene derivatives. Finally, weak functional groups are removed from the benzene derivatives.

Ultrafast Carbon Dioxide Sorption Kinetics Using Lithium Silicate Nanowires.

PubMed

Nambo, Apolo; He, Juan; Nguyen, Tu Quang; Atla, Veerendra; Druffel, Thad; Sunkara, Mahendra

2017-06-14

In this paper, the Li 4 SiO 4 nanowires (NWs) were shown to be promising for CO 2 capture with ultrafast kinetics. Specifically, the nanowire powders exhibited an uptake of 0.35 g g -1 of CO 2 at an ultrafast adsorption rate of 0.22 g g -1 min -1 at 650-700 °C. Lithium silicate (Li 4 SiO 4 ) nanowires and nanopowders were synthesized using a "solvo-plasma" technique involving plasma oxidation of silicon precursors mixed with lithium hydroxide. The kinetic parameter values (k) extracted from sorption kinetics obtained using NW powders are 1 order of magnitude higher than those previously reported for the Li 4 SiO 4 -CO 2 reaction system. The time scales for CO 2 sorption using nanowires are approximately 3 min and two orders magnitude faster compared to those obtained using lithium silicate powders with spherical morphologies and aggregates. Furthermore, Li 4 SiO 4 nanowire powders showed reversibility through sorption-desorption cycles indicating their suitability for CO 2 capture applications. All of the morphologies of Li 4 SiO 4 powders exhibited a double exponential behavior in the adsorption kinetics indicating two distinct time constants for kinetic and the mass transfer limited regimes.

Short communication: Identification of subclinical cow mastitis pathogens in milk by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Barreiro, J R; Ferreira, C R; Sanvido, G B; Kostrzewa, M; Maier, T; Wegemann, B; Böttcher, V; Eberlin, M N; dos Santos, M V

2010-12-01

Subclinical mastitis is a common and easily disseminated disease in dairy herds. Its routine diagnosis via bacterial culture and biochemical identification is a difficult and time-consuming process. In this work, we show that matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allows bacterial identification with high confidence and speed (1 d for bacterial growth and analysis). With the use of MALDI-TOF MS, 33 bacterial culture isolates from milk of different dairy cows from several farms were analyzed, and the results were compared with those obtained by classical biochemical methods. This proof-of-concept case demonstrates the reliability of MALDI-TOF MS bacterial identification, and its increased selectivity as illustrated by the additional identification of coagulase-negative Staphylococcus species and mixed bacterial cultures. Matrix-assisted laser desorption-ionization mass spectrometry considerably accelerates the diagnosis of mastitis pathogens, especially in cases of subclinical mastitis. More immediate and efficient animal management strategies for mastitis and milk quality control in the dairy industry can therefore be applied. Copyright © 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Diffusive sampling of methylene chloride with solid phase microextraction.

PubMed

Chen, Cheng-Yao; Hsiech, Chunming; Lin, Jia-Ming

2006-12-29

This study examined the characteristics of a solid phase microextraction (SPME) assembly as a passive sampler to determine the short-term exposure level (STEL) of methylene chloride. Two types of SPME fibers and six sampling-related factors were chosen and nested in an L(18) Taguchi's orthogonal array. Samples were thermally desorpted and analyzed by gas chromatograph equipped with an electron capture detector (GC/ECD). The use of 85-mum Carboxen/polydimethylsiloxane (Car/PDMS) fibers resulted in greater adsorbed mass, which was highly correlated with the product of concentration and sampling time (r>0.99, p<0.0001), than 85-microm polyacrylate fibers. The sampling rate (SR) of the 85-microm Carboxen/polydimethylsiloxane fibers was not significantly affected by variations in relative humidity (0-80%) and coexistent toluene (none to 100 ppm). Variance of sampling rate was predominantly attributed to the diffusive path length (86.4%) and sampling time (5.7%). With diffusive paths of 3, 10 and 15 mm, the sampling rates of 85-microm Carboxen/polydimethylsiloxane fibers for methylene chloride were 1.4 x 10(-2), 7.7 x 10(-3) and 5.1 x1 0(-3)mL min(-1), respectively. The measured sampling rates were greater than the theoretical values, and decreased with increment of sampling time until they came to constant.

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

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

Smith, R. Scott; May, Robert A.; Kay, Bruce D.

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do notmore » align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.« less

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces.

PubMed

Smith, R Scott; May, R Alan; Kay, Bruce D

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from graphene-covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature-programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multilayer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The nonalignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

Reaction and Aggregation Dynamics of Cell Surface Receptors

NASA Astrophysics Data System (ADS)

Wang, Michelle Dong

This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

Fate of As(V)-treated nano zero-valent iron: determination of arsenic desorption potential under varying environmental conditions by phosphate extraction.

PubMed

Dong, Haoran; Guan, Xiaohong; Lo, Irene M C

2012-09-01

Nano zero-valent iron (NZVI) offers a promising approach for arsenic remediation, but the spent NZVI with elevated arsenic content could arouse safety concerns. This study investigated the fate of As(V)-treated NZVI (As-NZVI), by examining the desorption potential of As under varying conditions. The desorption kinetics of As from As-NZVI as induced by phosphate was well described by a biphasic rate model. The effects of As(V)/NZVI mass ratio, pH, and aging time on arsenic desorption from As-NZVI by phosphate were investigated. Less arsenic desorption was observed at lower pH or higher As(V)/NZVI mass ratio, where stronger complexes (bidentate) formed between As(V) and NZVI corrosion products as indicated by FTIR analysis. Compared with the fresh As-NZVI, the amount of phosphate-extractable As significantly decreased in As-NZVI aged for 30 or 60 days. The results of the sequential extraction experiments demonstrated that a larger fraction of As was sorbed in the crystalline phases after aging, making it less susceptible to phosphate displacement. However, at pH 9, a slightly higher proportion of phosphate-extractable As was observed in the 60-day sample than in the 30-day sample. XPS results revealed the transformation of As(V) to more easily desorbed As(III) during aging and a higher As(III)/As(V) ratio in the 60-day sample at pH 9, which might have resulted in the higher desorption. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics of Cd(ii) adsorption and desorption on ferrihydrite: experiments and modeling.

PubMed

Liang, Yuzhen; Tian, Lei; Lu, Yang; Peng, Lanfang; Wang, Pei; Lin, Jingyi; Cheng, Tao; Dang, Zhi; Shi, Zhenqing

2018-05-15

The kinetics of Cd(ii) adsorption/desorption on ferrihydrite is an important process affecting the fate, transport, and bioavailability of Cd(ii) in the environment, which was rarely systematically studied and understood at quantitative levels. In this work, a combination of stirred-flow kinetic experiments, batch adsorption equilibrium experiments, high-resolution transmission electron microscopy (HR-TEM), and mechanistic kinetic modeling were used to study the kinetic behaviors of Cd(ii) adsorption/desorption on ferrihydrite. HR-TEM images showed the open, loose, and sponge-like structure of ferrihydrite. The batch adsorption equilibrium experiments revealed that higher pH and initial metal concentration increased Cd(ii) adsorption on ferrihydrite. The stirred-flow kinetic results demonstrated the increased adsorption rate and capacity as a result of the increased pH, influent concentration, and ferrihydrite concentration. The mechanistic kinetic model successfully described the kinetic behaviors of Cd(ii) during the adsorption and desorption stages under various chemistry conditions. The model calculations showed that the adsorption rate coefficients varied as a function of solution chemistry, and the relative contributions of the weak and strong ferrihydrite sites for Cd(ii) binding varied with time at different pH and initial metal concentrations. Our model is able to quantitatively assess the contributions of each individual ferrihydrite binding site to the overall Cd(ii) adsorption/desorption kinetics. This study provided insights into the dynamic behavior of Cd(ii) and a predictive modeling tool for Cd(ii) adsorption/desorption kinetics when ferrihydrite is present, which may be helpful for the risk assessment and management of Cd contaminated sites.

Importance of the structure and nanoporosity of organic matter on the desorption kinetics of benzo[a]pyrene in sediments.

PubMed

Huang, Youda; Zhang, Dainan; Duan, Dandan; Yang, Yu; Xiong, Yongqiang; Ran, Yong

2017-06-01

The desorption kinetics and mechanism were investigated using a Tenax extraction technique on different sediments spiked with radiocarbon-labeled benzo[a]pyrene (BaP). Five sedimentary fractions were sequentially fractionated, and the only nonhydrolyzable organic carbon fractions (NHC) were characterized using advanced solid-state 13 C nuclear magnetic resonance spectroscopy (NMR), improved six end-member model, and a CO 2 gas adsorption technique. The sediments contained high percentages of algaenan and/or sporopollenin but low percentages of black carbon and lignin. A first-order, two-compartment kinetics model described the desorption process very well (R 2  > 0.990). Although some of the organic carbon fractions were significantly related to the desorption kinetics parameters, the NHC fractions showed the highly significant correlation. Moreover, the nanoporosity or specific surface area (SSA) of the NHC fractions was highly related to their OC contents and aliphatic C (R 2  = 0.960, p < 0.01). The multiple regression equations among the desorption kinetics parameters, structural parameters, and nanoporosity were well established (R 2 =>0.999). Nanoporosity and aromatic C were the dominant contributors. Furthermore, the enhanced percentages of desorbed BaP at elevated temperatures significantly showed a linear regression with the structure and nanoporosity. To our knowledge, the above evidence demonstrates for the first time that the transfer (or diffusion) of BaP in the nanopores of condensed aromatic components is the dominant mechanism of the desorption kinetics of BaP at organic matter particle scale. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of a Detailed Surface Chemistry Framework in DSMC

NASA Technical Reports Server (NTRS)

Swaminathan-Gopalan, K.; Borner, A.; Stephani, K. A.

2017-01-01

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

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

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

2015-12-21

Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

Enhanced desorption of persistent organic pollutants from microplastics under simulated physiological conditions.

PubMed

Bakir, Adil; Rowland, Steven J; Thompson, Richard C

2014-02-01

Microplastics have the potential to uptake and release persistent organic pollutants (POPs); however, subsequent transfer to marine organisms is poorly understood. Some models estimating transfer of sorbed contaminants to organisms neglect the role of gut surfactants under differing physiological conditions in the gut (varying pH and temperature), examined here. We investigated the potential for polyvinylchloride (PVC) and polyethylene (PE) to sorb and desorb (14)C-DDT, (14)C-phenanthrene (Phe), (14)C-perfluorooctanoic acid (PFOA) and (14)C-di-2-ethylhexyl phthalate (DEHP). Desorption rates of POPs were quantified in seawater and under simulated gut conditions. Influence of pH and temperature was examined in order to represent cold and warm blooded organisms. Desorption rates were faster with gut surfactant, with a further substantial increase under conditions simulating warm blooded organisms. Desorption under gut conditions could be up to 30 times greater than in seawater alone. Of the POP/plastic combinations examined Phe with PE gave the highest potential for transport to organisms. Copyright © 2013 Elsevier Ltd. All rights reserved.

Does bioavailability limit biodegradation? A comparison of hydrocarbon biodegradation and desorption rates in aged soils.

PubMed

Huesemann, Michael H; Hausmann, Tom S; Fortman, Tim J

2004-08-01

In order to determine whether bioavailability limits the biodegradability of petroleum hydrocarbons in aged soils, both the biodegradation and abiotic desorption rates of PAHs and n-alkanes were measured at various time points in six different aged soils undergoing slurry bioremediation treatment. Alkane biodegradation rates were always much greater than the respective desorption rates, indicating that these saturated hydrocarbons apparently do not need to be dissolved into the aqueous phase prior to metabolism by soil microorganisms. The biodegradation of PAHs was generally not mass-transfer rate limited during the initial phase, while it often became so at the end of the treatment period when biodegradation rates equaled abiotic desorption rates. However, in all cases where PAH biodegradation was not observed or PAH removal temporarily stalled, bioavailability limitations were not deemed responsible for this recalcitrance since these PAHs desorbed rapidly from the soil into the aqueous phase. Consequently, aged PAHs that are often thought to be recalcitrant due to bioavailability limitations may not be so and therefore may pose a greater risk to environmental receptors than previously thought.

Does Bioavailability Limit Biodegradability? A Comparison of Hydrocarbon Biodegradation and Desorption Rates in Aged Soils

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

Huesemann, Michael H.; Hausmann, Tom S.; Fortman, Timothy J.

In order to determine whether bioavailability limits the biodegradability of petroleum hydrocarbons in aged soils, both the biodegradation and abiotic desorption rates of PAHs and n-alkanes were measured at various time points in six different aged soils undergoing slurry bioremediation treatment. Alkane biodegradation rates were always much greater than the respective desorption rates, indicating that these saturated hydrocarbons do not need to be transferred into the aqueous phase prior to metabolism by soil microorganisms. The biodegradation of PAHs was generally not mass-transfer rate limited during the initial phase, while it often became so at the end of the treatment periodmore » when biodegradation rates equaled abiotic desorption rates. However, in all cases where PAH biodegradation was not observed or PAH removal temporarily stalled, bioavailability limitations were not deemed responsible for this recalcitrance since these PAHs desorbed rapidly from the soil into the aqueous phase. Consequently, aged PAHs that are often thought to be recalcitrant due to bioavailability limitations may not be so and therefore may pose a greater risk to environmental receptors than previously thought.« less

Adsorption-desorption kinetics of soft particles onto surfaces

NASA Astrophysics Data System (ADS)

Osberg, Brendan; Gerland, Ulrich

A broad range of physical, chemical, and biological systems feature processes in which particles randomly adsorb on a substrate. Theoretical models usually assume ``hard'' (mutually impenetrable) particles, but in soft matter physics the adsorbing particles can be effectively compressible, implying ``soft'' interaction potentials. We recently studied the kinetics of such soft particles adsorbing onto one-dimensional substrates, identifying three novel phenomena: (i) a gradual density increase, or ''cramming'', replaces the usual jamming behavior of hard particles, (ii) a density overshoot, can occur (only for soft particles) on a time scale set by the desorption rate, and (iii) relaxation rates of soft particles increase with particle size (on a lattice), while hard particles show the opposite trend. The latter occurs since unjamming requires desorption and many-bodied reorganization to equilibrate -a process that is generally very slow. Here we extend this analysis to a two-dimensional substrate, focusing on the question of whether the adsorption-desorption kinetics of particles in two dimensions is similarly enriched by the introduction of soft interactions. Application to experiments, for example the adsorption of fibrinogen on two-dimensional surfaces, will be discussed.

Desorption isotherms of salted minced pork using K-lactate as a substitute for NaCl.

PubMed

Muñoz, I; Arnau, J; Costa-Corredor, A; Gou, P

2009-12-01

The aim of this study was to obtain and compare water desorption isotherms of ground meat containing NaCl (0.107kg NaCl/kg raw-meat dry matter) and/or K-lactate as NaCl substitute at two different levels of molar substitution (30% and 100%). A thin layer of salted ground meat was dried and sampled at pre-determined times. The moisture content of the samples and their water activities (a(w)) were measured at 5°C and 25°C. Results showed that ground meat with NaCl and/or different K-lactate contents had a similar water desorption isotherm for a(w) ranging from 0.7 to 1.0. Below 0.7, the water equilibrium content fell with small decreases in a(w) faster for meat with NaCl than for meat with K-lactate. K-lactate could reduce the excessive hardening at the surface of salted meat products. Experimental desorption isotherms were compared to those estimated using two approaches of the Ross equation. Models provided a good fit for the experimental data.

Measurement of toxic volatile organic compounds in indoor air of semiconductor foundries using multisorbent adsorption/thermal desorption coupled with gas chromatography-mass spectrometry.

PubMed

Wu, Chien-Hou; Lin, Ming-Nan; Feng, Chien-Tai; Yang, Kuang-Ling; Lo, Yu-Shiu; Lo, Jiunn-Guang

2003-05-09

A method for the qualitative and quantitative analysis of volatile organic compounds (VOCs) in the air of class-100 clean rooms at semiconductor fabrication facilities was developed. Air samples from two semiconductor factories were collected each hour on multisorbent tubes (including Carbopack B, Carbopack C, and Carbosieve SIII) with a 24-h automatic active sampling system and analyzed using adsorption/thermal desorption coupled with gas chromatography-mass spectrometry. Experimental parameters, including thermal desorption temperature, desorption time, and cryofocusing temperature, were optimized. The average recoveries and the method detection limits for the target compounds were in the range 94-101% and 0.31-0.89 ppb, respectively, under the conditions of a 1 L sampling volume and 80% relative humidity. VOCs such as acetone, isopropyl alcohol, 2-heptanone, and toluene, which are commonly used in the semiconductor and electronics industries, were detected and accurately quantified with the established method. Temporal variations of the analyte concentrations observed were attributed to the improper use of organic solvents during operation.

Study of processes influencing bioavailability of pesticides in wood-soil systems: Effect of different factors.

PubMed

Marín-Benito, J M; Herrero-Hernández, E; Rodríguez-Cruz, M S; Arienzo, M; Sánchez-Martín, M J

2017-05-01

Lignocellulosic wastes and by-products containing lignin are now available in large amounts from forestry and industrial activities, and could be promising organic materials for the biosorption of pesticides by soils in order to reduce point-source pollution. Adding these materials to soil requires understanding the process of pesticide sorption-desorption by wood-soils, as sorption capacity could increase, with changes in pesticide bioavailability and final fate. The objective of this work was to study the effect that pine and oak wood added to soils had on the sorption/desorption of the pesticides linuron, alachlor, and metalaxyl. Experiments were conducted with two sandy loam and sandy clay soils each amended with two wood doses (5% and 50%) after different incubation times (0, 5 and 12 months). A low wood dose (5%) had no significant impact on the sorption (K f ) of alachlor, but K f increased for linuron (up to 5.4-1.7 times) and metalaxyl (up to 4.4 and 8.6 times) in all wood-soil systems. The results were not significantly different after different incubation times. The desorption results indicated that wood decreases the sorption irreversibility of alachlor, and increases that of linuron and metalaxyl, with a varying effect of the wood-soil incubation time. The addition of a high wood dose to soil (50%) was more significant for increasing the sorption of all the pesticides, and the sorbed amounts remaining after desorption (>49% for linuron, >33% for alachlor and >6% for metalaxyl), although there was no apparent discrimination between the two types of woods. The role of the nature of the organic carbón (K oc values) for sorption was evidenced for alachlor and metalaxyl, but not for linuron. These outcomes are of interest for extending wood application to soil as a barrier for avoiding environmental risk by point-source pollution due to the use and management of pesticides in farming systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Sorption isotherm characteristics of aonla flakes.

PubMed

Alam, Md Shafiq; Singh, Amarjit

2011-06-01

The equilibrium moisture content was determined for un-osmosed and osmosed (salt osmosed and sugar osmosed) aonla flakes using the static method at temperatures of 25, 40,50, 60 and 70 °C over a range of relative humidities from 20 to 90%. The sorption capacity of aonla decreased with an increase in temperature at constant water activity. The sorption isotherms exhibited hysteresis, in which the equilibrium moisture content was higher at a particular equilibrium relative humidity for desorption curve than for adsorption. The hysteresis effect was more pertinent for un-osmosed and salt osmosed samples in comparison to sugar osmosed samples. Five models namely the modified Chung Pfost, modified Halsey, modified Henderson, modified Exponential and Guggenheim-Anderson-de Boer (GAB) were evaluated to determine the best fit for the experimental data. For both adsorption and desorption process of aonla fruit, the equilibrium moisture content of un-osmosed and osmosed aonla samples can be predicted well by GAB model as well as modified Exponential model. Moreover, the modified Exponential model was found to be the best for describing the sorption behaviour of un-osmosed and salt osmosed samples while, GAB model for sugar osmosed aonla samples.

Towards High-Resolution Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry Coupled to Shear Force Microscopy

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

Nguyen, Son N.; Sontag, Ryan L.; Carson, James P.

Constant mode ambient mass spectrometry imaging (MSI) of tissue sections with high lateral resolution of better than 10 µm was performed by combining shear force microscopy with nanospray desorption electrospray ionization (nano-DESI). Shear force microscopy enabled precise control of the distance between the sample and nano-DESI probe during MSI experiments and provided information on sample topography. Proof-of-concept experiments were performed using lung and brain tissue sections representing spongy and dense tissues, respectively. Topography images obtained using shear force microscopy were comparable to the results obtained using contact profilometry over the same region of the tissue section. Variations in tissue heightmore » were found to be dependent on the tissue type and were in the range of 0-5 µm for lung tissue and 0-3 µm for brain tissue sections. Ion images of phospholipids obtained in this study are in good agreement with literature data. Normalization of nano-DESI MSI images to the signal of the internal standard added to the extraction solvent allowed us to construct high-resolution ion images free of matrix effects.« less

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

PubMed

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Time-resolved spectroscopy at surfaces and adsorbate dynamics: Insights from a model-system approach

NASA Astrophysics Data System (ADS)

Boström, Emil; Mikkelsen, Anders; Verdozzi, Claudio

2016-05-01

We introduce a model description of femtosecond laser induced desorption at surfaces. The substrate part of the system is taken into account as a (possibly semi-infinite) linear chain. Here, being especially interested in the early stages of dissociation, we consider a finite-size implementation of the model (i.e., a finite substrate), for which an exact numerical solution is possible. By time-evolving the many-body wave function, and also using results from a time-dependent density functional theory description for electron-nuclear systems, we analyze the competition between several surface-response mechanisms and electronic correlations in the transient and longer time dynamics under the influence of dipole-coupled fields. Our model allows us to explore how coherent multiple-pulse protocols can impact desorption in a variety of prototypical experiments.

Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory.

PubMed

Gao, Li; Pal, Partha Pratim; Seideman, Tamar; Guisinger, Nathan P; Guest, Jeffrey R

2016-02-04

Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionization induced by inelastic tunneling electrons. The observed current independence of the desorption yield suggests that the vibrational excitation is a single-electron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (∼2 eV), as would be expected from the identified desorption mechanism.

Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory

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

Gao, L.; Pal, Partha P.; Seideman, Tamar

2016-02-04

Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionizationmore » induced by inelastic tunneling electrons. The observed current-independence of the desorption yield suggests that the vibrational excitation is a singleelectron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (~ 2 eV), as would be expected from the identified desorption mechanism« less

Update on the direct n-n scattering experiment at the reactor YAGUAR

NASA Astrophysics Data System (ADS)

Stephenson, S. L.; Crawford, B. E.; Furman, W. I.; Lychagin, E. V.; Muzichka, A. Yu.; Nekhaev, G. V.; Sharapov, E. I.; Shvetsov, V. N.; Strelkov, A. V.; Levakov, B. G.; Lyzhin, A. E.; Chernukhin, Yu. I.; Howell, C. R.; Mitchell, G. E.; Tornow, W.; Showalter-Bucher, R. A.

2013-10-01

The first direct measurement of the 1S0 neutron-neutron scattering experiment using the YAGUAR aperiodic reactor at the Russian Federal Nuclear Center - All Russian Research Institute of Technical Physics has preliminary results. Thermal neutrons are scattered from a thermal neutron ``gas'' within the scattering chamber of the reactor and measured via time-of-flight. These initial results show an unexpectedly large thermal neutron background now understood to be from radiation-induced desorption within the scattering chamber. Analysis of the neutron time-of-flight spectra suggests neutron scattering from H2 and possibly H2O molecules. An experimental value for the desorption yield ηγ of 0.02 molecules/gamma agrees with modeled results. Techniques to reduce the effect of the nonthermal desorption will be presented. This work was supported in part by ISTC project No. 2286, Russia Found. Grant 01-02-17181, the US DOE grants Nos. DE-FG02-97-ER41042 and DE-FG02-97-ER41033, and by the US NSF through Award Nos. 0107263 and 0555652.

Comparison of two thin-film microextractions for the analysis of estrogens in aqueous tea extract and environmental water samples by high performance liquid chromatography-ultraviolet detection.

PubMed

Cai, Pei-Shan; Li, Dan; Chen, Jing; Xiong, Chao-Mei; Ruan, Jin-Lan

2015-04-15

Two thin-film microextractions (TFME), octadecylsilane (ODS)-polyacrylonitrile (PAN)-TFME and polar enhanced phase (PEP)-PAN-TFME have been proposed for the analysis of bisphenol-A, diethylstilbestrol and 17β-estradiol in aqueous tea extract and environmental water samples followed by high performance liquid chromatography-ultraviolet detection. Both thin-films were prepared by spraying. The influencing factors including pH, extraction time, desorption solvent, desorption volume, desorption time, ion strength and reusability were investigated. Under the optimal conditions, the two TFME methods are similar in terms of the analytical performance evaluated by standard addition method. The limits of detection for three estrogens in environmental water and aqueous tea extract matrix ranged from 1.3 to 1.6 and 2.8 to 7.1 ng mL(-1) by the two TFME methods, respectively. Both approaches were applied for the analysis of analytes in real aqueous tea extract and environmental water samples, presenting satisfactory recoveries ranged from 87.3% to 109.4% for the spiked samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improved conditions for the application of solid phase microextraction prior to HPLC-FLD analysis of anatoxin-a.

PubMed

Rellán, Sandra; Gago-Martínez, Ana

2007-10-01

Solid phase microextraction coupled with high performance liquid chromatography with fluorescence detection has been optimized and evaluated for a simple, rapid, and selective analysis of anatoxin-a. Four kinds of fiber (100 microm polydimethylsiloxane, 60 microm polydimethylsiloxane/divinylbenzene, 50 microm Carbowax/templated resin-100, and 85 microm polyacrylate) were evaluated for an efficient extraction of the toxin. Parameters relating to the desorption step, such as desorption mode, solvent composition, time for both static and dynamic desorption, as well as carryover, have been studied and optimized. The derivatization process was investigated using NBD-F as derivatizing reagent. Anatoxin-a derivative was formed when the anatoxin-a-loaded fiber was inserted in a vial containing 5 microL of NBD-F. Variables affecting extraction such us ionic strength, temperature, and time have been also optimized. The results obtained showed linearity in the range of 10-2000 ng and a limit of detection of 0.29 ng/mL in river water. The presented method has been applied to different environmental samples.

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

NASA Technical Reports Server (NTRS)

Yakshinskiy, B. V.; Madey, T. E.

2003-01-01

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

Evaluation of B. subtilis SPB1 biosurfactants' potency for diesel-contaminated soil washing: optimization of oil desorption using Taguchi design.

PubMed

Mnif, Inès; Sahnoun, Rihab; Ellouze-Chaabouni, Semia; Ghribi, Dhouha

2014-01-01

Low solubility of certain hydrophobic soil contaminants limits remediation process. Surface-active compounds can improve the solubility and removal of hydrophobic compounds from contaminated soils and, consequently, their biodegradation. Hence, this paper aims to study desorption efficiency of oil from soil of SPB1 lipopeptide biosurfactant. The effect of different physicochemical parameters on desorption potency was assessed. Taguchi experimental design method was applied in order to enhance the desorption capacity and establish the best washing parameters. Mobilization potency was compared to those of chemical surfactants under the newly defined conditions. Better desorption capacity was obtained using 0.1% biosurfacatnt solution and the mobilization potency shows great tolerance to acidic and alkaline pH values and salinity. Results show an optimum value of oil removal from diesel-contaminated soil of about 87%. The optimum washing conditions for surfactant solution volume, biosurfactant concentration, agitation speed, temperature, and time were found to be 12 ml/g of soil, 0.1% biosurfactant, 200 rpm, 30 °C, and 24 h, respectively. The obtained results were compared to those of SDS and Tween 80 at the optimal conditions described above, and the study reveals an effectiveness of SPB1 biosurfactant comparable to the reported chemical emulsifiers. (1) The obtained findings suggest (a) the competence of Bacillus subtilis biosurfactant in promoting diesel desorption from soil towards chemical surfactants and (b) the applicability of this method in decontaminating crude oil-contaminated soil and, therefore, improving bioavailability of hydrophobic compounds. (2) The obtained findings also suggest the adequacy of Taguchi design in promoting process efficiency. Our findings suggest that preoptimized desorption process using microbial-derived emulsifier can contribute significantly to enhancement of hydrophobic pollutants' bioavailability. This study can be complemented with the investigation of potential role in improving the biodegradation of the diesel adsorbed to the soil.

Temperature-dependent sorption of naphthalene, phenanthrene, and pyrene to low organic carbon aquifer sediments

USGS Publications Warehouse

Piatt, Joseph J.; Backhus, Debera A.; Capel, Paul D.; Eisenreich, Steven J.

1996-01-01

Sorption experiments were conducted with naphthalene, phenanthrene, and pyrene on low organic carbon sediments at 4 and 26 °C using batch and column techniques. Experimental controls ensured the absence of biologic and photolytic activity and colloid-free solution supernatants. Equilibrium distribution coefficients (Kd) increased 1.1−1.6 times with a decrease in temperature of 22 °C. Fraction instantaneous sorption (F) values did not change significantly with a decrease in temperature of 22 °C. Desorption rate constants (k2) decreased 1.2−2.6 times with a decrease in temperature of 22 °C. Times to equilibrium were at least 40 h. The magnitude of observed Kd and k2 values and the effect of temperature on Kd (e.g., low enthalpy of sorption) are consistent with sorbate partitioning between the aqueous phase and small amounts of organic matter (foc = 0.02%) on the sediments. The temperature dependence of Kd and k2 may be small as compared to the effects of heterogeneities in field-scale aquifer systems. Thus, thermal gradients may not be of major importance in most saturated subsurface regimes when predicting solute transport. However, aquifer remediation pump-and-treat times could be decreased because increased temperature decreases both retardation and tailing.

Desorption of Benzene, 1,3,5-Trifluorobenzene, and Hexafluorobenzene from a Graphene Surface: The Effect of Lateral Interactions on the Desorption Kinetics.

PubMed

Smith, R Scott; Kay, Bruce D

2018-05-17

The desorption of benzene, 1,3,5-trifluorobenzene (TFB), and hexafluorobenzene (HFB) from a graphene covered Pt(111) substrate was investigated using temperature-programmed desorption (TPD). All three species have well-resolved monolayer and second-layer desorption peaks. The desorption spectra for submonolayer coverages of benzene and HFB are consistent with first-order desorption kinetics. In contrast, the submonolayer TPD spectra for TFB align on a common leading-edge, which is indicative of zero-order desorption kinetics. The desorption behavior of the three molecules can be correlated with the strength of the quadrupole moments. Calculations (second-order Møller-Plesset perturbation and density functional theory) show that the potential minimum for coplanar TFB dimers is more than a factor of 2 greater than that for either benzene or HFB dimers. The calculations support the interpretation that benzene and HFB are less likely to form the two-dimensional islands that are needed for submonolayer zero-order desorption kinetics.

Constant-load delayed fracture test of atmospherically corroded high strength steels

NASA Astrophysics Data System (ADS)

Akiyama, Eiji; Matsukado, Katsuhiro; Li, Songjie; Tsuzaki, Kaneaki

2011-07-01

Constant load tests of circumferentially notched round bar specimens of high strength steels after cyclic corrosion test and outdoor exposure have been performed to demonstrate that delayed fracture occurs when the hydrogen content from the environment, H E, exceeds the critical hydrogen content for delayed fracture, H C. During the constant load tests the humidity around the specimen was increased in stepwise manner to increase hydrogen entry. After fracture the specimen was kept at the humidity long enough to homogenize hydrogen in the specimen and to obtain more quantitative hydrogen content by thermal desorption analysis. H E of the fractured specimens was higher than H C, and H E of the specimens not fractured was lower than H C. This result confirms that the balance between H C and H E determines the occurrence of delayed fracture and that hydrogen-content-based evaluation of susceptibility to delayed fracture is reasonable. To certify the increase of H E with increase in humidity, electrochemical hydrogen permeation test was carried out. The hydrogen permeation current density was increased especially at 98%RH. Enhancement of hydrogen entry with increase in CCT number was also shown by the test.

Desorption of Mercury(II) on Kaolinite in the Presence of Oxalate or Cysteine

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

Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

2011-01-01

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio- uptake of Hg in aquatic systems. We studied the desorption of Hg(II) on kaolinite in the presence of oxalate or cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, 7), ligand concentration (0.25, 1.0 mM), and temperature (15, 25, 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH-dependant. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed atmore » pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but it appeared to enhance the Hg(II) desorption afterwards. The effect of ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particles and in the solution probably can also affect the Hg(II) desorption.« less

Reconstruction and feature selection for desorption electrospray ionization mass spectroscopy imagery

NASA Astrophysics Data System (ADS)

Gao, Yi; Zhu, Liangjia; Norton, Isaiah; Agar, Nathalie Y. R.; Tannenbaum, Allen

2014-03-01

Desorption electrospray ionization mass spectrometry (DESI-MS) provides a highly sensitive imaging technique for differentiating normal and cancerous tissue at the molecular level. This can be very useful, especially under intra-operative conditions where the surgeon has to make crucial decision about the tumor boundary. In such situations, the time it takes for imaging and data analysis becomes a critical factor. Therefore, in this work we utilize compressive sensing to perform the sparse sampling of the tissue, which halves the scanning time. Furthermore, sparse feature selection is performed, which not only reduces the dimension of data from about 104 to less than 50, and thus significantly shortens the analysis time. This procedure also identifies biochemically important molecules for further pathological analysis. The methods are validated on brain and breast tumor data sets.

Characterization of Cryptosporidium parvum by Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

PubMed Central

Magnuson, Matthew L.; Owens, James H.; Kelty, Catherine A.

2000-01-01

Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) was used to investigate whole and freeze-thawed Cryptosporidium parvum oocysts. Whole oocysts revealed some mass spectral features. Reproducible patterns of spectral markers and increased sensitivity were obtained after the oocysts were lysed with a freeze-thaw procedure. Spectral-marker patterns for C. parvum were distinguishable from those obtained for Cryptosporidium muris. One spectral marker appears specific for the genus, while others appear specific at the species level. Three different C. parvum lots were investigated, and similar spectral markers were observed in each. Disinfection of the oocysts reduced and/or eliminated the patterns of spectral markers. PMID:11055915

Identification of Molds by Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

PubMed Central

Posteraro, Brunella

2016-01-01

ABSTRACT Although to a lesser extent than diagnostic bacteriology, matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) has recently revolutionized the diagnostic mycology workflow. With regard to filamentous fungi (or molds), the precise recognition of pathogenic species is important for rapid diagnosis and appropriate treatment, especially for invasive diseases. This review summarizes the current experience with MALDI-TOF MS-based identification of common and uncommon mold species of Aspergillus, Fusarium, Mucorales, dimorphic fungi, and dermatophytes. This experience clearly shows that MALDI-TOF MS holds promise as a fast and accurate identification tool, particularly with common species or typical strains of filamentous fungi. PMID:27807151

Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction.

PubMed

Jochmann, Maik A; Yuan, Xue; Schmidt, Torsten C

2007-03-01

In the present study a headspace solid-phase dynamic extraction method coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) for the trace determination of volatile halogenated hydrocarbons and benzene from groundwater samples was developed and evaluated. As target compounds, benzene as well as 11 chlorinated and brominated hydrocarbons (vinyl chloride, dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, bromoform) of environmental and toxicological concern were included in this study. The analytes were extracted using a SPDE needle device, coated with a poly(dimethylsiloxane) with 10% embedded activated carbon phase (50-microm film thickness and 56-mm film length) and were analyzed by GC/MS in full-scan mode. Parameters that affect the extraction yield such as extraction and desorption temperature, salting-out, extraction and desorption flow rate, extraction volume and desorption volume, the number of extraction cycles, and the pre-desorption time have been evaluated and optimized. The linearity of the HS-SPDE-GC/MS method was established over several orders of magnitude. Method detection limits (MDLs) for the compounds investigated ranged between 12 ng/L for cis-dichloroethylene and trans-dichloroethylene and 870 ng/L for vinyl chloride. The method was thoroughly validated, and the precision at two concentration levels (0.1 mg/L and a concentration 5 times above the MDL) was between 3.1 and 16% for the analytes investigated. SPDE provides high sensitivity, short sample preparation and extraction times and a high sample throughput because of full automation. Finally, the applicability to real environmental samples is shown exemplarily for various groundwater samples from a former waste-oil recycling facility. Groundwater from the site showed a complex contamination with chlorinated volatile organic compounds and aromatic hydrocarbons.

Kinetics of Zn sorption-desorption using a thin disk flow method

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

Hinz, C.; Selim, H.M.

1999-02-01

In this study the authors investigated the kinetics of Zn sorption and desorption using a short column or thin disk method. The method is based on continuous flow through a thin soil layer where the effluent was collected using a fraction collector. Two soils were used: a Windsor soil and Mahan soil. Breakthrough results (BTCs) for different flow velocities indicated that Zn sorption is instantaneous and equilibrium retention is dominant when a pulse of Zn with a concentration of 2.62 [times] 10[sup [minus]5] M is applied. However, based on flow interruption, time-dependent Zn sorption-desorption processes were most pronounced when themore » applied Zn pulse concentration was two orders of magnitude lower. This confirms earlier findings of concentration-dependent kinetics from batch experiments on Windsor soil. The removal of organic matter and iron oxide, based on peroxide and peroxide/dithionite-treatments, resulted in doubling and quadrupling Zn retention, respectively, compared with the untreated Windsor soil. Differences between the untreated, peroxide-, and peroxide/dithionite-treated Windsor soils were most pronounced at low input Zn concentrations, suggesting that more specific sites became available as a result of the different treatments. At high input Zn concentrations, increases of specific sites may not be significant. For the treated soil, stronger sorption and desorption kinetic behavior was exhibited compared with the untreated soil. Diffusion into soil minerals or surface-controlled reactions may cause such behavior.« less

Desorption corona beam ionization source for mass spectrometry.

PubMed

Wang, Hua; Sun, Wenjian; Zhang, Junsheng; Yang, Xiaohui; Lin, Tao; Ding, Li

2010-04-01

A novel Desorption Corona Beam Ionization (DCBI) source for direct analysis of samples from surface in mass spectrometry is reported. The DCBI source can work under ambient conditions without time-consuming sample pretreatments. The source shares some common features with another ionization source - Direct Analysis in Real Time (DART), developed earlier. For example, helium was used as the discharge gas (although only corona discharge is involved in the present source), and heating of the discharge gas is required for sample desorption. However, the difference between the two sources is substantial. In the present source, a visible thin corona beam extending out around 1 cm can be formed by using a hollow needle/ring electrode structure. This feature would greatly facilitate localizing sampling areas and performing imaging/profiling experiments. The DCBI source is also capable of performing progressive temperature scans between room temperature and 450 degrees C in order to sequentially desorb samples from the surface and, therefore, to achieve a rough separation of the individual components in a complex mixture, resulting in less congestion in the mass spectrum acquired. Mass spectra for a broad range of compounds (pesticides, veterinary additives, OTC drugs, explosive materials) have been acquired using the DCBI source. For most of the compounds tested, the heater temperature required for efficient desorption is at least 150 degrees C. The molecular weight of the sample that can be desorbed/ionized is normally below 600 dalton even at the highest heater temperature, which is mainly limited by the volatility of the sample.

First-principles study of water desorption from montmorillonite surface.

PubMed

Zhang, Yao; Meng, Yingfeng; Liu, Houbin; Yang, Mingli

2016-05-01

Knowledge about water desorption is important to give a full picture of water diffusion in montmorillonites (MMT), which is a driving factor in MMT swelling. The desorption paths and energetics of water molecules from the surface of MMT with trapped Li(+), Na(+) or K(+) counterions were studied using periodic density functional theory calculations. Two paths--surface and vacuum desorption--were designed for water desorption starting from a stationary structure in which water bonds with both the counterion and the MMT surface. Surface desorption is energetically more favorable than vacuum desorption due to water-surface hydrogen bonds that help stabilize the intermediate structure of water released from the counterion. The energy barriers of water desorption are in the order of Li(+) > Na(+) > K(+), which can be attributed to the short ionic radius of Li(+), which favors strong binding with the water molecule. The temperature dependence of water adsorption and desorption rates were compared based on the computed activation energies. Our calculations reveal that the water desorption on the MMT surface has a different mechanism from water adsorption, which results from surface effects favoring stabilization of water conformers during the desorption process.

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

PubMed

Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

2018-06-08

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

Removal of chlorine from Illinois coal by high-temperature leaching: Final report, March 1--December 31, 1987

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

Chen, Han Lin

1988-03-01

The objectives of this research are to: (1) conduct experimental investigations of the removal of chlorine from coal by high- temperature leaching; (2) identify important factors affecting the chlorine removal process; (3) understand the mechanisms involved; and (4) develop a mathematical model to describe the process. A generalized mathematical model based on diffusion and relaxation has been developed for water leaching of chlorine from coal. The model has been fitted to four different samples of Illinois No. 6 coal: C22175, C22651, C8601, and C8602. The weight percent of chlorine ranged from 0.42 to 0.82. The experimental data on these samplesmore » covered a temperature range of 297 to 370K and a particle size range of 60 to 325 mesh. Based on the type of coal and the conditions of leaching, it was found that 40 to 80% of the original chlorine could be leached from the coal matrix. The model based on diffusion-relaxation concept predicted the leaching data within +-5% average absolute deviation. The diffusion rate constants at different temperatures were correlated to Arrhenius type relations. Attempts made to correlate the constants in the Arrhenius equations with the chlorine content in coal and with particle size have been discussed. The water leaching data were used to extract Fickian diffusivities based on the time required for 50% desorption. The calculated diffusivity values ranged from 0.6 to 3 /times/ 10/sup /minus/11/ cm/sup 2//sec. The effect of chemical additives on the rate of leaching has also been studied. Both HNO/sub 3/ and NH/sub 4/OH were used as additives. 28 refs., 3 figs., 7 tabs.« less

Dielectric Interactions and the Prediction of Retention Times of Pesticides in Supercritical Fluid Chromatography with CO2

NASA Astrophysics Data System (ADS)

Alvarez, Guillermo A.; Baumanna, Wolfram

2005-02-01

A thermodynamic model for the partition of a solute (pesticide) between two immiscible phases, such as the stationary and mobile phases of supercritical fluid chromatography with CO2, is developed from first principles. A key ingredient of the model is the result of the calculation made by Liptay of the energy of interaction of a polar molecule with a dielectric continuum, which represents the solvent. The strength of the interaction between the solute and the solvent, which may be considered a measure of the solvent power, is characterized by a function g = (ɛ - 1)/(2ɛ +1), where ɛ is the dielectric constant of the medium, which is a function of the temperature T and the pressure P. Since the interactions between the nonpolar supercritical CO2 solvent and the slightly polar pesticide molecules are considered to be extremely weak, a regular solution model is appropriate from the thermodynamic point of view. At constant temperature, the model predicts a linear dependence of the logarithm of the capacity factor (lnk) of the chromatographic experiment on the function g = g(P), as the pressure is varied, with a slope which depends on the dipole moment of the solute, dispersion interactions and the size of the solute cavity in the solvent. At constant pressure, once the term containing the g (solvent interaction) factor is subtracted from lnk, a plot of the resulting term against the inverse of temperature yields the enthalpy change of transfer of the solute from the mobile (supercritical CO2) phase to the stationary (adsorbent) phase. The increase in temperature with the consequent large volume expansion of the supercritical fluid lowers its solvent strength and hence the capacity factor of the column (or solute retention time) increases. These pressure and temperature effects, predicted by the model, agree excellently with the experimental retention times of seven pesticides. Beyond a temperature of about 393 K, where the liquid solvent densities approach those of a gas (and hence the solvent strength becomes negligible), a dramatic loss of the retention times of all pesticides is observed in the experiments; this is attributed to desorption of the solute from the stationary phase, as predicted by Le Châtelier's principle for the (exothermic) adsorption process.

Comparison between Thermal Desorption Tubes and Stainless Steel Canisters Used for Measuring Volatile Organic Compounds in Petrochemical Factories

PubMed Central

Chang, Cheng-Ping; Lin, Tser-Cheng; Lin, Yu-Wen; Hua, Yi-Chun; Chu, Wei-Ming; Lin, Tzu-Yu; Lin, Yi-Wen; Wu, Jyun-De

2016-01-01

Objective: The purpose of this study was to compare thermal desorption tubes and stainless steel canisters for measuring volatile organic compounds (VOCs) emitted from petrochemical factories. Methods: Twelve petrochemical factories in the Mailiao Industrial Complex were recruited for conducting the measurements of VOCs. Thermal desorption tubes and 6-l specially prepared stainless steel canisters were used to simultaneously perform active sampling of environmental air samples. The sampling time of the environmental air samples was set up on 6h close to a full work shift of the workers. A total of 94 pairwise air samples were collected by using the thermal adsorption tubes and stainless steel canisters in these 12 factories in the petrochemical industrial complex. To maximize the number of comparative data points, all the measurements from all the factories in different sampling times were lumped together to perform a linear regression analysis for each selected VOC. Pearson product–moment correlation coefficient was used to examine the correlation between the pairwise measurements of these two sampling methods. A paired t-test was also performed to examine whether the difference in the concentrations of each selected VOC measured by the two methods was statistically significant. Results: The correlation coefficients of seven compounds, including acetone, n-hexane, benzene, toluene, 1,2-dichloroethane, 1,3-butadiene, and styrene were >0.80 indicating the two sampling methods for these VOCs’ measurements had high consistency. The paired t-tests for the measurements of n-hexane, benzene, m/p-xylene, o-xylene, 1,2-dichloroethane, and 1,3-butadiene showed statistically significant difference (P-value < 0.05). This indicated that the two sampling methods had various degrees of systematic errors. Looking at the results of six chemicals and these systematic errors probably resulted from the differences of the detection limits in the two sampling methods for these VOCs. Conclusions: The comparison between the concentrations of each of the 10 selected VOCs measured by the two sampling methods indicted that the thermal desorption tubes provided high accuracy and precision measurements for acetone, benzene, and 1,3-butadiene. The accuracy and precision of using the thermal desorption tubes for measuring the VOCs can be improved due to new developments in sorbent materials, multi-sorbent designs, and thermal desorption instrumentation. More applications of thermal desorption tubes for measuring occupational and environmental hazardous agents can be anticipated. PMID:26585828

Comparison between Thermal Desorption Tubes and Stainless Steel Canisters Used for Measuring Volatile Organic Compounds in Petrochemical Factories.

PubMed

Chang, Cheng-Ping; Lin, Tser-Cheng; Lin, Yu-Wen; Hua, Yi-Chun; Chu, Wei-Ming; Lin, Tzu-Yu; Lin, Yi-Wen; Wu, Jyun-De

2016-04-01

The purpose of this study was to compare thermal desorption tubes and stainless steel canisters for measuring volatile organic compounds (VOCs) emitted from petrochemical factories. Twelve petrochemical factories in the Mailiao Industrial Complex were recruited for conducting the measurements of VOCs. Thermal desorption tubes and 6-l specially prepared stainless steel canisters were used to simultaneously perform active sampling of environmental air samples. The sampling time of the environmental air samples was set up on 6 h close to a full work shift of the workers. A total of 94 pairwise air samples were collected by using the thermal adsorption tubes and stainless steel canisters in these 12 factories in the petrochemical industrial complex. To maximize the number of comparative data points, all the measurements from all the factories in different sampling times were lumped together to perform a linear regression analysis for each selected VOC. Pearson product-moment correlation coefficient was used to examine the correlation between the pairwise measurements of these two sampling methods. A paired t-test was also performed to examine whether the difference in the concentrations of each selected VOC measured by the two methods was statistically significant. The correlation coefficients of seven compounds, including acetone, n-hexane, benzene, toluene, 1,2-dichloroethane, 1,3-butadiene, and styrene were >0.80 indicating the two sampling methods for these VOCs' measurements had high consistency. The paired t-tests for the measurements of n-hexane, benzene, m/p-xylene, o-xylene, 1,2-dichloroethane, and 1,3-butadiene showed statistically significant difference (P-value < 0.05). This indicated that the two sampling methods had various degrees of systematic errors. Looking at the results of six chemicals and these systematic errors probably resulted from the differences of the detection limits in the two sampling methods for these VOCs. The comparison between the concentrations of each of the 10 selected VOCs measured by the two sampling methods indicted that the thermal desorption tubes provided high accuracy and precision measurements for acetone, benzene, and 1,3-butadiene. The accuracy and precision of using the thermal desorption tubes for measuring the VOCs can be improved due to new developments in sorbent materials, multi-sorbent designs, and thermal desorption instrumentation. More applications of thermal desorption tubes for measuring occupational and environmental hazardous agents can be anticipated. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Evaluation of ozone generation and indoor organic compounds removal by air cleaners based on chamber tests

NASA Astrophysics Data System (ADS)

Yu, Kuo-Pin; Lee, Grace Whei-May; Hsieh, Ching-Pei; Lin, Chi-Chi

2011-01-01

Ozone can cause many health problems, including exacerbation of asthma, throat irritation, cough, chest ache, shortness of breath, and respiratory infections. Air cleaners are one of the sources of indoor ozone, and thus the evaluation of ozone generated by air cleaners is desired significant issue. Most evaluation methods proposed are based on chamber tests. However, the adsorption and desorption of ozone on the wall of test chamber and the deposition of ozone resulted from the surface reaction can influence the evaluation results. In this study, we developed a mass balance model that took the adsorption, desorption and deposition of ozone into consideration to evaluate the effective ozone emission rates of six selected air cleaners. The experiments were conducted in a stainless steel chamber with a volume of 11.3 m 3 at 25 °C and 60% relative humidity. The adsorption, desorption and deposition rate constants of ozone obtained by fitting the model to the experimental data were k a = 0.149 ± 0.052 m h -1, k d = 0.013 ± 0.007 h -1, and k r = 0.050 ± 0.020 h -1, respectively. The effective ozone emission rates of Air Cleaners No. 1, 2, and 3 ranged between 13,400-24,500 μg h -1, 7190-10,400 μg h -1, and 4880-6560 μg h -1, respectively, which were more stable than those of No.4, 5, and 6. The effective ozone emission rates of Air Cleaners No. 4, 5, and 6 increased with the time of operation which might be relevant to the decrease of ozone removal by the "aging" filter installed in these cleaners. The removal of toluene and formaldehyde by these six air cleaners were also evaluated and the clean air delivery rates (CADRs) of these two pollutants ranged from non-detectable to 0.42 ± 0.08 m 3 h -1, and from non-detectable to 0.75 ± 0.07 m 3 h -1, respectively. The CADRs showed an insignificant relationship with the effective ozone emission rates. Thus, the removal of toluene and formaldehyde might be resulted from the adsorption on the filters and the decomposition by the high-voltage electric discharge or the ionization that generated ozone.

Contribution of thermal energy to initial ion production in matrix-assisted laser desorption/ionization observed with 2,4,6-trihydroxyacetophenone.

PubMed

Lai, Yin-Hung; Chen, Bo-Gaun; Lee, Yuan Tseh; Wang, Yi-Sheng; Lin, Sheng Hsien

2014-08-15

Although several reaction models have been proposed in the literature to explain matrix-assisted laser desorption/ionization (MALDI), further study is still necessary to explore the important ionization pathways that occur under the high-temperature environment of MALDI. 2,4,6-Trihydroxyacetophenone (THAP) is an ideal compound for evaluating the contribution of thermal energy to an initial reaction with minimum side reactions. Desorbed neutral THAP and ions were measured using a crossed-molecular beam machine and commercial MALDI-TOF instrument, respectively. A quantitative model incorporating an Arrhenius-type desorption rate derived from transition state theory was proposed. Reaction enthalpy was calculated using GAUSSIAN 03 software with dielectric effect. Additional evidence of thermal-induced proton disproportionation was given by the indirect ionization of THAP embedded in excess fullerene molecules excited by a 450 nm laser. The quantitative model predicted that proton disproportionation of THAP would be achieved by thermal energy converted from a commonly used single UV laser photon. The dielectric effect reduced the reaction Gibbs free energy considerably even when the dielectric constant was reduced under high-temperature MALDI conditions. With minimum fitting parameters, observations of pure THAP and THAP mixed with fullerene both agreed with predictions. Proton disproportionation of solid THAP was energetically favorable with a single UV laser photon. The quantitative model revealed an important initial ionization pathway induced by the abrupt heating of matrix crystals. In the matrix crystals, the dielectric effect reduced reaction Gibbs free energy under typical MALDI conditions. The result suggested that thermal energy plays an important role in the initial ionization reaction of THAP. Copyright © 2014 John Wiley & Sons, Ltd.

Mechanical desorption of a single chain: unusual aspects of phase coexistence at a first-order transition.

PubMed

Skvortsov, Alexander M; Klushin, Leonid I; Polotsky, Alexey A; Binder, Kurt

2012-03-01

The phase transition occurring when a single polymer chain adsorbed at a planar solid surface is mechanically desorbed is analyzed in two statistical ensembles. In the force ensemble, a constant force applied to the nongrafted end of the chain (that is grafted at its other end) is used as a given external control variable. In the z-ensemble, the displacement z of this nongrafted end from the surface is taken as the externally controlled variable. Basic thermodynamic parameters, such as the adsorption energy, exhibit a very different behavior as a function of these control parameters. In the thermodynamic limit of infinite chain length the desorption transition with the force as a control parameter clearly is discontinuous, while in the z-ensemble continuous variations are found. However, one should not be misled by a too-naive application of the Ehrenfest criterion to consider the transition as a continuous transition: rather, one traverses a two-phase coexistence region, where part of the chain is still adsorbed and the other part desorbed and stretched. Similarities with and differences from two-phase coexistence at vapor-liquid transitions are pointed out. The rounding of the singularities due to finite chain length is illustrated by exact calculations for the nonreversal random walk model on the simple cubic lattice. A new concept of local order parameter profiles for the description of the mechanical desorption of adsorbed polymers is suggested. This concept give evidence for both the existence of two-phase coexistence within single polymer chains for this transition and the anomalous character of this two-phase coexistence. Consequences for the proper interpretation of experiments performed in different ensembles are briefly mentioned.

Determination of soil–water sorption coefficients of volatile methylsiloxanes

PubMed Central

Kozerski, Gary E; Xu, Shihe; Miller, Julie; Durham, Jeremy

2014-01-01

The sorption behaviors of 4 cyclic and linear volatile methyl siloxane (VMS) compounds between water and organic matter in 3 United Kingdom soils were studied by a batch equilibrium method using13C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [13C]-VMS in the soil and aqueous phases were measured directly by extraction and gas chromatography–mass spectrometry techniques. All VMS compounds were sorbed rapidly, reaching constant distributions in all soils by 24 h. Desorption kinetics were very rapid, with reattainment of equilibrium within 1 h. In the main, linear isotherms were observed for aqueous concentrations at or below 4% of the solubility limits. The average sorption organic carbon partition coefficient (log KOC) values across soils were 4.23 for D4, 5.17 for D5, 4.32 for L3, and 5.13 for L4, with standard deviations of 0.09 to 0.34. Desorption KOC values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in KOC values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, KOC values for the VMS compounds were significantly lower than expected on the basis of their octanol–water partition coefficients. A linear free energy relationship analysis showed that these differences could be rationalized quantitatively in terms of the inherent characteristics of the VMS compounds, combined with the differences in solvation properties of organic matter and octanol. Environ Toxicol Chem 2014; 33:1937–1945. PMID:24862578

Tenax TA extraction to understand the rate-limiting factors in methyl-β-cyclodextrin-enhanced bioremediation of PAH-contaminated soil.

PubMed

Sun, Mingming; Luo, Yongming; Teng, Ying; Christie, Peter; Jia, Zhongjun; Li, Zhengao

2013-06-01

The effectiveness of many bioremediation systems for PAH-contaminated soil may be constrained by low contaminant bioaccessibility due to limited aqueous solubility or large sorption capacity. Information on the extent to which PAHs can be readily biodegraded is of vital importance in the decision whether or not to remediate a contaminated soil. In the present study the rate-limiting factors in methyl-β-cyclodextrin (MCD)-enhanced bioremediation of PAH-contaminated soil were evaluated. MCD amendment at 10 % (w/w) combined with inoculation with the PAH-degrading bacterium Paracoccus sp. strain HPD-2 produced maximum removal of total PAHs of up to 35 %. The desorption of PAHs from contaminated soil was determined before and after 32 weeks of bioremediation. 10 % (w/w) MCD amendment (M2) increased the Tenax extraction of total PAHs from 12 to 30 % and promoted degradation by up to 26 % compared to 6 % in the control. However, the percentage of Tenax extraction for total PAHs was much larger than that of degradation. Thus, in the control and M2 treatment it is likely that during the initial phase the bioaccessibility of PAHs is high and biodegradation rates may be limited by microbial processes. On the other hand, when the soil was inoculated with the PAH-degrading bacterium (CKB and MB2), the slowly and very slowly desorbing fractions (F sl and F vl ) became larger and the rate constants of slow and very slow desorption (k sl and k vl ) became extremely small after bioremediation, suggesting that desorption is likely rate limiting during the second, slow phase of biotransformation. These results have practical implications for site risk assessment and cleanup strategies.

Controlled long-term release of small peptide hormones using a new microporous polypropylene polymer: its application for vasopressin in the Brattleboro rat and potential perinatal use

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

Kruisbrink, J.; Boer, G.J.

1984-12-01

Based on drug release by microporous hollow fibers and the recent introduction of microporous polymers, a new technique was developed for controlled delivery of peptides. Small-diameter microporous polypropylene tubing, lumen-loaded with microgram quantities of vasopressin, and coated with collodion, releases vasopressin after in vitro immersion slowly (1-100 ng/d) and constantly for months. The mechanism of pseudo-zero-order delivery is based on high adsorption of vasopressin, keeping the void volume concentration of dissolved vasopressin constant, which is consequently a constant driving force of outward diffusion. The collodion coating prevents the entry of proteinaceous compounds which would result in rapid desorption of vasopressin.more » The present delivery module provides a lasting release for other peptides as well (lysine-vasopressin, oxytocin, alpha-melanocyte-stimulating hormone and, to a lesser extent, Met-enkephalin). The microporous polymer-collodion device is biocompatible and, loaded with vasopressin, successfully alleviates the diabetes insipidus of Brattleboro rats deficient for vasopressin. Subcutaneous implantation normalized diuresis for a period of 60 d and constant urine vasopressin excretion is observed. When the commercially available osmotic minipump is too large for implantation, the small size of the present controlled-delivery system allows peptide treatment of young and immature laboratory rats, even if located in utero.« less

Quantifying the flow efficiency in constant-current capacitive deionization.

PubMed

Hawks, Steven A; Knipe, Jennifer M; Campbell, Patrick G; Loeb, Colin K; Hubert, McKenzie A; Santiago, Juan G; Stadermann, Michael

2018-02-01

Here we detail a previously unappreciated loss mechanism inherent to capacitive deionization (CDI) cycling operation that has a substantial role determining performance. This mechanism reflects the fact that desalinated water inside a cell is partially lost to re-salination if desorption is carried out immediately after adsorption. We describe such effects by a parameter called the flow efficiency, and show that this efficiency is distinct from and yet multiplicative with other highly-studied adsorption efficiencies. Flow losses can be minimized by flowing more feed solution through the cell during desalination; however, this also results in less effluent concentration reduction. While the rationale outlined here is applicable to all CDI cell architectures that rely on cycling, we validate our model with a flow-through electrode CDI device operated in constant-current mode. We find excellent agreement between flow efficiency model predictions and experimental results, thus giving researchers simple equations by which they can estimate this distinct loss process for their operation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparative Proteomic Analysis of Three Gelatinous Chinese Medicines and Their Authentications by Tryptic-digested Peptides Profiling using Matrix-assisted Laser Desorption/Ionization-time of Flight/Time of Flight Mass Spectrometry.

PubMed

Yang, Huan; Zheng, Jie; Wang, Hai-Yan; Li, Nan; Yang, Ya-Ya; Shen, Yu-Ping

2017-01-01

Gelatinous Chinese medicines (GCMs) including Asini Corii Colla, Testudinis Carapacis ET Plastri Colla, and Cervi Cornus Colla, were made from reptile shell or mammalian skin or deer horn, and consumed as a popular tonic, as well as hemopoietic and hemostatic agents. Misuse of them would not exert their functions, and fake or adulterate products have caused drug market disorder and affected food and drug safety. GCMs are rich in denatured proteins, but insufficient in available DNA fragments, hence commonly used cytochrome c oxidase I barcoding was not successful for their authentication. In this study, we performed comparative proteomic analysis of them and their animal origins to identify the composition of intrinsic proteins for the first time. A reliable and convenient approach was proposed for their authentication, by the incorporation of sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two-dimensional electrophoresis, and matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry (MALDI-TOF/TOF-MS). A total of 26 proteins were identified from medicinal parts of original animals, and GCMs proteins presented in a dispersive manner in electrophoresis analyses due to complicated changes in the structure of original proteins caused by long-term decoction and the addition of ingredients during their manufacturing. In addition, by comparison of MALDI-TOF/TOF-MS profiling, 19 signature peptide fragments originated from the protein of GCM products were selected according to criteria. These could assist in the discrimination and identification of adulterates of GCMs and other ACMs for their form of raw medicinal material, the pulverized, and even the complex. Comparative proteomic analysis of three gelatinous Chinese medicines was conducted, and their authentications were based on tryptic-digested peptides profiling using matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry. Abbreviations used: GCMs: Gelatinous Chinese medicines, COI: Cytochrome c oxidase I, SDS-PAGE: Sodium dodecyl sulfate polyacrylamide gel electrophoresis, 2-DE: Two-dimensional electrophoresis, MALDI-TOF/TOF-MS: Matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry, LC: Liquid chromatography, ChP: Chinese Pharmacopoeia, HPLC: High performance liquid chromatography, LC-ESI + -MS: Liquid chromatography-electro spray ionization-mass spectrometry, IEF: isoelectric focusing, HCCA: α-Cyano-4-hydroxycinnamic acid.

Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

NASA Technical Reports Server (NTRS)

Bergin, E. A.; Langer, W. D.; Goldsmith, P. F.

1995-01-01

We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

[Separation and identification of bovine lactoferricin by high performance liquid chromatography-matrix-assisted laser desorption/ionization time of flight/ time of flight mass spectrometry].

PubMed

An, Meichen; Liu, Ning

2010-02-01

A high performance liquid chromatography-matrix-assisted laser desorption/ionization time of flight/time of flight mass spectrometry (HPLC-MALDI-TOF/TOF MS) method was developed for the separation and identification of bovine lactoferricin (LfcinB). Bovine lactoferrin was hydrolyzed by pepsin and then separated by ion exchange chromatography and reversed-phase liquid chromatography (RP-LC). The antibacterial activities of the fractions from RP-LC separation were determined and the protein concentration of the fraction with the highest activity was measured, whose sequence was indentified by MALDI-TOF/TOF MS. The relative molecular mass of LfcinB was 3 124.89 and the protein concentration was 18.20 microg/mL. The method of producing LfcinB proposed in this study has fast speed, high accuracy and high resolution.

Modified solvothermal synthesis of cobalt ferrite (CoFe2O4) magnetic nanoparticles photocatalysts for degradation of methylene blue with H2O2/visible light

NASA Astrophysics Data System (ADS)

Kalam, Abul; Al-Sehemi, Abdullah G.; Assiri, Mohammed; Du, Gaohui; Ahmad, Tokeer; Ahmad, Irfan; Pannipara, M.

2018-03-01

Different grads of magnetic nano-scaled cobalt ferrites (CoFe2O4) photocatalysts were synthesized by modified Solvothermal (MST) process with and without polysaccharide. The indigenously synthesized photocatalysts were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), thermo gravimetric analysis (TGA), Fourier transform infrared (FT-IR), UV-visible (UV-vis) spectroscopy and N2 adsorption-desorption isotherm method. The Fourier transform infrared spectroscopy study showed the Fe-O stretching vibration 590-619 cm-1, confirming the formation of metal oxide. The crystallite size of the synthesized photocatalysts was found in the range between 20.0 and 30.0 nm. The surface area of obtained magnetic nanoparticles is found to be reasonably high in the range of 63.0-76.0 m2/g. The results shown that only MST-2 is the most active catalyst for photo-Fenton like scheme for fast photodegradation action of methylene blue dye, this is possible due to optical band gap estimated of 2.65 eV. Captivatingly the percentage of degradation efficiency increases up to 80% after 140 min by using MST-2 photocatalyst. Photocatalytic degradation of methylene blue (MB) dye under visible light irradiation with cobalt ferrite magnetic nanoparticles followed first order kinetic constant and rate constant of MST-2 is almost 2.0 times greater than MST-1 photocatalyst.

Effects of substrate temperature on properties of pulsed dc reactively sputtered tantalum oxide films

NASA Astrophysics Data System (ADS)

Jain, Pushkar; Juneja, Jasbir S.; Bhagwat, Vinay; Rymaszewski, Eugene J.; Lu, Toh-Ming; Cale, Timothy S.

2005-05-01

The effects of substrate heating on the stoichiometry and the electrical properties of pulsed dc reactively sputtered tantalum oxide films over a range of film thickness (0.14 to 5.4 μm) are discussed. The film stoichiometry, and hence the electrical properties, of tantalum oxide films; e.g., breakdown field, leakage current density, dielectric constant, and dielectric loss are compared for two different cases: (a) when no intentional substrate/film cooling is provided, and (b) when the substrate is water cooled during deposition. All other operating conditions are the same, and the film thickness is directly related to deposition time. The tantalum oxide films deposited on the water-cooled substrates are stoichiometric, and exhibit excellent electrical properties over the entire range of film thickness. ``Noncooled'' tantalum oxide films are stoichiometric up to ~1 μm film thickness, beyond that the deposited oxide is increasingly nonstoichiometric. The presence of partially oxidized Ta in thicker (>~1 μm) noncooled tantalum oxide films causes a lower breakdown field, higher leakage current density, higher apparent dielectric constant, and dielectric loss. The growth of nonstoichiometric tantalum oxide in thicker noncooled films is attributed to decreased surface oxygen concentration due to oxygen recombination and desorption at higher film temperatures (>~100 °C). The quantitative results presented reflect experience with a specific piece of equipment; however, the procedures presented can be used to characterize deposition processes in which film stoichiometry can change.

Fate and transport with material response characterization of green sorption media for copper removal via desorption process.

PubMed

Chang, Ni-Bin; Houmann, Cameron; Lin, Kuen-Song; Wanielista, Martin

2016-07-01

Multiple adsorption and desorption cycles are required to achieve the reliable operation of copper removal and recovery. A green sorption media mixture composed of recycled tire chunk, expanded clay aggregate, and coconut coir was evaluated in this study for its desorptive characteristics as a companion study of the corresponding adsorption process in an earlier publication. We conducted a screening of potential desorbing agents, batch desorption equilibrium and kinetic studies, and batch tests through 3 adsorption/desorption cycles. The desorbing agent screening revealed that hydrochloric acid has good potential for copper desorption. Equilibrium data fit the Freundlich isotherm, whereas kinetic data had high correlation with the Lagergren pseudo second-order model and revealed a rapid desorption reaction. Batch equilibrium data over 3 adsorption/desorption cycles showed that the coconut coir and media mixture were the most resilient, demonstrating they could be used through 3 or more adsorption/desorption cycles. FE-SEM imaging, XRD, and EDS analyses supported the batch adsorption and desorption results showing significant surface sorption of CuO species in the media mixture and coconut coir, followed by partial desorption using 0.1 M HCl as a desorbing agent. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dynamic Determination of Some Optical and Electrical Properties of Galena Natural Mineral: Potassium Ethyl Xanthate Solution Interface

NASA Astrophysics Data System (ADS)

Todoran, D.; Todoran, R.; Anitas, E. M.; Szakacs, Zs.

2017-12-01

This paper presents results concerning optical and electrical properties of galena natural mineral and of the interface layer formed between it and the potassium ethyl xanthate solution. The applied experimental method was differential optical reflectance spectroscopy over the UV-Vis/NIR spectral domain. Computations were made using the Kramers-Kronig formalism. Spectral dependencies of the electron loss functions, determined from the reflectance data obtained from the polished mineral surface, display van Hove singularities, leading to the determination of its valence band gap and electron plasma energy. Time dependent measurement of the spectral dispersion of the relative reflectance of the film formed at the interface, using the same computational formalism, leads to the dynamical determination of the spectral variation of its optical and electrical properties. We computed behaviors of the dielectric constant (dielectric permittivity), the dielectric loss function, refractive index and extinction coefficient, effective valence number and of the electron loss functions. The measurements tend to stabilize when the dynamic adsorption-desorption equilibrium is reached at the interface level.

Etching of Silicon in HBr Plasmas for High Aspect Ratio Features

NASA Technical Reports Server (NTRS)

Hwang, Helen H.; Meyyappan, M.; Mathad, G. S.; Ranade, R.

2002-01-01

Etching in semiconductor processing typically involves using halides because of the relatively fast rates. Bromine containing plasmas can generate high aspect ratio trenches, desirable for DRAM and MEMS applications, with relatively straight sidewalk We present scanning electron microscope images for silicon-etched trenches in a HBr plasma. Using a feature profile simulation, we show that the removal yield parameter, or number of neutrals removed per incident ion due to all processes (sputtering, spontaneous desorption, etc.), dictates the profile shape. We find that the profile becomes pinched off when the removal yield is a constant, with a maximum aspect ratio (AR) of about 5 to 1 (depth to height). When the removal yield decreases with increasing ion angle, the etch rate increases at the comers and the trench bottom broadens. The profiles have ARs of over 9:1 for yields that vary with ion angle. To match the experimentally observed etched time of 250 s for an AR of 9:1 with a trench width of 0.135 microns, we find that the neutral flux must be 3.336 x 10(exp 17)sq cm/s.

Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

PubMed

He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

2016-09-01

Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix.

Formaldehyde sorption and desorption characteristics of gypsum wallboard

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

Matthews, T.G.; Hawthorne, A.R.; Thompson, C.V.

1987-07-01

The sorption and subsequent desorption of formaldehyde (CH/sub 2/O) vapor from unpainted gypsum wallboard have been investigated in environmental chamber experiments conducted at 23 /sup 0/C, 50% relative humidity, an air exchange to board loading ratio of 0.43 m/h, and CH/sub 2/O concentrations ranging from 0 to 0.50 mg/m/sup 3/. Both CH/sub 2/O sorption and CH/sub 2/O desorption processes are described by a three-parameter, single-exponential model with an exponential lifetime of 2.9 +/- 0.1 days. The storage capacity of gypsum board for CH/sub 2/O vapor results in a time-dependent buffer to changes in CH/sub 2/O vapor concentration surrounding the boardmore » but appears to cause only a weak, permanent loss mechanism for CH/sub 2/O vapor. Prior to significant depletion of sorbed CH/sub 2/O, desorption rates from CH/sub 2/O-exposed gypsum board exhibit a linear dependence with negative slope on CH/sub 2/O vapor concentration. Analogous CH/sub 2/O emissions properties have been observed for pressed-wood products bonded with urea-formaldehyde resins. 17 references, 5 figures.« less

Formaldehyde sorption and desorption characteristics of gypsum wallboard

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

Matthews, T.G.; Hawthorne, A.R.; Thompson, C.V.

1986-01-01

The sorption and subsequent desorption of formaldehyde (CH/sub 2/O) vapor from unpainted gypsum wallboard has been investigated in environmental chamber experiments conducted at 23/sup 0/C, 50% relative humidity, an air exchange to board loading ratio of 0.43 m/h, and CH/sub 2/O concentrations ranging from 0 to 0.50 mg/m/sup 3/. Both CH/sub 2/O sorption and desorption processes are described using a three-parameter, single-exponential model with an exponential lifetime of 2.9 +- 0.1 days. The storage capacity of gypsum board for CH/sub 2/O vapor results in a time-dependent buffer to changes in CH/sub 2/O vapor concentration surrounding the board, but appears tomore » cause only a weak, permanent loss mechanism for CH/sub 2/O vapor. Short-term CH/sub 2/O desorption rates from CH/sub 2/O-exposed gypsum board (prior to significant depletion of sorbed CH/sub 2/O) exhibit a linear dependence with negative slope on CH/sub 2/O vapor concentration analogous to CH/sub 2/O emissions from pressed-wood products bonded with urea-formaldehyde resins.« less

Irreversibility of 2,4-Dichlorophenoxyacetic Acid Sorption onto a Volcanic Ash Soil

NASA Astrophysics Data System (ADS)

Mon, E.; Kawamoto, K.; Komatsu, T.; Moldrup, P.

2008-12-01

Pesticide sorption and desorption in soils are key processes governing fate and transport of pesticides in the soil environment. The irreversibility (or hysteresis) in the processes of pesticide sorption and desorption needs to be known to accurately predict behavior of pesticides in soil systems. 2,4-dichlorophenoxyacetic acid (2,4-D) is a widely used pesticide in agriculture fields. However, only few studies of 2,4-D adsorption onto Andosols (volcanic ash soils) have been published, and the knowledge of 2,4-D desorption onto Andosols is very limited. In this study, a volcanic ash soil sampled from a pasture site in Nishi-Tokyo, Japan was used as a sorbent in order to investigate the irreversibility of 2,4-D sorption. For comparison, a pure clay mineral (kaolinite) obtained from Clay Science Society of Japan (CSSJ) was also used. 2,4-D solutions with three concentrations (0.011, 0.022 and 0.045 mmol/L) were prepared in artificial rain water (ARW= 0.085mM NaCl + 0.015mM CaCl2) to simulate field conditions. To prepare the sample solutions, the solid mass/liquid volume ratio of 1:10 was used for both sorbents (volcanic ash soil and kaolinite). The experiments were conducted in triplicate using a batch method under different pH conditions to examine the effect of pH. Desorption was measured during a equilibration procedure: After removal of 7 mL of supernatant in the sorption step, 7 mL of ARW excluding 2,4-D was added to the sample solution after which, it was equilibrated and centrifuged. The procedure was performed sequentially three or four times to obtain a desorption isotherm. Sorption and desorption generally followed Freundlich isotherms. The results showed markedly effects of pH on 2,4-D sorption and desorption in both the soil and kaolinite, with the percentage of sorption increasing with decreasing pH whereas the percentage of desorption decreased. There was a larger adsorption-desorption hysteresis in the volcanic ash soil as compared to kaolinite. Moreover, the largest hysteresis was found under the lowest pH condition indicating that the hysteretic effect likely depended on the variation of pH. In summary, the volcanic ash soil exhibited higher sorption coefficients and hysteresis than kaolinite, likely due to soil properties such as high organic matter content and the presence of different clay minerals.

Photon stimulated desorption from oxidized Al(110). [Surface hydroxyls

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

Johnson, E.D.; Garrett, R.F.; Knotek, M.L.

1987-01-01

We have studied oxide films on Al(110) by photon stimulated desorption (PSD) on the Bell Labs U4 PGM at the National Synchrotron Light Source. Utilizing a time of flight technique we have obtained ion energy distribution (IED) and relative ion yield (RIY) data at the Al 2p and O 1s edges for oxides prepared at various temperatures. These initial studies suggest that different sites for the surface hydroxyls exist, that they can be selectively prepared, and examined by PSD. 15 refs., 9 figs.

The role of surface charging during the coadsorption of mercaptohexanol to DNA layers on gold: direct observation of desorption and layer reorientation.

PubMed

Arinaga, K; Rant, U; Tornow, M; Fujita, S; Abstreiter, G; Yokoyama, N

2006-06-20

We study the coadsorption of mercaptohexanol onto preimmobilized oligonucleotide layers on gold. Monitoring the position of the DNA relative to the surface by optical means directly shows the mercaptohexanol-induced desorption of DNA and the reorientation of surface-tethered strands in situ and in real time. By simultaneously recording the electrochemical electrode potential, we are able to demonstrate that changes in the layer conformation are predominantly of electrostatic origin and can be reversed by applying external bias to the substrate.

Experimental study on desorption characteristics of SAPO-34 and ZSM-5 zeolite

NASA Astrophysics Data System (ADS)

Yuan, Z. X.; Zhang, X.; Wang, W. C.; Du, C. X.; Liu, Z. B.; Chen, Y. C.

2018-03-01

The dynamic characteristics of SAPO-34 and ZSM-5 zeolite in the desorption process have been experimentally studied with the gravimetric method. The weight change of the test sample was recorded continually for different conditions of temperature and pressure. The curve of the desorption degree with the temperature and the pressure was obtained and discussed. With the intrinsic different micro-structure, the two zeolites showed distinguished characteristics of the desorption. In contrast to an S-shaped desorption curve of the SAPO-34, the ZSM-5 showed an exponential desorption curve. In comparison, the desorption characteristics of the ZSM-5 were better than that of the SAPO-34 in the temperature range of 40 °C 90 °C. Nevertheless, the effect of the pressure on the desorption degree was stronger for the SAPO-34 than for the ZSM-5. Further analysis revealed that the desorption speed was affected more strongly by the temperature than by the pressure.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1987-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possible role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1985-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possibile role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Catalytic Activation of Mg-Doped GaN by Hydrogen Desorption Using Different Metal Thin Layers

NASA Astrophysics Data System (ADS)

Wei, Tongbo; Wang, Junxi; Liu, Naixin; Lu, Hongxi; Zeng, Yiping; Wang, Guohong; Li, Jinmin

2010-10-01

The annealing of Mg-doped GaN with Pt and Mo layers has been found to effectively improve the hole concentration of such material by more than 2 times as high as those in the same material without metal. Compared with the Ni and Mo catalysts, Pt showed good activation effect for hydrogen desorption and ohmic contact to the Ni/Au electrode. Despite the weak hydrogen desorption, Mo did not diffuse into the GaN epilayer in the annealing process, thus suppressing the carrier compensation phenomenon with respect to Ni and Pt depositions, which resulted in the high activation of Mg acceptors. For the GaN activated with the Ni, Pt, and Mo layers, the blue emission became dominant, followed by a clear peak redshift and the degradation of photoluminescence signal when compared with that of GaN without metal.

Flash Desorption/Mass Spectrometry for the Analysis of Less- and Nonvolatile Samples Using a Linearly Driven Heated Metal Filament

NASA Astrophysics Data System (ADS)

Usmanov, Dilshadbek T.; Ninomiya, Satoshi; Hiraoka, Kenzo

2013-11-01

In this paper, the important issue of the desorption of less- and nonvolatile compounds with minimal sample decomposition in ambient mass spectrometry is approached using ambient flash desorption mass spectrometry. The preheated stainless steel filament was driven down and up along the vertical axis in 0.3 s. At the lowest position, it touched the surface of the sample with an invasion depth of 0.1 mm in 50 ms (flash heating) and was removed from the surface (fast cooling). The heating rate corresponds to ~104 °C/s at the filament temperature of 500 °C. The desorbed gaseous molecules were ionized by using a dielectric barrier discharge ion source, and the produced ions were detected by a time-of-flight (TOF) mass spectrometer. Less-volatile samples, such as pharmaceutical tablets, narcotics, explosives, and C60 gave molecular and protonated molecule ions as major ions with thermal decomposition minimally suppressed. For synthetic polymers (PMMA, PLA, and PS), the mass spectra reflected their backbone structures because of the suppression of the sequential thermal decompositions of the primary products. The present technique appears to be suitable for high-throughput qualitative analyses of many types of solid samples in the range from a few ng to 10 μg with minimal sample consumption. Some contribution from tribodesorption in addition to thermal desorption was suggested for the desorption processes. [Figure not available: see fulltext.

Effect of Grain Size on Differential Desorption of Volatile Species and on Non-ideal MHD Diffusivity

NASA Astrophysics Data System (ADS)

Zhao, Bo; Caselli, Paola; Li, Zhi-Yun

2018-05-01

We developed a chemical network for modeling the chemistry and non-ideal MHD effects from the collapsing dense molecular clouds to protostellar disks. First, we re-formulated the cosmic-ray desorption rate by considering the variations of desorption rate over the grain size distribution. We find that the differential desorption of volatile species is amplified by the grains larger than 0.1 μm, because larger grains are heated to a lower temperature by cosmic-rays and hence more sensitive to the variations in binding energies. As a result, atomic nitrogen N is ˜2 orders of magnitude more abundant than CO; N2H+ also becomes a few times more abundant than HCO+ due to the increased gas-phase N2. However, the changes in ionization fraction due to freeze-out and desorption only have minor effects on the non-ideal MHD diffusivities. Our chemical network confirms that the very small grains (VSGs: below a few 100 Å) weakens the efficiency of both ambipolar diffusion and Hall effect. In collapsing dense cores, a maximum ambipolar diffusion is achieved when truncating the MRN size distribution at 0.1 μm, and for a maximum Hall effect, the truncation occurs at 0.04 μm. We conclude that the grain size distribution is crucial to the differential depletion between CO and N2 related molecules, as well as to the non-ideal MHD diffusivities in dense cores.

Examination of a New Desorption Method for Solid Adsorption Method of Working Environment Measurement －Attempt to Improve Desorption Efficiency of Organic Solvents from a Coconut-Shell-Activated Carbon Using Surfactant Solutions－.

PubMed

Hinoue, Mitsuo; Hori, Hajime

2017-01-01

For a new desorption method development for working environment measurement, desorption efficiency of organic solvent vapors from an activated carbon was examined using desorption solutions that consisted of anionic and nonionic surfactants. Ten μl of an aqueous solution of isopropyl alcohol or methyl ethyl ketone diluted with distilled water was spiked into a 10 ml vial with a coconut-shell-activated carbon (100 mg). The vial was left for 24 h, and 5 ml a desorption solution was added. Afterwards, the vial was put into an incubator at 60°C and left for 24 h, then the desorption efficiency was determined by analyzing the headspace gas in the vial with a gas chromatograph equipped with flame ionization detector. By adding one or four kinds of nonionic surfactants to the aqueous solution containing two kinds of anionic surfactants, the effect adding nonionic surfactant to the desorption efficiency was investigated, but improvement of desorption efficiency was not observed. On the other hand, desorption efficiency varied depending on the production lot of the coconut-shell-activated carbon tube used as the adsorbent.

Rapid Detection and Identification of Candidemia by Direct Blood Culturing on Solid Medium by Use of Lysis-Centrifugation Method Combined with Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS).

PubMed

Idelevich, Evgeny A; Grünastel, Barbara; Becker, Karsten

2017-01-01

Candida sepsis is a life-threatening condition with increasing prevalence. In this study, direct blood culturing on solid medium using a lysis-centrifugation procedure enabled successful Candida species identification by matrix-assisted laser desorption-ionization time of flight mass spectrometry on average 3.8 h (Sabouraud agar) or 7.4 h (chocolate agar) before the positivity signal for control samples in Bactec mycosis-IC/F or Bactec Plus aerobic/F bottles, respectively. Direct culturing on solid medium accelerated candidemia diagnostics compared to that with automated broth-based systems. Copyright © 2016 American Society for Microbiology.

Classification of Astrocytomas and Oligodendrogliomas from Mass Spectrometry Data Using Sparse Kernel Machines

PubMed Central

Huang, Jacob; Gholami, Behnood; Agar, Nathalie Y. R.; Norton, Isaiah; Haddad, Wassim M.; Tannenbaum, Allen R.

2013-01-01

Glioma histologies are the primary factor in prognostic estimates and are used in determining the proper course of treatment. Furthermore, due to the sensitivity of cranial environments, real-time tumor-cell classification and boundary detection can aid in the precision and completeness of tumor resection. A recent improvement to mass spectrometry known as desorption electrospray ionization operates in an ambient environment without the application of a preparation compound. This allows for a real-time acquisition of mass spectra during surgeries and other live operations. In this paper, we present a framework using sparse kernel machines to determine a glioma sample’s histopathological subtype by analyzing its chemical composition acquired by desorption electrospray ionization mass spectrometry. PMID:22256188

Catalytically Enhanced Hydrogen Sorption in Mg-MgH2 by Coupling Vanadium-Based Catalyst and Carbon Nanotubes

PubMed Central

Kadri, Atikah; Jia, Yi; Chen, Zhigang; Yao, Xiangdong

2015-01-01

Mg (MgH2)-based composites, using carbon nanotubes (CNTs) and pre-synthesized vanadium-based complex (VCat) as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of 6.50 wt. % of hydrogen per minute and 6.50 wt. % of hydrogen release in 10 min at 200 °C and 300 °C, respectively. The temperature programmed desorption (TPD) results reveal that coupling VCat and CNTs reduces both peak and onset temperatures by more than 60 °C and 114 °C, respectively. In addition, the presence of both VCat and CNTs reduces the enthalpy and entropy of desorption of about 7 kJ/mol H2 and 11 J/mol H2·K, respectively, as compared to those of the commercial MgH2, which ascribe to the decrease of desorption temperature. From the study of the effect of CNTs milling time, it is shown that partially destroyed CNTs (shorter milling time) are better to enhance the hydrogen sorption performance.

A Versatile Integrated Ambient Ionization Source Platform.

PubMed

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-30

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.

Development of a Dual Plasma Desorption/Ionization System for the Noncontact and Highly Sensitive Analysis of Surface Adhesive Compounds

PubMed Central

Aida, Mari; Iwai, Takahiro; Okamoto, Yuki; Kohno, Satoshi; Kakegawa, Ken; Miyahara, Hidekazu; Seto, Yasuo; Okino, Akitoshi

2017-01-01

We developed a dual plasma desorption/ionization system using two plasmas for the semi-invasive analysis of compounds on heat-sensitive substrates such as skin. The first plasma was used for the desorption of the surface compounds, whereas the second was used for the ionization of the desorbed compounds. Using the two plasmas, each process can be optimized individually. A successful analysis of phenyl salicylate and 2-isopropylpyridine was achieved using the developed system. Furthermore, we showed that it was possible to detect the mass signals derived from a sample even at a distance 50 times greater than the distance from the position at which the samples were detached. In addition, to increase the intensity of the mass signal, 0%–0.02% (v/v) of hydrogen gas was added to the base gas generated in the ionizing plasma. We found that by optimizing the gas flow rate through the addition of a small amount of hydrogen gas, it was possible to obtain the intensity of the mass signal that was 45–824 times greater than that obtained without the addition of hydrogen gas. PMID:29234573

A Versatile Integrated Ambient Ionization Source Platform

NASA Astrophysics Data System (ADS)

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-01

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. [Figure not available: see fulltext.

Reversibility of radiocaesium sorption on illite

NASA Astrophysics Data System (ADS)

de Koning, Arjan; Comans, Rob N. J.

2004-07-01

Adsorption of trace amounts of radiocaesium on NH 4-, K-, and Na-saturated Fithian illite and subsequent desorption by 1 M NH 4 showed that a substantial amount of radiocaesium (44%, 46%, and 91% for NH 4-, K-, and Na-illite, respectively) cannot be desorbed after only 5 min of adsorption. Our results suggest that this instantaneous fixation is caused by the collapse of the frayed edges of the clay mineral and the relatively high concentration of radiocaesium building up in solution in the batch desorption experiments. Consequently, commonly applied high-NH 4 extractions underestimate truly exchangeable amounts of radiocaesium in soils and sediments containing illitic clay minerals. The rate of desorption of trace amounts of radiocaesium from the solids using high NH 4 or Cs concentrations has a half-life of about 2 yr, reflecting radiocaesium desorption from (partially) collapsed interlayers. Extraction of radiocaesium from illite after 5 min of contact time with a Cs-selective adsorbent or a 1 × 10 -6 M CsCl solution shows that 100% of the bound radiocaesium is readily available. The desorption rate in the presence of a Cs-selective adsorbent has a half-life of about 0.2 yr. Desorption of radiocaesium from illite using different ammonium concentrations shows that radiocaesium partitioning follows reversible ion-exchange theory if the NH 4 concentration is below 1 × 10 -4 M, and sufficient time (weeks) is allowed for the reaction to proceed. Thus, radiocaesium sorption reversibility in the natural environment is much higher than generally assumed, and equilibrium solid/liquid partitioning may be assumed for the long-term modelling of radiocaesium mobility in the natural environment. In the particular case of anoxic freshwater sediments with very high NH 4 concentrations in the pore waters (up to several mmol.L -1), collapse of the frayed edges of illite may occur, influencing radiocaesium partitioning. If collapse occurs before radiocaesium adsorbs to illite, high caesium sorption reversibility as measured by high-NH 4 extraction can be expected because further collapse of the frayed edges during the extraction procedure will be limited. This effect has indeed been observed earlier in the extraction of radiocaesium from anoxic freshwater sediments with high-NH 4 solutions and was as yet unexplained.

Changes induced on the surfaces of small Pd clusters by the thermal desorption of CO

NASA Technical Reports Server (NTRS)

Doering, D. L.; Poppa, H.; Dickinson, J. T.

1980-01-01

The stability and adsorption/desorption properties of supported Pd crystallites less than 5 nm in size were studied by Auger electron spectroscopy and repeated flash thermal desorption of CO. The Pd particles were grown epitaxially on heat-treated, UHV-cleaved mica at a substrate temperature of 300 C and a Pd impingement flux of 10 to the 13th atoms/sq cm s. Auger analysis allowed in situ measurement of relative particle dispersion and contamination, while FTD monitored the CO desorption properties. The results show that significant changes in the adsorption properties can be detected. Changes in the Pd Auger signal and the desorption spectrum during the first few thermal cycles are due to particle coalescence and facetting and the rate of this change is dependent on the temperature and duration of the desorption. Significant reductions in the amplitude of the desorptions peak occur during successive CO desorptions which are attributed to increases of surface carbon, induced by the desorption of CO. The contamination process could be reversed by heat treatment in oxygen or hydrogen

Persistent photoconductivity in ZnO nanowires: Influence of oxygen and argon ambient

NASA Astrophysics Data System (ADS)

Madel, M.; Huber, F.; Mueller, R.; Amann, B.; Dickel, M.; Xie, Y.; Thonke, K.

2017-03-01

ZnO nanowires typically show persistent photoconductivity (PPC), which depends in their temporal behaviour on the ambient. We investigate ZnO nanowires in oxygen and argon ambient and analyze the PPC both on the short and on the long time scale to sort out the underlying mechanisms. Wavelength dependent excitation shows the energy barrier for the PPC to be around 150 meV below the band gap of ZnO, independent of the ambient atmosphere. In photocurrent measurements at constant wavelength, a log-logistic dependence of the conductivity on the partial oxygen pressure is observed. The experimental results are compared to a model of Bonasewicz et al. [J. Electrochem. Soc. 133, 2270 (1986)] and can be explained by oxygen adsorption processes occurring on the surface of the ZnO nanowires. From temperature dependent measurements of the decay times in oxygen and argon ambient, the related activation energies for the fast and slow decay processes are determined. Comparing our results to theoretical calculations of energy levels of intrinsic defects [Janotti and Van de Walle, Phys. Status Solidi B 248, 799 (2011)], we find oxygen vacancies to be related to the fast decay processes, whereas adsorption and desorption processes of oxygen on the ZnO nanowire surface account for the slow part.

Advanced structural analysis of nanoporous materials by thermal response measurements.

PubMed

Oschatz, Martin; Leistner, Matthias; Nickel, Winfried; Kaskel, Stefan

2015-04-07

Thermal response measurements based on optical adsorption calorimetry are presented as a versatile tool for the time-saving and profound characterization of the pore structure of porous carbon-based materials. This technique measures the time-resolved temperature change of an adsorbent during adsorption of a test gas. Six carbide and carbon materials with well-defined nanopore architecture including micro- and/or mesopores are characterized by thermal response measurements based on n-butane and carbon dioxide as the test gases. With this tool, the pore systems of the model materials can be clearly distinguished and accurately analyzed. The obtained calorimetric data are correlated with the adsorption/desorption isotherms of the materials. The pore structures can be estimated from a single experiment due to different adsorption enthalpies/temperature increases in micro- and mesopores. Adsorption/desorption cycling of n-butane at 298 K/1 bar with increasing desorption time allows to determine the pore structure of the materials in more detail due to different equilibration times. Adsorption of the organic test gas at selected relative pressures reveals specific contributions of particular pore systems to the increase of the temperature of the samples and different adsorption mechanisms. The use of carbon dioxide as the test gas at 298 K/1 bar provides detailed insights into the ultramicropore structure of the materials because under these conditions the adsorption of this test gas is very sensitive to the presence of pores smaller than 0.7 nm.

Evaluation of Water Repellency in Petroleum Drilling Cuttings Treated by Thermal Desorption: Implications for Use in Construction and Agriculture

NASA Astrophysics Data System (ADS)

Domínguez-Rodríguez, Verónica I.; Guzmán-Osorio, Francisco J.; Adams Schroeder, Randy H.; Bautista-Margulis, Raúl G.

2010-05-01

Thermal desorption is one of many methods used for the remediation of hydrocarbon contaminated soils and similar materials. It has several advantages over competing technologies, especially with respect to treatment times. While the biological treatment of contaminated soils may take several months depending principally on the type of hydrocarbons and starting concentration, thermal desorption typically takes less than one month, depending on the treatment capacities of the equipment involved, and the volume of material requiring treatment. In the petroleum producing region of southeastern Mexico, this has been one of the principal methods used for the treatment of drilling cuttings, due mostly to the short time required. As with most remediation projects, as well as in the treatment of exploration and production (E&P) wastes, the criteria used to consider the remediation finalized is the concentration of hydrocarbons in the treated material. This is based on the supposition that at some (relatively low) hydrocarbon concentration, the toxicological affects are reduced to acceptable levels. However, little attention has been paid to the physical-chemical properties of supposedly treated material, which may suffer from water repellency, especially in thermal treatment methods. This could greatly reduce the options for final use of treated materials, especially to support plant growth. Conversely, there may be some construction uses of treated material in which some water repellence could be beneficial (caps for land fills, for example). Considering the relevance of the physical-chemical impacts of petroleum on soil and similar materials, we felt it was important to evaluate the efficiency of the principal method used to treat E&P wastes in Mexico (thermal desporption) based on these factors. In this study different operating conditions (temperature and residence time) of a sub-pilot scale thermal desorption unit were evaluated with respect not only to reduction in hydrocarbon concentration, but also based on water repellency. To our knowledge this is the first study of this type. Water repellency severity was measured in petroleum drilling cuttings which had been treated by thermal desorption to reduce the concentration of total petroleum hydrocarbons (TPHs). The initial TPH concentration in the untreated material was 16850mg/Kg (dry). The prototype batch rotary oven used in this study was operated at 25 rpm, at three temperatures and three treatment times: at 150, 200, and 300°C, for 10, 15, and 20 minutes. Four of the nine treatments complied with the Mexican environmental norm (TPH less than 3000 mg/Kg), these being: at 200°C for 20 minutes and at 300°C for 10, 15 and 20 minutes. The treatments at 150°C resulted in a TPH reduction insufficient to comply with Mexican norm, and also resulted in high MED values (3,46 - 3,67). At 200°C, the decrease in repellency was directly proportional to the treatment time (r=-0,950), with a final value of MED=2,61 after 20 minutes. At 300°C, an increase in water repellency was observed to be directly proportional to the treatment time (r=0,9997), with a final value of MED=3,73 (severe repellence) after 20 minutes. This may be due to the partial combustion (rather than only desorption) of hydrocarbons at this temperature, and their deposition on soil surfaces. Based on these observations, operating conditions of 200°C for 20 minutes are recommended to achieve effective thermal desorption while reducing water repellency in the treated material. If a final material with more severe water repellency is desired for use in construction, a higher operation temperature is required (300°C) for at least 15-20 minutes.

Competitive adsorption of heavy metal ions on carbon nanotubes and the desorption in simulated biofluids.

PubMed

Ma, Xin; Yang, Sheng-Tao; Tang, Huan; Liu, Yuanfang; Wang, Haifang

2015-06-15

Carbon nanotubes (CNTs) had meaningful adsorption capacities for Pb(2+), Cu(2+), Zn(2+) and Cd(2+), while Pb(2+) showed the highest adsorption in the competitive adsorption evaluations. The desorption behaviors of heavy metal ions were completely different in various biofluids, where the desorption was significantly influenced by pH and the presence of proteins/other cations. The desorption was most effective in simulated stomach juice, and much less effective in other simulated biofluids. More Pb(2+) stuck to CNTs than others, resulting in less desorption. Interestingly, the competitive desorption behaviors of four ions were largely changed comparing to the individual desorption behaviors. The implications to the biosafety evaluations and synergistic effects of CNT are discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

N2 and CO Desorption Energies from Water Ice

NASA Astrophysics Data System (ADS)

Fayolle, Edith C.; Balfe, Jodi; Loomis, Ryan; Bergner, Jennifer; Graninger, Dawn; Rajappan, Mahesh; Öberg, Karin I.

2016-01-01

The relative desorption energies of CO and N2 are key to interpretations of observed interstellar CO and N2 abundance patterns, including the well-documented CO and N2H+ anti-correlations in disks, protostars, and molecular cloud cores. Based on laboratory experiments on pure CO and N2 ice desorption, the difference between CO and N2 desorption energies is small; the N2-to-CO desorption energy ratio is 0.93 ± 0.03. Interstellar ices are not pure, however, and in this study we explore the effect of water ice on the desorption energy ratio of the two molecules. We present temperature programmed desorption experiments of different coverages of 13CO and 15N2 on porous and compact amorphous water ices and, for reference, of pure ices. In all experiments, 15N2 desorption begins a few degrees before the onset of 13CO desorption. The 15N2 and 13CO energy barriers are 770 and 866 K for the pure ices, 1034-1143 K and 1155-1298 K for different submonolayer coverages on compact water ice, and 1435 and 1575 K for ˜1 ML of ice on top of porous water ice. For all equivalent experiments, the N2-to-CO desorption energy ratio is consistently 0.9. Whenever CO and N2 ice reside in similar ice environments (e.g., experience a similar degree of interaction with water ice) their desorption temperatures should thus be within a few degrees of one another. A smaller N2-to-CO desorption energy ratio may be present in interstellar and circumstellar environments if the average CO ice molecules interacts more with water ice compared to the average N2 molecules.

Sorption, degradation and transport phenomena of alcohol ethoxysulfates in agricultural soils. Laboratory studies.

PubMed

Fernández-Ramos, C; Rodríguez-Gómez, R; Reis, M S; Zafra-Gómez, A; Verge, C; de Ferrer, J A; Pérez-Pascual, M; Vílchez, J L

2017-03-01

In the present work, laboratory studies were conducted in order to determine and model the sorption, degradation and transport processes of alcohol ethoxysulfates (AES), one of the most important groups of anionic surfactants. Adsorption/desorption isotherms were obtained for several structurally related AES ethoxymers (homologue AES-C 12 E n with n = 0-10 ethoxymer units and homologue AES-C 14 E n with n = 0-7 ethoxymer units) using a batch equilibrium method. Data were fitted to a linear and a Freundlich isotherm models. Additionally, experiments in continuous-flow soil columns were also carried out and the breakthrough curves observed for each compound were studied. Breakthrough curves were used to determine the fundamental parameters of the transport model (hydrodynamic dispersion coefficient, degradation rate constant and adsorption/desorption isotherm slope), that is the main phenomena that take place simultaneously when AES move through agricultural soil. When the results obtained for the AES ethoxymers are combined, they reveal a clear and consistent trend towards a sorption increase with the number of ethoxylated units and with the length of the alkyl chain that opens the possibility to estimate the values of the transport parameters for other structurally related ethoxymers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Excessive Counterion Condensation on Immobilized ssDNA in Solutions of High Ionic Strength

PubMed Central

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-01-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (ηrel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, ηrel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations. PMID:14645075

Excessive counterion condensation on immobilized ssDNA in solutions of high ionic strength.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-12-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (etarel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, etarel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations.

Noise analysis and relaxation experiments of transport of hydrophobic anions across lipid membranes at equilibrium and nonequilibrium.

PubMed

Junges, R; Kolb, H A

1983-06-01

Under equilibrium and nonequilibrium steady-state conditions, the spectral intensity of current noise SJ(f) generated by the transport of hydrophobic anions across lipid bilayer membranes was investigated. The experimental results were compared with different reaction models. SJ(f) showed a characteristic increase proportional to f2 between frequency-independent tails at low and high frequencies. This gradient was found to be independent of applied voltage which indicates the contribution of a single voltage-dependent reaction step of ion translocation across the membrane. From the shape of SJ(f) at low frequencies the rate constant of ion desorption from the membrane into the aqueous phase could be estimated. Unambiguous evidence for the application of a general model, which includes the coupling of slow ion diffusion in the aqueous phase to ion adsorption/desorption at the membrane interface, could not be obtained from the low-frequency shape of SJ(f). The shot noise of this ion transport determines the amplitude of SJ(f) at high frequencies which decreases with increasing voltage applied. Analysis of voltage-jump current-relaxation experiments and of current noise carried out on one membrane yielded significant differences of the derived ion partition coefficient. This deviation is qualitatively described on the basis of incomplete reaction steps.

Perfluoroalkyl substances in a firefighting training ground (FTG), distribution and potential future release.

PubMed

Baduel, Christine; Paxman, Christopher J; Mueller, Jochen F

2015-10-15

The present study investigates the occurrence and fate of 15 perfluoroalkyl substances (PFASs) and one fluorotelomer sulfonate from a firefighting training ground (FTG) that was contaminated by intensive use of aqueous film forming foams (AFFF). The contamination levels and their spatial and vertical distribution are assessed in the structure. At the surface of the pad, perfluorooctane sulphonate (PFOS) is the dominant PFASs measured, with concentration varying from 10 to 200 μg g(-1). PFASs were also detected in a concrete core at up to 12 cm depth, suggesting the vertical movement and higher transport potential of shorter chain compounds. The estimated mass load of linear PFOS in this specific pad was >300 g with a total of 1.7 kg for the sum of all PFASs analyzed. The kinetics of desorption of PFOS, PFOA and 6:2FTS from the concrete into an overlaying static water volume has been measured under field conditions at two constant temperatures. Fitting the desorption data and estimated rainfall/runoff to a kinetic model suggests that this and similar firefighting training pads will likely remain a source of PFASs for many decades (t0.5=25 years for PFOS). Copyright © 2015 Elsevier B.V. All rights reserved.

Fabrication of polyaniline-coated halloysite nanotubes by in situ chemical polymerization as a solid-phase microextraction coating for the analysis of volatile organic compounds in aqueous solutions.

PubMed

Abolghasemi, Mir Mahdi; Arsalani, Naser; Yousefi, Vahid; Arsalani, Mahmood; Piryaei, Marzieh

2016-03-01

We have synthesized an organic-inorganic polyaniline-halloysite nanotube composite by an in situ polymerization method. This nanocomposite is immobilized on a stainless-steel wire and can be used as a fiber coating for solid-phase microextraction. It was found that our new solid-phase microextraction fiber is an excellent adsorbent for the extraction of some volatile organic compounds in aqueous samples in combination with gas chromatography and mass spectrometry. The coating can be prepared easily, is mechanically stable, and exhibits relatively high thermal stability. It is capable of extracting phenolic compounds from water samples. Following thermal desorption, the phenols were quantified by gas chromatography with mass spectrometry. The effects of extraction temperature, extraction time, sample ionic strength, stirring rate, pH, desorption temperature and desorption time were studied. Under optimal conditions, the repeatability for one fiber (n = 5), expressed as the relative standard deviation, is between 6.2 and 9.1%. The detection limits range from 0.005 to 4 ng/mL. The method offers the advantage of being simple to use, with a shorter analysis time, lower cost of equipment and higher thermal stability of the fiber in comparison to conventional methods of analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, R.J.; Cecchi, J.L.

1983-07-26

This invention relates generally to the field of gas desorption from metals; and, more particularly, to a method of enhancing the selective desorption of a particular isotope of a gas from metals. Enhanced selective desorption is especially useful in the operation of fusion devices.

Adsorption and Desorption of Hydrogen by Gas-Phase Palladium Clusters Revealed by In Situ Thermal Desorption Spectroscopy.

PubMed

Takenouchi, Masato; Kudoh, Satoshi; Miyajima, Ken; Mafuné, Fumitaka

2015-07-02

Adsorption and desorption of hydrogen by gas-phase Pd clusters, Pdn(+), were investigated by thermal desorption spectroscopy (TDS) experiments and density functional theory (DFT) calculations. The desorption processes were examined by heating the clusters that had adsorbed hydrogen at room temperature. The clusters remaining after heating were monitored by mass spectrometry as a function of temperature up to 1000 K, and the temperature-programmed desorption (TPD) curve was obtained for each Pdn(+). It was found that hydrogen molecules were released from the clusters into the gas phase with increasing temperature until bare Pdn(+) was formed. The threshold energy for desorption, estimated from the TPD curve, was compared to the desorption energy calculated by using DFT, indicating that smaller Pdn(+) clusters (n ≤ 6) tended to have weakly adsorbed hydrogen molecules, whereas larger Pdn(+) clusters (n ≥ 7) had dissociatively adsorbed hydrogen atoms on the surface. Highly likely, the nonmetallic nature of the small Pd clusters prevents hydrogen molecule from adsorbing dissociatively on the surface.

Identification of anaerobic bacteria by Bruker Biotyper matrix-assisted laser desorption ionization-time of flight mass spectrometry with on-plate formic acid preparation.

PubMed

Schmitt, Bryan H; Cunningham, Scott A; Dailey, Aaron L; Gustafson, Daniel R; Patel, Robin

2013-03-01

Identification of anaerobic bacteria using phenotypic methods is often time-consuming; methods such as 16S rRNA gene sequencing are costly and may not be readily available. We evaluated 253 clinical isolates of anaerobic bacteria using the Bruker MALDI Biotyper (Bruker Daltonics, Billerica, MA) matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) system with a user-supplemented database and an on-plate formic acid-based preparation method and compared results to those of conventional identification using biochemical testing or 16S rRNA gene sequencing. A total of 179 (70.8%) and 232 (91.7%) isolates were correctly identified to the species and genus levels, respectively, using manufacturer-recommended score cutoffs. MALDI-TOF MS offers a rapid, inexpensive method for identification of anaerobic bacteria.

Application of electron stimulated desorption techniques to measure the isotherm and the mean residence time of hydrogen physisorbed on a metal surface

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

Arakawa, Ichiro, E-mail: ich.arakawa@gakushuin.ac.jp; Shimizu, Hideyuki; Kawarabuki, Taku

2015-03-15

Electron stimulated desorption techniques were applied to probe the density of H{sub 2} physisorbed on a cold surface. The adsorption isotherm of H{sub 2} on a copper surface was measured in the equilibrium pressure range between 10{sup −9} and 10{sup −4} Pa at surface temperatures of 6.5 and 4.2 K. The mean residence times of H{sub 2} on copper were obtained from the observation of the time development of the surface density in a transitional state approaching equilibrium, and are 50–500 s for the coverage between 1 and 0.18 at 4.2 K of the substrate temperature. The adsorption energies of 1.18–1.27 kJ/mol, and themore » condensation coefficient of 0.074–0.018 were also deduced.« less

Extremely low-outgassing material: 0.2% beryllium copper alloy

NASA Astrophysics Data System (ADS)

Watanabe, Fumio

2004-01-01

Exploration for low-outgassing materials for use in ultrahigh vacuum and extreme high-vacuum systems is one of the most important topics of a vacuum researcher. We have found that a copper alloy containing 0.2% beryllium (0.2% BeCu) can attain an extremely low hydrogen outgassing rate of 10-14 Pa (H2) m/s order. Almost the entire surface of 0.2% BeCu is dominated by a BeO layer, after a 400 °C×72 h prebakeout treatment in an ultrahigh vacuum. This layer functions as a barrier to the processes of oxidization and permeation of hydrogen. In addition, this layer resists carbon contamination. Temperature-programmed desorption spectra show only a single peak for water at 150 °C and small quantities of any other desorption gases. Therefore, an in situ bakeout process in which the temperature simply ramps up to 150 °C and immediately ramps back down is enough for degassing; it does not require an ordinary sustained-temperature bakeout. Using an outgassing sample consisting of 0.2% BeCu disks housed in a 0.2% BeCu nipple chamber, a lowest outgassing rate of the 5.6×10-14 Pa (H2) m/s was measured by the pressure-rise method after pump cutoff. The pressure-rise versus time curve was completely nonlinear. It rises over time to a constant slope of 1/2 in a log-log plot, due to hydrogen diffusion from the bulk, but this requires over a week at room temperature. The hydrogen outgassing from the 0.2% BeCu bulk is completely dominated by a diffusion-limited mechanism. This article will describe why we obtain such low-outgassing rates with 0.2% BeCu. It is based on the observed surface changes with prebakeout treatment seen by x-ray photoelectron spectroscopy, and the improvement of hydrogen outgassing measurements by the pressure-rise method. A comparison is made to ordinary stainless steel. In addition, the concept of an outgassing reduction method will be discussed from a review of the published ultralow-outgassing data and reduction methods. .

Laser-stimulated desorption of organic molecules from surfaces, as a method of increasing the efficiency of ion mobility spectrometry analysis.

PubMed

Akmalov, Artem E; Chistyakov, Alexander A; Kotkovskii, Gennadii E

2017-08-01

Application of laser-induced desorption was investigated as a method of increasing the efficiency of gas phase analyzers on principles of field asymmetric ion mobility spectrometry. Mass spectrometric data of investigations of laser desorption of pentaerythritoltetranitrate molecules and cyclotetramethylenetetranitramine molecules from quartz substrate under vacuum were obtained. Laser sources a Nd 3+ :YAG with nanosecond pulse duration (λ = 532 nm) and a continuous wave diode laser (λ = 440 nm) were used. It was shown that both laser sources have different desorption abilities. This is expressed in various time of appearance of desorbed products that is caused by different heating mechanisms of surface layer. The desorbed quantity under action of both laser sources exceeds the detection threshold for all modern gas phase analyzers. It should be noted that despite the presence of surface dissociation of explosives under laser radiation, the quantity of nondissociated molecules is large enough for detection by ion mobility and field asymmetric ion mobility spectrometers. The optimal parameters of laser radiation for effective removal (evaporation) molecules of low-volatile compounds from surfaces are defined. The conclusion about preferable use of a Nd 3+ :YAG laser for increasing the detection ability of detectors based on ion mobility spectrometry was made.

Astrochem: Abundances of chemical species in the interstellar medium

NASA Astrophysics Data System (ADS)

Maret, Sébastien; Bergin, Edwin A.

2015-07-01

Astrochem computes the abundances of chemical species in the interstellar medium, as function of time. It studies the chemistry in a variety of astronomical objects, including diffuse clouds, dense clouds, photodissociation regions, prestellar cores, protostars, and protostellar disks. Astrochem reads a network of chemical reactions from a text file, builds up a system of kinetic rates equations, and solves it using a state-of-the-art stiff ordinary differential equation (ODE) solver. The Jacobian matrix of the system is computed implicitly, so the resolution of the system is extremely fast: large networks containing several thousands of reactions are usually solved in a few seconds. A variety of gas phase process are considered, as well as simple gas-grain interactions, such as the freeze-out and the desorption via several mechanisms (thermal desorption, cosmic-ray desorption and photo-desorption). The computed abundances are written in a HDF5 file, and can be plotted in different ways with the tools provided with Astrochem. Chemical reactions and their rates are written in a format which is meant to be easy to read and to edit. A tool to convert the chemical networks from the OSU and KIDA databases into this format is also provided. Astrochem is written in C, and its source code is distributed under the terms of the GNU General Public License (GPL).

Biodegradation of persistent organics can overcome adsorption-desorption hysteresis in biological activated carbon systems.

PubMed

Abromaitis, V; Racys, V; van der Marel, P; Meulepas, R J W

2016-04-01

In Biological Activated Carbon (BAC) systems, persistent organic pollutants can be removed through a combination of adsorption, desorption and biodegradation. These processes might be affected by the presence of other organics, especially by the more abundant easily-biodegradable organics, like acetate. In this research these relations are quantified for the removal of the persistent pharmaceutical metoprolol. Acetate did not affect the adsorption and desorption of metoprolol, but it did greatly enhance the metoprolol biodegradation. At least part of the BAC biomass growing on acetate was also able to metabolise metoprolol, although metoprolol was only converted after the acetate was depleted. The presence of easily-degradable organics like acetate in the feeding water is therefore beneficial for the removal of metoprolol in BAC systems. The isotherms obtained from metoprolol adsorption and desorption experiments showed that BAC systems are subject to hysteresis; for AC bioregeneration to take place the microbial biomass has to reduce the concentration at the AC-biomass interface 2.7 times compared to the concentration at which the carbon was being loaded. However, given the threshold concentration of the MET degrading microorganisms (<0.08 μg/L) versus the average influent concentration (1.3 μg/L), bioregeneration is feasible. Copyright © 2016 Elsevier Ltd. All rights reserved.

On-fiber furan formation from volatile precursors: a critical example of artefact formation during Solid-Phase Microextraction.

PubMed

Adams, An; Van Lancker, Fien; De Meulenaer, Bruno; Owczarek-Fendor, Agnieszka; De Kimpe, Norbert

2012-05-15

For the analysis of furan, a possible carcinogen formed during thermal treatment of food, Solid-Phase Microextraction (SPME) is a preferred and validated sampling method. However, when volatile furan precursors are adsorbed on the carboxen/PDMS fiber, additional amounts of furan can be formed on the fiber during thermal desorption, as shown here for 2-butenal and furfural. No significant increase in furan amounts was found upon heating the furan precursor 2-butenal, indicating that the furan amounts formed during precursor heating experiments are negligible as compared to the additional amounts of furan formed during fiber desorption. This artefactual furan formation increased with increasing desorption time, but especially with increasing desorption temperature. Although this effect was most pronounced on the Carboxen/PDMS SPME-fiber, it was also noted on two other SPME-fibers tested (PDMS and DVB/Carboxen/PDMS). The general impact on furan data from food and model systems in literature will depend on the amounts of volatile precursors present, but will probably remain limited. However, considering the importance of this worldwide food contaminant, special care has to be taken during SPME-analysis of furan. Especially when performing precursor studies, static headspace sampling should preferably be applied for furan analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

2015-08-01

A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

Analysis of nonderivatized steroids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using C70 fullerene as matrix.

PubMed

Montsko, Gergely; Vaczy, Alexandra; Maasz, Gabor; Mernyak, Erzsebet; Frank, Eva; Bay, Csaba; Kadar, Zalan; Ohmacht, Robert; Wolfling, Janos; Mark, Laszlo

2009-10-01

Neutral steroid hormones are currently analyzed by gas or liquid chromatography/mass spectrometry based methods. Most of the steroid compounds, however, lack volatility and do not contain polar groups, which results in inadequate chromatographic behavior and low ionization efficiency. Derivatization of the steroids to form more volatile, thermostable, and charged products solves this difficulty, but the derivatization of compounds with unknown chemical moieties is not an easy task. In this study, a rapid, high-throughput, sensitive matrix-assisted laser desorption/ionization time-of-flight mass spectrometry method is described using C(70) fullerene as a matrix compound. The application of the method is demonstrated for five general sex steroids and for synthetic steroid compounds in both negative and positive ionization modes.

Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Lu, I.-Chung; Chu, Kuan Yu; Lin, Chih-Yuan; Wu, Shang-Yun; Dyakov, Yuri A.; Chen, Jien-Lian; Gray-Weale, Angus; Lee, Yuan-Tseh; Ni, Chi-Kung

2015-07-01

The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.

The effect of chars and their water extractable organic carbon (WEOC) fractions on atrazine adsorption-desorption processes

NASA Astrophysics Data System (ADS)

Cavoski, I.; Jablonowski, N.; Burauel, P.; Miano, T.

2012-04-01

Chars are carbonaceous material produced from different type of biomass by pyrolysis. They are known as highly effective adsorbents for atrazine therefore limiting its degradation and its diffusion into the aqueous phase. The aim of the present work is to study the effects of different chars and char's derived WEOC on atrazine sorption-desorption processes. The five chars been used in this study derived from: 1) fast pyrolysis from hard wood (FP1); 2) flash pyrolysis from soft wood (FP2); 3) slow pyrolysis from deciduous wood (CC); 4) gasification from deciduous wood (GC) and 5) the market, purchased as activated charcoal standard (AC). Short-term batch equilibration tests were conducted to assess the sorption-desorption behavior of 14C-labeled atrazine on the chars, with a special focus on the desorption behavior using successive dilution method with six consecutive desorption step. Chars and their WEOC were physically and chemically characterized. Results demonstrate that biomass and pyrolysis process used to produce chars affect their physical and chemical properties, and atrazine adsorption-desorption behavior. Atrazine desorption resulted from the positive and competitive interactions between WEOC and chars surfaces. WEOC pool play important role in atrazine adsorption-desorption behavior. FP1 and FP2 with higher concentration of WEOC showed higher desorption rates, whereas GC, CC and AC with insignificant WEOC concentration strongly adsorb atrazine with low desorption rates. According to our results, when high WEOC pools chars are concerned, an increase in atrazine desorption can be observed but further studies would help in confirming the present results.

Kinetics of thorium and particle cycling along the U.S. GEOTRACES North Atlantic Transect

NASA Astrophysics Data System (ADS)

Lerner, Paul; Marchal, Olivier; Lam, Phoebe J.; Buesseler, Ken; Charette, Matthew

2017-07-01

The high particle reactivity of thorium has resulted in its widespread use in tracing processes impacting marine particles and their chemical constituents. The use of thorium isotopes as tracers of particle dynamics, however, largely relies on our understanding of how the element scavenges onto particles. Here, we estimate apparent rate constants of Th adsorption (k1), Th desorption (k-1), bulk particle degradation (β-1), and bulk particle sinking speed (w) along the water column at 11 open-ocean stations occupied during the GEOTRACES North Atlantic Section (GA03). First, we provide evidence that the budgets of Th isotopes and particles at these stations appear to be generally dominated by radioactive production and decay sorption reactions, particle degradation, and particle sinking. Rate parameters are then estimated by fitting a Th and particle cycling model to data of dissolved and particulate 228,230,234Th, 228Ra, particle concentrations, and 234,238U estimates based on salinity, using a nonlinear programming technique. We find that the adsorption rate constant (k1) generally decreases with depth across the section: broadly, the time scale 1 /k1 averages 1.0 yr in the upper 1000 m and (1.4-1.5) yr below. A positive relationship between k1 and particle concentration (P) is found, i.e., k1 ∝Pb , where b ≥ 1 , consistent with the notion that k1 increases with the number of surface sites available for adsorption. The rate constant ratio, K =k1 / (k-1 +β-1) , which measures the collective influence of rate parameters on Th scavenging, averages 0.2 for most stations and most depths. We clarify the conditions under which K / P is equivalent to the distribution coefficient, KD, test that the conditions are met at the stations, and find that K / P decreases with P, in line with a particle concentration effect (dKD / dP < 0). In contrast to the influence of colloids as envisioned by the Brownian pumping hypothesis, we provide evidence that the particle concentration effect arises from the joint effect of P on the rate constants for thorium attachment to, and detachment from, particles.

Fabrication of graphene/Fe3O4@polythiophene nanocomposite and its application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples.

PubMed

Mehdinia, Ali; Khodaee, Nader; Jabbari, Ali

2015-04-08

Polythiophene (PT) was used as a surface modifier of graphene/Fe3O4 (G/Fe3O4) composite to increase merit of it, and also overcome some limitations and disadvantages of using G/Fe3O4 alone as solid phase extraction (SPE) sorbent. An in-situ chemical polymerization method was employed to prepare G/Fe3O4@PT nanocomposites. Application of this newly designed material in the magnetic SPE (MSPE) of polycyclic aromatic hydrocarbons (PAHs), as model analytes, in the environmental water samples was investigated. The characterization of the hybrid material was performed using transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray analysis, Fourier transform-infrared (FT-IR) spectroscopy and vibrating sample magnetometry. Seven important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent, initial sample volume and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 4 min for extraction time, 20 mg for sorbent amount, 100mL for initial sample volume, toluene as desorption solvent, 0.6 mL for desorption solvent volume, 6 min for desorption time and 30% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. Detection limits were in the range of 0.009-0.020 μg L(-1) in the real matrix. The calibration curves were linear over the concentration ranges from 0.03 to 80 μg L(-1) with correlation coefficients (R(2)) between 0.995 and 0.998 for all the analytes. Relative standard deviations were ranged from 4.3 to 6.3%. Appropriate recovery values, in the range of 83-107%, were also obtained for the real sample analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

NASA Technical Reports Server (NTRS)

Getty, Stephanie; Brickerhoff, William; Cornish, Timothy; Ecelberger, Scott; Floyd, Melissa

2012-01-01

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Thin-film microextraction coupled to LC-ESI-MS/MS for determination of quaternary ammonium compounds in water samples.

PubMed

Boyacı, Ezel; Sparham, Chris; Pawliszyn, Janusz

2014-01-01

The dual nature of the quaternary ammonium compounds, having permanently charged hydrophilic quaternary ammonium heads and long-chain hydrophobic tails, makes the sample preparation step and analysis of these compounds challenging. A high-throughput method based on thin-film solid-phase microextraction (SPME) and liquid chromatography mass spectrometry was developed for simultaneous quantitative analysis of nine benzylic and aliphatic quaternary ammonium compounds. Chromatographic separation and detection of analytes were obtained in reverse-phase mode in 8 min using a triple quadrupole mass spectrometer. Hydrophilic lipophilic balance particle-coated blades were found to be the most suitable among the different coatings tested in terms of recoveries and carryover on the blades. For desorption solvents, 70/30, v/v (A/B) with 0.1 % formic acid (where A is 10 mM ammonium acetate in acetonitrile/water (95/5 , v/v) and B is 0.1 %  (v/v) formic acid in isopropyl alcohol) was shown to be the most efficient solvent for the desorption of the analytes from the SPME sorbent. The SPME method was optimised in terms of extraction, pH, and preconditioning, as well as extraction and desorption times. Optimum conditions were 45 min of extraction time and 15 min of desorption time, all with agitation. The extraction was found to be optimum in a range of pH 6.0 to 8.0, which is consistent with the natural pH of water samples. Wide linear dynamic ranges with the developed method were obtained for each compound, enabling the application of the method for a wide range of concentrations. The developed method was validated according to the Food and Drug Administration criteria. The proposed method is the first SPME-based approach describing the applicability of the high-throughput thin-film SPME in a 96-well system for analysis of such challenging compounds.

Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry applied to virus identification

PubMed Central

Calderaro, Adriana; Arcangeletti, Maria-Cristina; Rodighiero, Isabella; Buttrini, Mirko; Gorrini, Chiara; Motta, Federica; Germini, Diego; Medici, Maria-Cristina; Chezzi, Carlo; De Conto, Flora

2014-01-01

Virus detection and/or identification traditionally rely on methods based on cell culture, electron microscopy and antigen or nucleic acid detection. These techniques are good, but often expensive and/or time-consuming; furthermore, they not always lead to virus identification at the species and/or type level. In this study, Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) was tested as an innovative tool to identify human polioviruses and to identify specific viral protein biomarkers in infected cells. The results revealed MALDI-TOF MS to be an effective and inexpensive tool for the identification of the three poliovirus serotypes. The method was firstly applied to Sabin reference strains, and then to isolates from different clinical samples, highlighting its value as a time-saving, sensitive and specific technique when compared to the gold standard neutralization assay and casting new light on its possible application to virus detection and/or identification. PMID:25354905

Desorption in Mass Spectrometry.

PubMed

Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

2017-01-01

In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e. , ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed.

Water desorption from a confined biopolymer.

PubMed

Pradipkanti, L; Satapathy, Dillip K

2018-03-14

We study desorption of water from a confined biopolymer (chitosan thin films) by employing temperature dependent specular X-ray reflectivity and spectroscopic ellipsometry. The water desorption is found to occur via three distinct stages with significantly different desorption rates. The distinct rates of water desorption are attributed to the presence of different kinds of water with disparate mobilities inside the biopolymer film. We identify two characteristic temperatures (T c1 and T c2 ) at which the water desorption rate changes abruptly. Interestingly, the characteristic temperatures decrease with decreasing the film thickness. The thickness dependence of the characteristic temperature is interpreted in the context of a higher mobility of polymer chains at the free surface for polymers under one-dimensional confinement.

Time-resolved chromatographic analysis and mechanisms in adsorption and catalysis.

PubMed

Roubani-Kalantzopoulou, Fani

2009-03-06

The main object of this review is the study of fundamentals of adsorption and heterogeneous catalysis, a benefit for the understanding of adsorptive and catalytic properties. This work aims to define and record, with the utmost accuracy, the phenomena and the possible reactions. A new methodology for the study of the adsorption is presented, which is a version of the well-known inverse gas chromatography. This reversed-flow inverse gas chromatography (RF-IGC) is technically very simple, and it is combined with a mathematical analysis that gives the possibility for the estimation of various physicochemical parameters related to adsorbent or catalyst characterization, under conditions compatible with the operation of real adsorbents and catalysts. On this base, this methodology has been successfully applied to the study of the impact of air pollutants, volatile organic and/or inorganic, on many solids such as marbles, ceramics, oxide-pigments of works of art, building materials, authentic statues of the Greek Archaeological Museums. Moreover, this methodology proved to be a powerful tool for studying the topography of active sites of heterogeneous surfaces in the nano-scale domain. Thus, some very important local quantities for the surface chemistry have been determined experimentally for many solids including thin films. These physicochemical local quantities (among which adsorption energy and entropy, surface diffusion coefficient, probability density function) have been determined from the experimental pairs of height of extra chromatographic peaks and time by a nonlinear least-squares method, through personal computer programs written in GW BASIC and lately in FORTRAN. Through the time-resolved analysis the surface characterization of the examined materials took place. In addition, the kinetic constants responsible for adsorption/desorption and surface chemical reactions have also been calculated. Thus, important answers have been provided to the following essential questions: (1) Can RF-IGC define the gnostic regions of adsorption/desorption, surface diffusion, surface reaction? Yes, irrefutably and undeniably. (2) Can RF-IGC deal with issues of catalysis, the existence of more than one reaction? Certainly yes. Indeed, it is impressive to observe the reactions "on line". (3) Can RF-IGC identify peaks of products and reactants simultaneously? Certainly yes. (4) Can RF-IGC be applied to thin films in a nano-scale domain? The answer is "definitely yes". (5) Can it kinetically follow the above? Yes, again.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption-Desorption Transition.

PubMed

Grebíková, Lucie; Whittington, Stuart G; Vancso, Julius G

2018-05-23

The adsorption-desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption-desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption-desorption transitions.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption–Desorption Transition

PubMed Central

2018-01-01

The adsorption–desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption–desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption–desorption transitions. PMID:29712430

Mathematical modeling of the adsorption/desorption characteristics of anthocyanins from muscadine (Vitis rotundifolia cv. Noble) juice pomace on Amberlite FPX66 resin in a fixed bed column.

PubMed

Uzdevenes, Chad G; Gao, Chi; Sandhu, Amandeep K; Yagiz, Yavuz; Gu, Liwei

2018-03-24

Muscadine grape pomace, a by-product of juicing and wine-making, contains significant amounts of anthocyanin 3,5-diglucosides, known to be beneficial to human health. The objective of this research was to use mathematical modeling to investigate the adsorption/desorption characteristics of these anthocyanins from muscadine grape pomace on Amberlite FPX66 resin in a fixed bed column. Anthocyanins were extracted using hot water and ultrasound, and the extracts were loaded onto a resin column at five bed depths (5, 6, 8, 10 and 12 cm) using three flow rates (4, 6 and 8 mL min -1 ). It was found that adsorption on the column fitted the bed depth service time (BDST) model and the empty bed residence time (EBRT) model. Desorption was achieved by eluting the column using ethanol at four concentrations (25, 40, 55 and 70% v/v) and could be described with an empirical sigmoid model. The breakthrough curves of anthocyanins fitted the BDST model for all three flow rates with R 2 values of 0.983, 0.992 and 0.984 respectively. The EBRT model was successfully employed to find the operating lines, which allow for column scale-up while still achieving similar results to those found in a laboratory operation. Desorption with 40% (v/v) ethanol achieved the highest recovery rate of anthocyanins at 79.6%. The mathematical models established in this study can be used in designing a pilot/industrial- scale column for the separation and concentration of anthocyanins from muscadine juice pomace. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Stir bar sorptive extraction and high performance liquid chromatographic determination of carvedilol in human serum using two different polymeric phases and an ionic liquid as desorption solvent.

PubMed

Talebpour, Zahra; Taraji, Maryam; Adib, Nuoshin

2012-05-04

This article presents a method employing stir bar coated with a film of poly (methyl methacrylate/ethyleneglycol dimethacrylate) (PA-EG) and polydimethylsiloxane (PDMS) in combination with liquid desorption (LD) using ionic liquid, followed by high performance liquid chromatography (HPLC) equipped with ultraviolet (UV) detection for the determination of carvedilol in human serum samples. Stir bar sorptive extraction (SBSE) variables, such as desorption and extraction time and temperature, desorption solvent and pH of the matrix were optimized, in order to achieve suitable analytical sensitivity in a short period of time. Also, the concentration effect of 1-methyl-3-octylimidazolium tetrafluoroborate [Omim][BF4] ionic liquid on the efficiency of LD was investigated. A comparison between PA-EG/SBSE and PDMS/SBSE was made by calculating the experimental recovery and partition coefficient (K), where PA-EG phase demonstrated to be an excellent alternative for the enrichment of the carvedilol from serum samples. The effect of [Omim][BF4] on carryover was studied and no carryover was observed. Under optimized experimental conditions, the analytical performance showed excellent linear dynamic range, with correlation coefficients higher than 0.999 and limits of detection and quantification of 0.3 and 1.0 ng mL(-1), respectively. Intra- and inter-day recovery ranged from 94 to 103% and the coefficients of variations were less than 3.2%. The proposed method was shown to be simple, highly sensitive and suitable for the measurement of trace concentration levels of carvedilol in biological fluid media. Copyright © 2012 Elsevier B.V. All rights reserved.

Staphylococcus aureus-Fibronectin Interactions with and without Fibronectin-Binding Proteins and Their Role in Adhesion and Desorption ▿

PubMed Central

Xu, Chun-Ping; Boks, Niels P.; de Vries, Joop; Kaper, Hans J.; Norde, Willem; Busscher, Henk J.; van der Mei, Henny C.

2008-01-01

Adhesion and residence-time-dependent desorption of two Staphylococcus aureus strains with and without fibronectin (Fn) binding proteins (FnBPs) on Fn-coated glass were compared under flow conditions. To obtain a better understanding of the role of Fn-FnBP binding, the adsorption enthalpies of Fn with staphylococcal cell surfaces were determined using isothermal titration calorimetry (ITC). Interaction forces between staphylococci and Fn coatings were measured using atomic force microscopy (AFM). The strain with FnBPs adhered faster and initially stronger to an Fn coating than the strain without FnBPs, and its Fn adsorption enthalpies were higher. The initial desorption was high for both strains but decreased substantially within 2 s. These time scales of staphylococcal bond ageing were confirmed by AFM adhesion force measurement. After exposure of either Fn coating or staphylococcal cell surfaces to bovine serum albumin (BSA), the adhesion of both strains to Fn coatings was reduced, suggesting that BSA suppresses not only nonspecific but also specific Fn-FnBP interactions. Adhesion forces and adsorption enthalpies were only slightly affected by BSA adsorption. This implies that under the mild contact conditions of convective diffusion in a flow chamber, adsorbed BSA prevents specific interactions but does allow forced Fn-FnBP binding during AFM or stirring in ITC. The bond strength energies calculated from retraction force-distance curves from AFM were orders of magnitude higher than those calculated from desorption data, confirming that a penetrating Fn-coated AFM tip probes multiple adhesins in the outermost cell surface that remain hidden during mild landing of an organism on an Fn-coated substratum, like that during convective diffusional flow. PMID:18952882

Influence of dissolved organic matter and activated carbon pore characteristics on organic micropollutant desorption.

PubMed

Aschermann, Geert; Zietzschmann, Frederik; Jekel, Martin

2018-04-15

By simulating decreasing inflow concentrations, the extent of desorption of organic micropollutants (OMP) from three activated carbons (AC) was examined in laboratory batch tests. The tested AC showed strong differences in pore size distribution and could therefore be characterized as typical micro-, meso- and macroporous AC, respectively. Adsorption and desorption conditions were varied by using drinking water (containing dissolved organic matter (DOM)) and DOM-free pure water as background solutions to examine the influence of DOM on OMP desorption for the different AC. Under ideal conditions (adsorption and desorption in pure water) adsorption of the tested OMP was found to be highly up to completely reversible for all tested AC. Under real conditions (adsorption and desorption in drinking water) additional DOM adsorption affects desorption in different ways depending on the AC pore structure. For the micro- and mesoporous AC, an increased irreversibility of OMP adsorption was found, which shows that DOM adsorption prevents OMP desorption. This could be referred to pore blockage effects that occur during the parallel adsorption of DOM and OMP. For the macroporous AC, DOM adsorption led to an enhanced OMP desorption which could be attributed to displacement processes. These results show that smaller pores tend to be blocked by DOM which hinders OMP from desorption. The overall larger pores of the macroporous AC do not get blocked which could allow (i) OMP to desorb and (ii) DOM to enter and displace OMP. Copyright © 2018 Elsevier Ltd. All rights reserved.

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

Selective concentration of aromatic bases from water with a resin adsorbent

USGS Publications Warehouse

Stuber, H.A.; Leenheer, J.A.

1983-01-01

Aromatic bases are concentrated from water on columns of a resin adsorbent and recovered by aqueous-acid elution. The degree of concentration attainable depends on the ratio of the capacity factor (k) of the neutral form of the amine to that of the ionized form. Capacity factors of ionic forms of amines on XAD-8 resin (a methylacrylic ester polymer) are greater than zero, ranging from 20 to 250 times lower than those of their neutral forms; they increase with increasing hydrophobicity of the amine. Thus, desorption by acid is an edition (k during desorption >0) rather than a displacement (k during desorption = 0) process. The degree of concentration attainable on XAD-8 resin varies with the hydrophobicity of the amine, being limited for hydrophilic solutes (for example, pyridine) by small neutral-form k's, reaching a maximum for amines of intermediate hydrophobicity (for example, quinoline), and decreasing for more hydrophobc solutes (for example, acridine) because of their large ionic-form k's.

Detection of trace ink compounds in erased handwritings using electrospray-assisted laser desorption ionization mass spectrometry.

PubMed

Kao, Yi-Ying; Cheng, Sy-Chyi; Cheng, Chu-Nian; Shiea, Jentaie; Ho, Hsiu-O

2014-06-01

Writings made with erasable pens on paper surfaces can either be rubbed off with an eraser or rendered invisible by changing the temperature of the ink. However, trace ink compounds still remain in the paper fibers even after rubbing or rendering. The detection of these ink compounds from erased handwritings will be helpful in knowing the written history of the paper. In this study, electrospray-assisted laser desorption ionization/mass spectrometry was used to characterize trace ink compounds remaining in visible and invisible ink lines. The ink compounds were desorbed from the paper surface by irradiating the handwritings with a pulsed laser beam; the desorbed analytes were subsequently ionized in an electrospray plume and detected by a quadrupole time-of-flight mass spectrometry mass analyzer. Because of the high spatial resolution of the laser beam, electrospray-assisted laser desorption ionization/mass spectrometry analysis resulted in minimal damage to the sample documents. Copyright © 2014 John Wiley & Sons, Ltd.

Matrix-free mass spectrometric imaging using laser desorption ionisation Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Goodwin, Richard J A; Pitt, Andrew R; Harrison, David; Weidt, Stefan K; Langridge-Smith, Pat R R; Barrett, Michael P; Logan Mackay, C

2011-04-15

Mass spectrometry imaging (MSI) is a powerful tool in metabolomics and proteomics for the spatial localization and identification of pharmaceuticals, metabolites, lipids, peptides and proteins in biological tissues. However, sample preparation remains a crucial variable in obtaining the most accurate distributions. Common washing steps used to remove salts, and solvent-based matrix application, allow analyte spreading to occur. Solvent-free matrix applications can reduce this risk, but increase the possibility of ionisation bias due to matrix adhesion to tissue sections. We report here the use of matrix-free MSI using laser desorption ionisation performed on a 12 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. We used unprocessed tissue with no post-processing following thaw-mounting on matrix-assisted laser desorption ionisation (MALDI) indium-tin oxide (ITO) target plates. The identification and distribution of a range of phospholipids in mouse brain and kidney sections are presented and compared with previously published MALDI time-of-flight (TOF) MSI distributions. Copyright © 2011 John Wiley & Sons, Ltd.

Sorption-desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis.

PubMed

Shirvani, Mehran; Kalbasi, Mahmoud; Shariatmadari, Hosein; Nourbakhsh, Farshid; Najafi, Bijan

2006-12-01

Sorption isotherms have been widely used to assess the heavy metal retention characteristics of soil particles. Desorption behavior of the retained metals, however, usually differ from that of sorption, leading to a lack of coincidence in the experimentally obtained sorption and desorption isotherms. In this study, we examine the nonsingularity of cadmium (Cd) sorption-desorption isotherms, to check the possible hysteresis and reversibility phenomena, in aqueous palygorskite, sepiolite and calcite systems. Sorption of Cd was carried out using a 24-h batch equilibration experiment with eight different Cd solution concentrations, equivalent to 20-100% of maximum sorption capacity of each mineral. Immediately after sorption, desorption took place using successive dilution method with five consecutive desorption steps. Both Cd sorption and desorption data were adequately described by Freundlich equation (0.81

The Release of Trapped Gases from Amorphous Solid Water Films: II. “Bottom-Up” Induced Desorption Pathways

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

May, Robert A.; Smith, R. Scott; Kay, Bruce D.

2013-03-14

In this (Paper II) and the preceding companion paper (Paper I) we investigate the mechanisms for the release of trapped gases from underneath of amorphous solid water (ASW) films. In Paper I, we focused on the low coverage (pressure) regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage (pressure) regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Papermore » I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that abrupt desorption bursts are due to pressure induced structural failure of the ASW overlyaer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores and connected pathways formed during ASW deposition. The extent of desorption and the lineshape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of the ASW is used vary the porosity of overlayer and confirm that the low temperature desorption pathway is due to porosity that is inherent in the ASW overlayer during deposition.« less

Segregation of O2 and CO on the surface of dust grains determines the desorption energy of O2

NASA Astrophysics Data System (ADS)

Noble, J. A.; Diana, S.; Dulieu, F.

2015-12-01

Selective depletion towards pre-stellar cores is still not understood. The exchange between the solid and gas phases is central to this mystery. The aim of this paper is to show that the thermal desorption of O2 and CO from a submonolayer mixture is greatly affected by the composition of the initial surface population. We have performed thermally programmed desorption (TPD) experiments on various submonolayer mixtures of O2 and CO. Pure O2 and CO exhibit almost the same desorption behaviour, but their desorption differs strongly when mixed. Pure O2 is slightly less volatile than CO, while in mixtures, O2 desorbs earlier than CO. We analyse our data using a desorption law linking competition for binding sites with desorption, based on the assumption that the binding energy distribution of both molecules is the same. We apply Fermi-Dirac statistics in order to calculate the adsorption site population distribution, and derive the desorbing fluxes. Despite its simplicity, the model reproduces the observed desorption profiles, indicating that competition for adsorption sites is the reason for lower temperature O2 desorption. CO molecules push-out or `dislodge' O2 molecules from the most favourable binding sites, ultimately forcing their early desorption. It is crucial to consider the surface coverage of dust grains in any description of desorption. Competition for access to binding sites results in some important discrepancies between similar kinds of molecules, such as CO and O2. This is an important phenomenon to be investigated in order to develop a better understanding of the apparently selective depletion observed in dark molecular clouds.

Mercury Sorption and Desorption on Gold: A Comparative Analysis of Surface Acoustic Wave and Quartz Crystal Microbalance-Based Sensors.

PubMed

Kabir, K M Mohibul; Sabri, Ylias M; Esmaielzadeh Kandjani, Ahmad; Matthews, Glenn I; Field, Matthew; Jones, Lathe A; Nafady, Ayman; Ippolito, Samuel J; Bhargava, Suresh K

2015-08-04

Microelectromechanical sensors based on surface acoustic wave (SAW) and quartz crystal microbalance (QCM) transducers possess substantial potential as online elemental mercury (Hg(0)) vapor detectors in industrial stack effluents. In this study, a comparison of SAW- and QCM-based sensors is performed for the detection of low concentrations of Hg(0) vapor (ranging from 24 to 365 ppbv). Experimental measurements and finite element method (FEM) simulations allow the comparison of these sensors with regard to their sensitivity, sorption and desorption characteristics, and response time following Hg(0) vapor exposure at various operating temperatures ranging from 35 to 75 °C. Both of the sensors were fabricated on quartz substrates (ST and AT cut quartz for SAW and QCM devices, respectively) and employed thin gold (Au) layers as the electrodes. The SAW-based sensor exhibited up to ∼111 and ∼39 times higher response magnitudes than did the QCM-based sensor at 35 and 55 °C, respectively, when exposed to Hg(0) vapor concentrations ranging from 24 to 365 ppbv. The Hg(0) sorption and desorption calibration curves of both sensors were found to fit well with the Langmuir extension isotherm at different operating temperatures. Furthermore, the Hg(0) sorption and desorption rate demonstrated by the SAW-based sensor was found to decrease as the operating temperature increased, while the opposite trend was observed for the QCM-based sensor. However, the SAW-based sensor reached the maximum Hg(0) sorption rate faster than the QCM-based sensor regardless of operating temperature, whereas both sensors showed similar response times (t90) at various temperatures. Additionally, the sorption rate data was utilized in this study in order to obtain a faster response time from the sensor upon exposure to Hg(0) vapor. Furthermore, comparative analysis of the developed sensors' selectivity showed that the SAW-based sensor had a higher overall selectivity (90%) than did the QCM counterpart (84%) while Hg(0) vapor was measured in the presence of ammonia (NH3), humidity, and a number of volatile organic compounds at the chosen operating temperature of 55 °C.

Desorption of radioactive cesium by seawater from the suspended particles in river water.

PubMed

Onodera, Masaki; Kirishima, Akira; Nagao, Seiya; Takamiya, Kouichi; Ohtsuki, Tsutomu; Akiyama, Daisuke; Sato, Nobuaki

2017-10-01

In 2011, the accident at the Fukushima-Daiichi nuclear power plant dispersed radioactive cesium throughout the environment, contaminating the land, rivers, and sea. Suspended particles containing clay minerals are the transportation medium for radioactive cesium from rivers to the ocean because cesium is strongly adsorbed between the layers of clay minerals, forming inner sphere complexes. In this study, the adsorption and desorption behaviors of radioactive cesium from suspended clay particles in river water have been investigated. The radioactive cesium adsorption and desorption experiments were performed with two kinds of suspended particulate using a batch method with 137 Cs tracers. In the cesium adsorption treatment performed before the desorption experiments, simulated river water having a total cesium concentration ([ 133+137 Cs + ] total ) of 1.3 nM (10 -9  mol/L) was used. The desorption experiments were mainly conducted at a solid-to-liquid ratio of 0.17 g/L. The desorption agents were natural seawater collected at 10 km north of the Fukushima-Daiichi nuclear power plant, artificial seawater, solutions of NaCl, KCl, NH 4 Cl, and 133 CsCl, and ultrapure water. The desorption behavior, which depends on the preloaded cesium concentration in the suspended particles, was also investigated. Based on the cesium desorption experiments using suspended particles, which contained about 1000 ng/g loaded cesium, the order of cesium desorption ratios for each desorption agent was determined as 1 M NaCl (80%) > 470 mM NaCl (65%) > 1 M KCl (30%) ≈ seawater (natural seawater and Daigo artificial seawater) > 1 M NH 4 Cl (20%) > 1 M 133 CsCl (15%) ≫ ultrapure water (2%). Moreover, an interesting result was obtained: The desorption ratio in the 470 mM NaCl solution was much higher than that in seawater, even though the Na + concentrations were identical. These results indicate that the cesium desorption mechanism is not a simple ion exchange reaction but is strongly related to structural changes in the clay minerals in the suspended particles. Hydrated Na + ions expand the interlayer distance of the clay minerals, resulting in the facile desorption of cesium; in contrast, dehydrated K + ions reduce the interlayer distance and inhibit the desorption of cesium. In conclusion, the desorption of cesium from the suspended particles is controlled by the presence of sodium and potassium ions and the preloaded cesium concentration in the suspended particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sources of Sodium in the Lunar Exosphere: Modeling Using Ground-Based Observations of Sodium Emission and Spacecraft Data of the Plasma

NASA Technical Reports Server (NTRS)

Sarantos, Menelaos; Killen, Rosemary M.; Sharma, A. Surjalal; Slavin, James A.

2009-01-01

Observations of the equatorial lunar sodium emission are examined to quantify the effect of precipitating ions on source rates for the Moon's exospheric volatile species. Using a model of exospheric sodium transport under lunar gravity forces, the measured emission intensity is normalized to a constant lunar phase angle to minimize the effect of different viewing geometries. Daily averages of the solar Lyman alpha flux and ion flux are used as the input variables for photon-stimulated desorption (PSD) and ion sputtering, respectively, while impact vaporization due to the micrometeoritic influx is assumed constant. Additionally, a proxy term proportional to both the Lyman alpha and to the ion flux is introduced to assess the importance of ion-enhanced diffusion and/or chemical sputtering. The combination of particle transport and constrained regression models demonstrates that, assuming sputtering yields that are typical of protons incident on lunar soils, the primary effect of ion impact on the surface of the Moon is not direct sputtering but rather an enhancement of the PSD efficiency. It is inferred that the ion-induced effects must double the PSD efficiency for flux typical of the solar wind at 1 AU. The enhancement in relative efficiency of PSD due to the bombardment of the lunar surface by the plasma sheet ions during passages through the Earth's magnetotail is shown to be approximately two times higher than when it is due to solar wind ions. This leads to the conclusion that the priming of the surface is more efficiently carried out by the energetic plasma sheet ions.

Phosphate removal from aqueous solution using iron oxides: Adsorption, desorption and regeneration characteristics.

PubMed

Ajmal, Zeeshan; Muhmood, Atif; Usman, Muhammad; Kizito, Simon; Lu, Jiaxin; Dong, Renjie; Wu, Shubiao

2018-05-24

Dynamics of phosphate (PO 4 3- ) adsorption, desorption and regeneration characteristics of three lab-synthesized iron oxides, ferrihydrite (F), goethite (G), and magnetite (M) were evaluated in this study. Batch experiments were conducted to evaluate the impact of several adsorption parameters including adsorbent dosage, reaction time, temperature, pH, and ionic strength. The results showed that PO 4 3- adsorption increased with reaction time and temperature while it decreased with an increase in solution pH. Adsorption isotherm data exhibited good agreement with the Freundlich and Langmuir model with maximum monolayer adsorption capacities of 66.6 mg·g -1 (F), 57.8 mg·g -1 (M), and 50.5 mg·g -1 (G). A thermodynamics evaluation produced ΔG < 0, ΔH > 0, and ΔS > 0, demonstrating that PO 4 3- adsorption onto tested minerals is endothermic, spontaneous, and disordered. The PO 4 3- removal mostly occurred via electrostatic attraction between the sorbate and sorbent surfaces. Moreover, the PO 4 3- sorption was reversible and could be desorbed at varying rates in both neutral and alkaline environments. The good desorption capacity has practical benefits for potential regeneration and re-use of the saturated particles in wastewater treatment systems. Copyright © 2018 Elsevier Inc. All rights reserved.

[Determination of carbendazim and thiabendazole in tomatoes by solid-phase microextraction coupled with high performance liquid chromatography and fluorescence detection].

PubMed

Hu, Yanxue; Yang, Xiumin; Wang, Zhi; Wang, Chun; Zhao, Jin

2005-11-01

A novel method for the determination of carbendazim (MBC) and thiabendazole (TBZ) in tomatoes by solid-phase microextraction (SPME) coupled with high performance liquid chromatography (HPLC) and fluorescence detection was developed. The experimental conditions of SPME, including extraction fiber, extraction time, extraction temperature, desorption time, desorption solvent, desorption mode, pH value, organic solvent and ionic strength, and HPLC conditions were optimized. The SPME for MBC and TBZ was performed on a 65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre for 50 min at room temperature with the solution being stirred at 1 100 r/min. The florescence detection was made at 315 nm with excitation wavelength at 280 nm. The method is linear for MBC and TBZ over the range assayed from 0.01 to 1.0 mg/kg tomatoes with the detection limits of 0.003 mg/kg and 0. 001 mg/kg and the correlation coefficients of 0.995 8 and 0.996 7, respectively. The average recoveries for MBC and TBZ were 83.5% and 85.6% with the relative standard deviations (RSDs) of 6.5% and 3.8%, respectively. The method is fast, simple, sensitive, solvent-free and suitable for the determination of MBC and TBZ in tomatoes.

Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

PubMed

Drenkova-Tuhtan, Asya; Mandel, Karl; Paulus, Anja; Meyer, Carsten; Hutter, Frank; Gellermann, Carsten; Sextl, Gerhard; Franzreb, Matthias; Steinmetz, Heidrun

2013-10-01

An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF). Copyright © 2013 Elsevier Ltd. All rights reserved.

Electrospun AOPAN/RC blend nanofiber membrane for efficient removal of heavy metal ions from water.

PubMed

Feng, Quan; Wu, Dingsheng; Zhao, Yong; Wei, Anfang; Wei, Qufu; Fong, Hao

2018-02-15

In this study, an innovative nano-material was prepared, which was ultilized to removal of heavy metal ions from wastewater. Polyacrylonitrile/cellulose acetate (PAN/CA) composite nanofibrous membranes were generated by the electronspinning technique first, and then amidoxime ployarcylonitrile/regenerate cellulose (AOPAN/RC) composite nanofibrous membranes were prepared by combining hydrolysis and amidoximation modification. The modification of composite nanofibers (AOPAN/RC) were consequently used in heavy metal ions adsorption. The characterizations of various different nanofibers were analyzed using scanning electron microscopy, Fourier transform infrared spectroscopy, surface area and pore size distribution analyzer and energy dispersive X-ray spectroscopy. Meantime, the adsorption equilibrium studies were studied. In addition, the saturation adsorption amount of nanofibrous membranes (at 25°C) for Fe(III), Cu(II) and Cd(II) of 7.47, 4.26 and 1.13mmolg -1 , respectively. The effects of pH value of solution, adsorption time and ions concentration on adsorption capacity were also investigated. Furthermore, the composite nanofibrous membranes after five times consecutive adsorption and desorption tests, the desorption rate of the Fe(III), Cu(II) and Cd(II) mental ions maintained more than 80% of their first desorption rate, AOPAN/RC composite nanofibrous reflected excellent resuability. Copyright © 2017 Elsevier B.V. All rights reserved.

Shift in Mass Transfer of Wastewater Contaminants from Microplastics in the Presence of Dissolved Substances.

PubMed

Seidensticker, Sven; Zarfl, Christiane; Cirpka, Olaf A; Fellenberg, Greta; Grathwohl, Peter

2017-11-07

In aqueous environments, hydrophobic organic contaminants are often associated with particles. Besides natural particles, microplastics have raised public concern. The release of pollutants from such particles depends on mass transfer, either in an aqueous boundary layer or by intraparticle diffusion. Which of these mechanisms controls the mass-transfer kinetics depends on partition coefficients, particle size, boundary conditions, and time. We have developed a semianalytical model accounting for both processes and performed batch experiments on the desorption kinetics of typical wastewater pollutants (phenanthrene, tonalide, and benzophenone) at different dissolved-organic-matter concentrations, which change the overall partitioning between microplastics and water. Initially, mass transfer is externally dominated, while finally, intraparticle diffusion controls release kinetics. Under boundary conditions typical for batch experiments (finite bath), desorption accelerates with increasing partition coefficients for intraparticle diffusion, while it becomes independent of partition coefficients if film diffusion prevails. On the contrary, under field conditions (infinite bath), the pollutant release controlled by intraparticle diffusion is not affected by partitioning of the compound while external mass transfer slows down with increasing sorption. Our results clearly demonstrate that sorption/desorption time scales observed in batch experiments may not be transferred to field conditions without an appropriate model accounting for both the mass-transfer mechanisms and the specific boundary conditions at hand.

Gas chromatography with mass spectrometry for the determination of phthalates preconcentrated by microextraction based on an ionic liquid.

PubMed

Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

2017-03-01

A new procedure is proposed for the analysis of migration test solutions obtained from plastic bottles used in the packaging of edible oils. Ultrasound-assisted emulsification microextraction with ionic liquids was applied for the preconcentration of six phthalate esters: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethylhexylphthalate, and di-n-octylphthalate. The enriched ionic liquid was directly analyzed by gas chromatography and mass spectrometry using direct insert microvial thermal desorption. The different factors affecting the microextraction efficiency, such as volume of the extracting phase (30 μL of the ionic liquid) and ultrasound application time (25 s), and the thermal desorption step, such as desorption temperature and time, and gas flow rate, were studied. Under the selected conditions, detection limits for the analytes were in the 0.012-0.18 μg/L range, while recovery assays provided values ranging from 80 to 112%. The use of butyl benzoate as internal standard increased the reproducibility of the analytical procedure. When the release of the six phthalate esters from the tested plastic bottles to liquid simulants was monitored using the optimized procedure, analyte concentrations of between 1.0 and 273 μg/L were detected. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

From conservative to reactive transport under diffusion-controlled conditions

NASA Astrophysics Data System (ADS)

Babey, Tristan; de Dreuzy, Jean-Raynald; Ginn, Timothy R.

2016-05-01

We assess the possibility to use conservative transport information, such as that contained in transit time distributions, breakthrough curves and tracer tests, to predict nonlinear fluid-rock interactions in fracture/matrix or mobile/immobile conditions. Reference simulated data are given by conservative and reactive transport simulations in several diffusive porosity structures differing by their topological organization. Reactions includes nonlinear kinetically controlled dissolution and desorption. Effective Multi-Rate Mass Transfer models (MRMT) are calibrated solely on conservative transport information without pore topology information and provide concentration distributions on which effective reaction rates are estimated. Reference simulated reaction rates and effective reaction rates evaluated by MRMT are compared, as well as characteristic desorption and dissolution times. Although not exactly equal, these indicators remain very close whatever the porous structure, differing at most by 0.6% and 10% for desorption and dissolution. At early times, this close agreement arises from the fine characterization of the diffusive porosity close to the mobile zone that controls fast mobile-diffusive exchanges. At intermediate to late times, concentration gradients are strongly reduced by diffusion, and reactivity can be captured by a very limited number of rates. We conclude that effective models calibrated solely on conservative transport information like MRMT can accurately estimate monocomponent kinetically controlled nonlinear fluid-rock interactions. Their relevance might extend to more advanced biogeochemical reactions because of the good characterization of conservative concentration distributions, even by parsimonious models (e.g., MRMT with 3-5 rates). We propose a methodology to estimate reactive transport from conservative transport in mobile-immobile conditions.

Desorption in Mass Spectrometry

PubMed Central

Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

2017-01-01

In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e., ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed. PMID:28337398

Volatile organic compounds and particulates as components of diesel engine exhaust gas

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

Schulz, H.; Bandeira de Melo, G.; Ousmanov, F.

1999-07-01

Volatile organic compounds (VOC) and soot particles have been determined in a Diesel`s exhaust gas. A new sampling method allowed the measurement of emissions of organic compounds (C{sub 1} to C{sub 20}) in a gas chromatogram at a detection limit of ca. 0.2 mg/m{sup 3}. Particles were collected with a filter bed of ceramic particles and characterized by temperature programmed desorption (TPD) and oxidation (TPO). Engine runs were always performed at a fixed and constant air to fuel equivalence ratio ({lambda}) and with a constant volumetric efficiency, because these parameters strongly influenced the emissions in terms of both composition andmore » order of magnitude. The effective combustion temperature again strongly governed the nature of the emissions. Model fuels, composed of individual paraffins and aromatics and additions of sulfur compounds and an organic nitrate (for cetane number enhancement) were used. The results contribute to the understanding of the origin of specific emissions from Diesel engines. These newly developed methods are recommended for further application.« less

Optimizing the Temporal Resolution of Fast-Scan Cyclic Voltammetry

PubMed Central

2012-01-01

Electrochemical detection with carbon-fiber microelectrodes has become an established method to monitor directly the release of dopamine from neurons and its uptake by the dopamine transporter. With constant potential amperometry (CPA), the measured current provides a real time view of the rapid concentration changes, but the method lacks chemical identification of the monitored species and markedly increases the difficulty of signal calibration. Monitoring with fast-scan cyclic voltammetry (FSCV) allows species identification and concentration measurements but often exhibits a delayed response time due to the time-dependent adsorption/desorption of electroactive species at the electrode. We sought to improve the temporal resolution of FSCV to make it more comparable to CPA by increasing the waveform repetition rate from 10 to 60 Hz with uncoated carbon-fiber electrodes. The faster acquisition led to diminished time delays of the recordings that tracked more closely with CPA measurements. The measurements reveal that FSCV at 10 Hz underestimates the normal rate of dopamine uptake by about 18%. However, FSCV collection at 10 and 60 Hz provide identical results when a dopamine transporter (DAT) blocker such as cocaine is bath applied. To verify further the utility of this method, we used transgenic mice that overexpress DAT. After accounting for the slight adsorption delay time, FSCV at 60 Hz adequately monitored the increased uptake rate that arose from overexpression of DAT and, again, was similar to CPA results. Furthermore, the utility of collecting data at 60 Hz was verified in an anesthetized rat by using a higher scan rate (2400 V/s) to increase sensitivity and the overall signal. PMID:22708011

[Effects of selective cutting disturbance on soil phosphorus adsorption and desorption in a Korean pine and broad-leaved mixed forest in the Xiaoxing'an Mountains, China.

PubMed

Zhang, Xin; Gu, Hui Yan; Chen, Xiang Wei

2018-01-01

This study examined the characteristics of phosphorus (P) adsorption and desorption in surface soil (0-10 cm) of a secondary forest after selective cutting disturbance at three levels of intensity (low, medium, high) in order to reveal the effects of different disturbance intensities on soil P adsorption and desorption. Maximum adsorption amount (Q m ), adsorption intensity factor, maximum buffer capacity, maximum desorption amount, average desorption rate and readily desorptable phosphorus were measured. Q m in the focal forests was 1383.93-1833.34 mg·kg -1 , and Q m in forests with middle and high disturbance intensities was significantly higher than that in forests with low disturbance intensity and in primary forests. P adsorption intensity was 0.024-0.059 L·mg -1 , and forests with high and low disturbance intensities increased the P adsorption intensity significantly. The maximum buffer capacity varied from 35.68 to 97.97 L·kg -1 , with the highest value found in the forest with the highest disturbance intensity. Selective cutting significantly reduced the potential for phosphorus supply in the forest soils. The maximum desorption amount, average desorption rate and readily desorptable phosphorus content in the focal forests were 526.32-797.54 mg·kg -1 , 14.7%-25.5% and 1.79-5.41 mg·kg -1 , respectively, indicating that the ability of soil to release phosphorus significantly decreased with increasing disturbance intensity. Selective cutting changed the phosphorus adsorption and desorption characteristics by reducing the supply and release of soil phosphorus.

Use of experimental design in the investigation of stir bar sorptive extraction followed by ultra-high-performance liquid chromatography-tandem mass spectrometry for the analysis of explosives in water samples.

PubMed

Schramm, Sébastien; Vailhen, Dominique; Bridoux, Maxime Cyril

2016-02-12

A method for the sensitive quantification of trace amounts of organic explosives in water samples was developed by using stir bar sorptive extraction (SBSE) followed by liquid desorption and ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The proposed method was developed and optimized using a statistical design of experiment approach. Use of experimental designs allowed a complete study of 10 factors and 8 analytes including nitro-aromatics, amino-nitro-aromatics and nitric esters. The liquid desorption study was performed using a full factorial experimental design followed by a kinetic study. Four different variables were tested here: the liquid desorption mode (stirring or sonication), the chemical nature of the stir bar (PDMS or PDMS-PEG), the composition of the liquid desorption phase and finally, the volume of solvent used for the liquid desorption. On the other hand, the SBSE extraction study was performed using a Doehlert design. SBSE extraction conditions such as extraction time profiles, sample volume, modifier addition, and acetic acid addition were examined. After optimization of the experimental parameters, sensitivity was improved by a factor 5-30, depending on the compound studied, due to the enrichment factors reached using the SBSE method. Limits of detection were in the ng/L level for all analytes studied. Reproducibility of the extraction with different stir bars was close to the reproducibility of the analytical method (RSD between 4 and 16%). Extractions in various water sample matrices (spring, mineral and underground water) have shown similar enrichment compared to ultrapure water, revealing very low matrix effects. Copyright © 2016 Elsevier B.V. All rights reserved.

Proteome-based bacterial identification using matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS): A revolutionary shift in clinical diagnostic microbiology.

PubMed

Nomura, Fumio

2015-06-01

Rapid and accurate identification of microorganisms, a prerequisite for appropriate patient care and infection control, is a critical function of any clinical microbiology laboratory. Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) is a quick and reliable method for identification of microorganisms, including bacteria, yeast, molds, and mycobacteria. Indeed, there has been a revolutionary shift in clinical diagnostic microbiology. In the present review, the state of the art and advantages of MALDI-TOF MS-based bacterial identification are described. The potential of this innovative technology for use in strain typing and detection of antibiotic resistance is also discussed. This article is part of a Special Issue entitled: Medical Proteomics. Copyright © 2014 Elsevier B.V. All rights reserved.

Rapid determination of trace nitrophenolic organics in water by combining solid-phase extraction with surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Chen, Y C; Shiea, J; Sunner, J

2000-01-01

A rapid technique for the screening of trace compounds in water by combining solid-phase extraction (SPE) with activated carbon surface-assisted laser desorption/ionization (SALDI) time-of-flight mass spectrometry is demonstrated. Activated carbon is used both as the sorbent in SPE and as the solid in the SALDI matrix system. This eliminates the need for an SPE elution process. After the analytes have been adsorbed on the surfaces of the activated carbon during SPE extraction, the activated carbon is directly mixed with the SALDI liquid and mass spectrometric analysis is performed. Trace phenolic compounds in water were used to demonstrate the effectiveness of the method. The detection limit for these compounds is in the ppb to ppt range. Copyright 2000 John Wiley & Sons, Ltd.

Direct detection of the plant pathogens Burkholderia glumae, Burkholderia gladioli pv. gladioli, and Erwinia chrysanthemi pv. zeae in infected rice seedlings using matrix assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Kajiwara, Hideyuki

2016-01-01

The plant pathogens Burkholderia glumae, Burkholderia gladioli pv. gladioli, and Erwinia chrysanthemi pv. zeae were directly detected in extracts from infected rice seedlings by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). This method did not require culturing of the pathogens on artificial medium. In the MALDI-TOF MS analysis, peaks originating from bacteria were found in extracts from infected rice seedlings. The spectral peaks showed significantly high scores, in spite of minor differences in spectra. The spectral peaks originating from host plant tissues did not affect this direct MALDI-TOF MS analysis for the rapid identification of plant pathogens. Copyright © 2015 Elsevier B.V. All rights reserved.

Recognition of Streptococcus pseudoporcinus Colonization in Women as a Consequence of Using Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry for Group B Streptococcus Identification.

PubMed

Suwantarat, Nuntra; Grundy, Maureen; Rubin, Mayer; Harris, Renee; Miller, Jo-Anne; Romagnoli, Mark; Hanlon, Ann; Tekle, Tsigereda; Ellis, Brandon C; Witter, Frank R; Carroll, Karen C

2015-12-01

During a 14-month period of using matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) for group B streptococcus (GBS) identification, we recovered 32 (1%) Streptococcus pseudoporcinus isolates from 3,276 GBS screening cultures from female genital sources (25 isolates from pregnant women and 7 from nonpregnant women). An additional two S. pseudoporcinus isolates were identified from a urine culture and a posthysterectomy wound culture. These isolates were found to cross-react with three different GBS antigen agglutination kits, PathoDx (Remel) (93%), Prolex (Pro-Lab Diagnostics) (38%), and Streptex (Remel) (53%). New approaches to bacterial identification in routine clinical microbiology laboratories may affect the prevalence of S. pseudoporcinus. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Headspace sorptive extraction-gas chromatography-mass spectrometry method to measure volatile emissions from human airway cell cultures.

PubMed

Yamaguchi, Mei S; McCartney, Mitchell M; Linderholm, Angela L; Ebeler, Susan E; Schivo, Michael; Davis, Cristina E

2018-05-12

The human respiratory tract releases volatile metabolites into exhaled breath that can be utilized for noninvasive health diagnostics. To understand the origin of this metabolic process, our group has previously analyzed the headspace above human epithelial cell cultures using solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS). In the present work, we improve our model by employing sorbent-covered magnetic stir bars for headspace sorptive extraction (HSSE). Sorbent-coated stir bar analyte recovery increased by 52 times and captured 97 more compounds than SPME. Our data show that HSSE is preferred over liquid extraction via stir bar sorptive extraction (SBSE), which failed to distinguish volatiles unique to the cell samples compared against media controls. Two different cellular media were also compared, and we found that Opti-MEM® is preferred for volatile analysis. We optimized HSSE analytical parameters such as extraction time (24 h), desorption temperature (300 °C) and desorption time (7 min). Finally, we developed an internal standard for cell culture VOC studies by introducing 842 ng of deuterated decane per 5 mL of cell medium to account for error from extraction, desorption, chromatography and detection. This improved model will serve as a platform for future metabolic cell culture studies to examine changes in epithelial VOCs caused by perturbations such as viral or bacterial infections, opening opportunities for improved, noninvasive pulmonary diagnostics. Copyright © 2018 Elsevier B.V. All rights reserved.

Chitosan/nanohydroxyapatite composite based scallop shells as an efficient adsorbent for mercuric ions: Static and dynamic adsorption studies.

PubMed

Hassan, Asaad F; Hrdina, Radim

2018-04-01

Chitosan/nanohydroxyapatite composites based on scallop shells (CP12, CP14 and CP21) were prepared with different chitosan: nanohydroxyapatite ratios (1:2, 1:4 and 2:1, respectively). Nanohydroxyapatite (P), chitosan(C) and their composites were characterized by means of TGA, XRD, N 2 adsorption/desorption analysis, SEM, Zeta potential and FTIR. The BET surface area ranged between 189 and 512 m 2 /g. Static adsorption of Hg +2 was tested for the effect of adsorbent dosage, pH, time and initial Hg +2 concentrations indicating that maximum static adsorption capacity was confirmed by CP12 (111.6 mg/g). Static adsorption well fitted with Langmuir adsorption isotherm and Pseudo-second order kinetic models. CP12 was selected for dynamic adsorption of Hg +2 considering the effect of bed height, flow rate and the effect of Hg +2 concentrations. Maximum dynamic adsorption capacity was confirmed at bed height of 3 cm, 2.0 mL/min flow rate and 300 mg/L as Hg +2 concentration with breakthrough time (t b ) and exhaustion time (t e ) of 9 and 21 h. Yoon-Nelson and Thomas models best described the experimental Hg +2 breakthrough curve model. After static adsorption, EDTA solution confirmed the maximum desorption efficiency. The validity of CP12 was tested through three cycles of column dynamic adsorption-desorption. Copyright © 2017 Elsevier B.V. All rights reserved.

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

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Carter, Richard J.

The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C).more » The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.« less

Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.

PubMed

Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C

2016-08-01

The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Oxidation of SO2 by NO2 and O3 on carbon - Implications to tropospheric chemistry

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Schryer, D. R.; Rogowski, R. S.

1984-01-01

The oxidation of SO2 to sulfate in air at 65 percent relative humidity on carbon particles was investigated gravimetrically in the presence of NO2 and O3. Approximately 1 mg samples of carbon black were exposed to continuously flowing ppbv mixtures of SO2, SO2 + NO2 and SO2 + O3 for prescribed periods of time before desorption into dry N2. Wet chemical analysis of the particles followed desorption. NO2 and O3 were found to have little, if any, effect relative to air on sulfate yields at the concentrations studied.

Rice husk grafted PMAA by ATRP in aqueous phase and its adsorption for Ce3+

NASA Astrophysics Data System (ADS)

Lin, Chao; Luo, Wenjun; Chen, Jindong; Zhou, Qi

2017-12-01

A monolithic biomass adsorbent, rice husk grafted poly (methyl acrylic acid) (RH-g-PMAA), was successfully synthesized via surface-initiated atom transfer radical polymerization (ATRP) through heterogeneous reactions in aqueous phase. Its adsorption capacity for Ce3+ reaches 122.51 mg g-1, which is about 12 times higher than that of raw rice husk. The experimental result on desorption and reusability shows that the adsorption capacity is still higher than 100 mg g-1 after six cycles and the desorption rate is almost 100% in every cycle. RH-g-PMAA can be separated from water easily because of its integrity.

A Compact Tandem Two-Step Laser Time-of-Flight Mass Spectrometer for In Situ Analysis of Non-Volatile Organics on Planetary Surfaces

NASA Technical Reports Server (NTRS)

Getty, Stephanie A.; Brinckerhoff, William B.; Li, Xiang; Elsila, Jamie; Cornish, Timothy; Ecelberger, Scott; Wu, Qinghao; Zare, Richard

2014-01-01

Two-step laser desorption mass spectrometry is a well suited technique to the analysis of high priority classes of organics, such as polycyclic aromatic hydrocarbons, present in complex samples. The use of decoupled desorption and ionization laser pulses allows for sensitive and selective detection of structurally intact organic species. We have recently demonstrated the implementation of this advancement in laser mass spectrometry in a compact, flight-compatible instrument that could feasibly be the centerpiece of an analytical science payload as part of a future spaceflight mission to a small body or icy moon.

Non-volatile analysis in fruits by laser resonant ionization spectrometry: application to resveratrol (3,5,4'-trihydroxystilbene) in grapes

NASA Astrophysics Data System (ADS)

Montero, C.; Orea, J. M.; Soledad Muñoz, M.; Lobo, R. F. M.; González Ureña, A.

A laser desorption (LD) coupled with resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass spectrometry (TOFMS) technique for non-volatile trace analysis compounds is presented. Essential features are: (a) an enhanced desorption yield due to the mixing of metal powder with the analyte in the sample preparation, (b) a high resolution, great sensitivity and low detection limit due to laser resonant ionisation and mass spectrometry detection. Application to resveratrol content in grapes demonstrated the capability of the analytical method with a sensitivity of 0.2 pg per single laser shot and a detection limit of 5 ppb.

Stability of IRA-45 solid amine resin as a function of carbon dioxide absorption and steam desorption cycling

NASA Technical Reports Server (NTRS)

Wood, Peter C.; Wydeven, Theodore

1987-01-01

The removal of CO2 from the NASA Space Station's cabin atmosphere, which may be undertaken by a solid-amine water (steam)-desorbed system, is presently evaluated with a view to long-term amine resin stability and adsorption/desorption cycling by means of an automated laboratory flow-testing facility. While the CO2-adsorption capacity of the IRA-45 amine resin used gradually decreased over time, the rate of degradation significantly decreased after the first 10 cycles. Attention is given to the presence (and possible need for removal) of trimethylamine in the process air downstream of the resin bed.

Testosterone sorption and desorption: effects of soil particle size.

PubMed

Qi, Yong; Zhang, Tian C; Ren, Yongzheng

2014-08-30

Soils contain a wide range of particles of different diameters with different mobility during rainfall events. Effects of soil particles on sorption and desorption behaviors of steroid hormones have not been investigated. In this study, wet sieve washing and repeated sedimentation methods were used to fractionate the soils into five ranges. The sorption and desorption properties and related mechanisms of testosterone in batch reactors filled with fractionated soil particles were evaluated. Results of sorption and desorption kinetics indicate that small soil particles have higher sorption and lower desorption rates than that of big ones. Thermodynamic results show the sorption processes are spontaneous and exothermal. The sorption capacity ranks as clay>silt>sand, depending mainly on specific surface area and surface functional groups. The urea control test shows that hydrogen bonding contributes to testosterone sorption onto clay and silt but not on sand. Desorption tests indicate sorption is 36-65% irreversible from clay to sand. Clays have highest desorption hysteresis among these five soil fractions, indicating small particles like clays have less potential for desorption. The results provide indirect evidence on the colloid (clay)-facilitated transport of hormones (micro-pollutants) in soil environments. Copyright © 2014 Elsevier B.V. All rights reserved.

Modeling of natural organic matter transport processes in groundwater.

PubMed Central

Yeh, T C; Mas-Pla, J; McCarthy, J F; Williams, T M

1995-01-01

A forced-gradient tracer test was conducted at the Georgetown site to study the transport of natural organic matter (NOM) in groundwater. In particular, the goal of this experiment was to investigate the interactions between NOM and the aquifer matrix. A detailed three-dimensional characterization of the hydrologic conductivity heterogeneity of the site was obtained using slug tests. The transport of a conservative tracer (chloride) was successfully reproduced using these conductivity data. Despite the good simulation of the flow field, NOM breakthrough curves could not be reproduced using a two-site sorption model with spatially constant parameters. Preliminary results suggest that different mechanisms for the adsorption/desorption processes, as well as their spatial variability, may significantly affect the transport and fate of NOM. PMID:7621798

Acoustic emission and sorptive deformation induced in coals of various rank by the sorption-desorption of gas

NASA Astrophysics Data System (ADS)

Majewska, Zofia; Ziętek, Jerzy

2007-09-01

Simultaneous measurements of acoustic emission (AE) and expansion/contraction of coal samples subjected to gas sorption-desorption processes were conducted on high-and medium-rank coal. The aim of this study was to examine the influence of the coal rank and type of sorbate on measured AE and strain characteristics. The experimental equipment employed in this study consisted of a pressure vessel and associated pressurisation and monitoring units. The arrangement of pressure-vacuum valves permitted the coal sample to be pressurised and depressurised. Carbon-dioxide and methane were used as sorbats. Acoustic emission and strains were recorded continuously for a period of 50 hours during sorption and for at least 12 hours during the desorption process. Tests were conducted on cylindrical coal samples at 298 K. The experimental data were presented as plots of AE basic parameters versus time and in strain diagrams. These studies lead to the following conclusions: 1. There are significant differences in AE and strain characteristics for the two systems (coal-CO2 and coal-CH4); 2. There is a direct influence of rank and type of coal on its behaviour during the sorption-desorption of gas. An attempt has been made to interpret the results obtained on the grounds of the copolymer model of coal structure. More research is needed into this topic in order to get a quantitative description of the observed facts.

Hydrogen desorption using honeycomb finned heat exchangers integrated in adsorbent storage systems

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

Corgnale, Claudio; Hardy, Bruce; Chahine, Richard

One of the main technical hurdles associated with adsorbent based hydrogen storage systems is relative to their ability to discharge hydrogen effectively, as dictated by fuel cell requirements. In this study, a new honeycomb finned heat exchanger concept was examined to evaluate its potential as a heat transfer system for hydrogen desorption. A bench scale 0.5 L vessel was equipped with the proposed heat exchanger, filled with MOF-5® adsorbent material. The heating power, required to desorb hydrogen, was provided by a 100 W electric heater placed in the center of the honeycomb structure. Two desorption tests, at room temperature andmore » under cryogenic temperatures, were carried out to evaluate the hydrogen desorption performance of the proposed system under different operating conditions. The bench scale vessel performance was verified from both an experimental and a modeling point of view, demonstrating the ability to desorb about 45% of the adsorbed hydrogen in reduced time and applying low heating power. Further modeling analyses were also carried out showing the potential of the proposed system to reach high hydrogen discharging rates at cryogenic temperature conditions and operating pressures between 100 bar and 5 bar. The proposed adsorption system also demonstrated to be able to discharge all the available hydrogen in less than 500 s operating at cryogenic conditions and with a nominal heating power of 100 W.« less

DART-MS analysis of inorganic explosives using high temperature thermal desorption†‡

PubMed Central

Sisco, Edward; Staymates, Matthew; Gillen, Greg

2018-01-01

An ambient mass spectrometry (MS) platform coupling resistive Joule heating thermal desorption (JHTD) and direct analysis in real time (DART) was implemented for the analysis of inorganic nitrite, nitrate, chlorate, and perchlorate salts. The resistive heating component generated discrete and rapid heating ramps and elevated temperatures, up to approximately 400 °C s−1 and 750 °C, by passing a few amperes of DC current through a nichrome wire. JHTD enhanced the utility and capabilities of traditional DART-MS for the trace detection of previously difficult to detect inorganic compounds. A partial factorial design of experiments (DOE) was implemented for the systematic evaluation of five system parameters. A base set of conditions for JHTD-DART-MS was derived from this evaluation, demonstrating sensitive detection of a range of inorganic oxidizer salts, down to single nanogram levels. DOE also identified JHTD filament current and in-source collision induced dissociation (CID) energy as inducing the greatest effect on system response. Tuning of JHTD current provided a method for controlling the relative degrees of thermal desorption and thermal decomposition. Furthermore, in-source CID provided manipulation of adduct and cluster fragmentation, optimizing the detection of molecular anion species. Finally, the differential thermal desorption nature of the JHTD-DART platform demonstrated efficient desorption and detection of organic and inorganic explosive mixtures, with each desorbing at its respective optimal temperature. PMID:29651308

Hydrogen desorption using honeycomb finned heat exchangers integrated in adsorbent storage systems

DOE PAGES

Corgnale, Claudio; Hardy, Bruce; Chahine, Richard; ...

2018-03-01

One of the main technical hurdles associated with adsorbent based hydrogen storage systems is relative to their ability to discharge hydrogen effectively, as dictated by fuel cell requirements. In this study, a new honeycomb finned heat exchanger concept was examined to evaluate its potential as a heat transfer system for hydrogen desorption. A bench scale 0.5 L vessel was equipped with the proposed heat exchanger, filled with MOF-5® adsorbent material. The heating power, required to desorb hydrogen, was provided by a 100 W electric heater placed in the center of the honeycomb structure. Two desorption tests, at room temperature andmore » under cryogenic temperatures, were carried out to evaluate the hydrogen desorption performance of the proposed system under different operating conditions. The bench scale vessel performance was verified from both an experimental and a modeling point of view, demonstrating the ability to desorb about 45% of the adsorbed hydrogen in reduced time and applying low heating power. Further modeling analyses were also carried out showing the potential of the proposed system to reach high hydrogen discharging rates at cryogenic temperature conditions and operating pressures between 100 bar and 5 bar. The proposed adsorption system also demonstrated to be able to discharge all the available hydrogen in less than 500 s operating at cryogenic conditions and with a nominal heating power of 100 W.« less

Role of carbon nano-materials in the analysis of biological materials by laser desorption/ionization-mass spectrometry.

PubMed

Najam-ul-Haq, M; Rainer, M; Szabó, Z; Vallant, R; Huck, C W; Bonn, G K

2007-03-10

At present, carbon nano-materials are being utilized in various procedures, especially in laser desorption/ionization-mass spectrometry (LDI-MS) for analyzing a range of analytes, which include peptides, proteins, metabolites, and polymers. Matrix-oriented LDI-MS techniques are very well established, with weak organic acids as energy-absorbing substances. Carbon materials, such as nano-tubes and fullerenes are being successfully applied in the small-mass range, where routine matrices have strong background signals. In addition, the role of carbon nano-materials is very well established in the fractionation and purification fields. Modified diamond powder and surfaces are utilized in binding peptides and proteins from complex biological fluids and analyzed by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). Polylysine-coated diamond is used for solid-phase extraction to pre-concentrate DNA oligonucleotides. Graphite is useful for desalting, pre-concentration, and as energy-absorbing material (matrix) in desorption/ionization. Carbon nano-tubes in their different derivatized forms are used as matrix materials for the analysis of a range of analytes, such as carbohydrates, amino acids, peptides, proteins, and some environmental samples by LDI-MS. Fullerenes are modified in different ways to bind serum entities analyzed through MALDI/TOF-MS and are subsequently utilized in their identifications. In addition, the fullerenes are a promising matrix in LDI-MS, but improvements are needed.

A food-grade process for isolation and partial purification of bacteriocins of lactic acid bacteria that uses diatomite calcium silicate.

PubMed Central

Coventry, M J; Gordon, J B; Alexander, M; Hickey, M W; Wan, J

1996-01-01

Bacteriocins, including nisin, pediocin PO2, brevicin 286, and piscicolin 126, were extracted from fermentation media by adsorption onto Micro-Cel (a food-grade diatomite calcium silicate anticaking agent) and subsequent desorption. The optimal conditions for desorption of piscicolin 126 were determined and applied to other bacteriocins, and the relative purities of the desorbed preparations were compared. Piscicolin was not successfully desorbed from Micro-Cel at pH 1.0 to 12.0, with organic solvents, or by increase of ionic strength up to 1 M NaCl. However, 25 and 75% of the bacteriocin activity was desorbed by using 1% sodium deoxycholate and 1% sodium dodecyl sulfate (SDS), respectively. Higher levels (up to 100%) of desorption were achieved by repeated elution or by an increase in surfactant concentration. Desorption of piscicolin with 1/10 volume of SDS solution resulted in a preparation with 10 times concentration in activity, equivalent to that of ammonium sulfate preparations (409,600 to 819,200 activity units/ml). Determination of organic nitrogen (N) content revealed that the desorbed piscicolin preparations were substantially free of proteinaceous substances (approximately 92 to 99%) compared with original culture supernatants and ammonium sulfate preparations. Nisin, pediocin, and brevicin were also desorbed with 1% SDS with a similar level of purification. PMID:8633875

Detection and identification of immobilized low-volatility organophosphates by desorption ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Hagan, Nathan A.; Cornish, Timothy J.; Pilato, Robert S.; van Houten, Kelly A.; Antoine, Miquel D.; Lippa, Timothy P.; Becknell, Alan F.; Demirev, Plamen A.

2008-12-01

Two desorption ionization mass spectrometry (MS) techniques - ultraviolet laser desorption/ionization (LDI) and desorption electrospray ionization (DESI) - have been used to detect and identify low-volatility organophosphates when deposited on surfaces or loaded into the pore volume of porous inorganic or polymeric organic powders. The insecticides malathion and dicrotophos were chosen for this study as simulants of low vapor pressure chemical warfare agents which are inherently difficult to detect directly by traditional methods. Both liquid and powdered forms of either insecticide were readily detected by LDI or DESI MS. LDI MS was performed on a miniaturized home-built time-of-flight (TOF) mass spectrometer and a commercial TOF/TOF instrument. For DESI MS, a home-built ion source was interfaced to a commercial quadrupole ion trap. In LDI, intact molecular ion signatures could be acquired by using an appropriate cationizing agent and powder additive in positive ion mode. Tandem MS was used to confirm the identity of each analyte based on the observed characteristic fragmentation pattern. In DESI, less than 100 pg of the liquid insecticides spotted on clean surfaces were detected, while detection limits for the powder-loaded preparations were lower than 1 [mu]g. The effects of sample surface, salt additives, nanoparticle admixtures, and analyte solubility on the LDI and DESI MS sensitivity have been investigated as well.

Modelling of discrete TDS-spectrum of hydrogen desorption

NASA Astrophysics Data System (ADS)

Rodchenkova, Natalia I.; Zaika, Yury V.

2015-12-01

High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

A Technique for Thermal Desorption Analyses Suitable for Thermally-Labile, Volatile Compounds.

PubMed

Alborn, Hans T

2018-02-01

Many plant and insect interactions are governed by odors released by the plants or insects and there exists a continual need for new or improved methods to collect and identify these odors. Our group has for some time studied below-ground, plant-produced volatile signals affecting nematode and insect behavior. The research requires repeated sampling of volatiles of intact plant/soil systems in the laboratory as well as the field with the help of probes to minimize unwanted effects on the systems we are studying. After evaluating solid adsorbent filters with solvent extraction or solid phase micro extraction fiber sample collection, we found dynamic sampling of small air volumes on Tenax TA filters followed by thermal desorption sample introduction to be the most suitable analytical technique for our applications. Here we present the development and evaluation of a low-cost and relatively simple thermal desorption technique where a cold trap cooled with liquid carbon dioxide is added as an integral part of a splitless injector. Temperature gradient-based focusing and low thermal mass minimizes aerosol formation and eliminates the need for flash heating, resulting in low sample degradation comparable to solvent-based on-column injections. Additionally, since the presence of the cold trap does not affect normal splitless injections, on-the-fly switching between splitless and thermal desorption modes can be used for external standard quantification.

The green tea polyphenol (-)-epigallocatechin gallate precipitates salivary proteins including alpha-amylase: biochemical implications for oral health.

PubMed

Hara, Kumiko; Ohara, Masaru; Hayashi, Ikue; Hino, Takamune; Nishimura, Rumi; Iwasaki, Yoriko; Ogawa, Tetsuji; Ohyama, Yoshihiko; Sugiyama, Masaru; Amano, Hideaki

2012-04-01

Green tea is a popular drink throughout the world, and it contains various components, including the green tea polyphenol (-)-epigallocatechin gallate (EGCG). Tea interacts with saliva upon entering the mouth, so the interaction between saliva and EGCG interested us, especially with respect to EGCG-protein binding. SDS-PAGE revealed that several salivary proteins were precipitated after adding EGCG to saliva. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) peptide mass fingerprinting indicated that the major proteins precipitated by EGCG were alpha-amylase, S100, and cystatins. Surface plasmon resonance revealed that EGCG bound to alpha-amylase at dissociation constant (K(d)) = 2.74 × 10(-6) M, suggesting that EGCG interacts with salivary proteins with a relatively strong affinity. In addition, EGCG inhibited the activity of alpha-amylase by non-competitive inhibition, indicating that EGCG is effective at inhibiting the formation of fermentable carbohydrates involved in caries formation. Interestingly, alpha-amylase reduced the antimicrobial activity of EGCG against the periodontal bacterium Aggregatibacter actinomycetemcomitans. Therefore, we considered that EGCG-salivary protein interactions might have both protective and detrimental effects with respect to oral health. © 2012 Eur J Oral Sci.

The construction, fouling and enzymatic cleaning of a textile dye surface.

PubMed

Onaizi, Sagheer A; He, Lizhong; Middelberg, Anton P J

2010-11-01

The enzymatic cleaning of a rubisco protein stain bound onto Surface Plasmon Resonance (SPR) biosensor chips having a dye-bound upper layer is investigated. This novel method allowed, for the first time, a detailed kinetic study of rubisco cleanability (defined as fraction of adsorbed protein removed from a surface) from dyed surfaces (mimicking fabrics) at different enzyme concentrations. Analysis of kinetic data using an established mathematical model able to decouple enzyme transfer and reaction processes [Onaizi, He, Middelberg, Chem. Eng. Sci. 64 (2008) 3868] revealed a striking effect of dyeing on enzymatic cleaning performance. Specifically, the absolute rate constants for enzyme transfer to and from a dye-bound rubisco stain were significantly higher than reported previously for un-dyed surfaces. These increased transfer rates resulted in higher surface cleanability. Higher enzyme mobility (i.e., higher enzyme adsorption and desorption rates) at the liquid-dye interface was observed, consistent with previous suggestions that enzyme surface mobility is likely correlated with overall enzyme cleaning performance. Our results show that reaction engineering models of enzymatic action at surfaces may provide insight able to guide the design of better stain-resistant surfaces, and may also guide efforts to improve cleaning formulations. Copyright 2010 Elsevier Inc. All rights reserved.

Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 1. Temperature effects on activity and selectivity

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

Singh, U.K.; Vannice, M.A.

2000-04-01

Liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) over Pt/SiO{sub 2} catalysts was studied in the temperature and pressure ranges 298--423 K and 7--21 atm, respectively. The reaction kinetics were shown to be free of artifacts arising from transport limitations and poisoning effects. The reaction rate in hexane at the solvent exhibited an activity minimum at 373 K. The initial turnover frequency for citral disappearance over 1.44% Pt/SiO{sub 2} catalyst at 20 atm H{sub 2} pressure decreased from 0.19 s{sup {minus}1} at 298 K to 0.02 s{sup {minus}1} at 373 K, but exhibited normal Arrhenius behavior between 373 and 423 K with anmore » activation energy of 7 kcal/mol. Reaction at 298 K produced substantial deactivation, with the rate decreasing by more than an order of magnitude during the first 4 h of reaction; however, reaction at temperatures greater than 373 K exhibited negligible deactivation and a constant rate up to citral conversions greater than 70%. These unusual temperature effects were modeled using Langmuir-Hinshelwood kinetics invoking dissociative adsorption of hydrogen, competitive adsorption between hydrogen and the organic compounds, and addition of the second hydrogen atom to each reactant as the rate-determining step. Decomposition of the unsaturated alcohol (either geraniol or nerol) was proposed to occur concurrently with the hydrogenation steps to yield adsorbed CO and carbonaceous species which cause the deactivation, but at higher temperatures these species could be removed from the Pt surface by desorption or rapid hydrogenation, respectively. The activity minimum observed in the present study is attributed to the relative rates of the alcohol decomposition reaction and CO desorption, with the decomposition reaction having an activation barrier lower than that for CO desorption.« less

Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

2013-01-01

Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

Chromium and fluoride sorption/desorption on un-amended and waste-amended forest and vineyard soils and pyritic material.

PubMed

Romar-Gasalla, Aurora; Santás-Miguel, Vanesa; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino; Fernández-Sanjurjo, María J

2018-05-22

Using batch-type experiments, chromium (Cr(VI)) and fluoride (F - ) sorption/desorption were studied in forest and vineyard soil samples, pyritic material, pine bark, oak ash, hemp waste and mussel shell, as well as on samples of forest and vineyard soil, and of pyritic material, individually treated with 48 t ha -1 of pine bark, oak ash, and mussel shell. Pine bark showed the highest Cr(VI) sorption (always > 97% of the concentration added) and low desorption (<1.5%). Pyritic material sorbed between 55 and 98%, and desorbed between 0.6 and 9%. Forest and vineyard soils, oak ash, mussel shell and hemp waste showed Cr(VI) sorption always < 32%, and desorption between 22 and 100%. Pine bark also showed the highest F - retention (sorption between 62 and 73%, desorption between 10 and 15%), followed by oak ash (sorption 60-69%, desorption 11-14%), forest soil (sorption 60-73%, desorption 19-36%), and pyritic material (sorption 60-67%, desorption 13-15%), whereas in vineyard sorption was 49-64%, and desorption 24-27%, and in hemp waste sorption was 26-36%, and desorption 41-59%. Sorption data showed better fitting to the Freundlich than to the Langmuir model, especially in the case of Cr(VI), indicating that multilayer sorption dominated. The addition of by-products to the forest and vineyard soils, and to the pyritic material, caused an overall increase in F - sorption, and decreased desorption. Furthermore, the pine bark amendment resulted in increases in Cr(VI) retention by both soils and the pyritic material. These results could be useful to favor the recycling of the by-products studied, aiding in the management of soils and degraded areas affected by Cr(VI) and F - pollution, and in the removal of both anions from polluted waters. Copyright © 2018 Elsevier Ltd. All rights reserved.

Study on Desorption Process of n-Heptane and Methyl Cyclohexane Using UiO-66 with Hierarchical Pores.

PubMed

Chen, Sijia; Zhang, Lin; Zhang, Zhao; Qian, Gang; Liu, Zongjian; Cui, Qun; Wang, Haiyan

2018-06-06

UiO-66 (UiO for University of Oslo), is a zirconium-based MOF with reverse shape selectivity, gives an alternative way to produce high purity n-heptane used for the manufacture of high-purity pharmaceuticals. Couple of studies have shown that UiO-66 gives a high selectivity on the separation of n-/iso-alkanes. However, the microporous structure of UiO-66 causes poor mass transport during the desorption process. In this work, hierarchical-pore UiO-66 (H-UiO-66) was synthesized and utilized as an adsorbent of n-heptane (nHEP) and methyl cyclohexane (MCH) for systematically studying the desorption process of n/iso-alkanes. A suite of physical methods, including XRD patterns verified the UiO-66 structures and HRTEM showed the existence of hierarchical pores. N2 adsorption-desorption isotherms further confirmed the size distribution of hierarchical pores in H-UiO-66. Of particular note, the MCH/nHEP selectivity of H-UiO-66 is similar with UiO-66 in the same adsorption conditions, the desorption process of nHEP/MCH from H-UiO-66 is dramatically enhanced, viz, the desorption rates for nHEP/MCH from H-UiO-66 is enhanced by 30%/23% as comparing to UiO-66 at most. Moreover, desorption activation energy (Ed) derived from temperature-programmed desorption (TPD) experiments indicate that the Ed for nHEP/MCH is lower on H-UiO-66, i.e., the Ed of MCH on H-UiO-66 is ~37% lower than that on UiO-66 at most, leading to a milder condition for the desorption process. The introduction of hierarchical structures will be applicable for the optimization of desorption process during separation on porous materials.

Evaluation of GeO desorption behavior in the metalGeO(2)Ge structure and its improvement of the electrical characteristics.

PubMed

Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

2010-06-15

The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metalGeO(2)Ge capacitors fabricated by thermal oxidation has been investigated. In the metalGeO(2)Ge stack, two processes of GeO desorption at different sites and at different temperatures were observed by thermal desorption spectroscopy measurements. The electrical characteristics of as-oxidized metalGeO(2)Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO(2)Ge interface during oxidation of Ge substrates. On the other hand, the electrical properties were drastically improved by a postmetallization annealing at low temperature resulting in a metal catalyzed GeO desorption from the top interface.

Day-night differences in the composition and sources of carbonaceous aerosol at a polluted regional background site in the Netherlands

NASA Astrophysics Data System (ADS)

Dusek, Ulrike; Broekema, Elise; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro

2017-04-01

The origin of carbonaceous aerosol differs during day- and night-time, because emissions from major sources such as traffic, biomass combustion, and secondary organic aerosol formation show a distinct diurnal pattern. Moreover, photochemical processing and evaporation of semi-volatile organic compounds are enhanced during day-time, due to the availability of sunlight and higher temperatures. Assessing day-night differences in sources and chemical composition can give an indication of the importance of local/regional carbon sources and processing, since day-night differences should be averaged out during long-range transport. If local sources dominate, one could expect a strong diurnal variation in the source profile, but if long-range transport dominates the diurnal variation would be much weaker. In this study we measure the isotopic (14C and 13C) and detailed chemical composition of the organic fraction of the aerosol on high volume PM2.5 filter samples that were collected separately during day and night time. Radiocarbon (14C) measurements are used to estimate three main aerosol sources of organic and elemental carbon (OC and EC): Fossil fuel combustion (ff), biomass combustion (bb), and biogenic sources (bio). The detailed chemical and stable isotopic composition are measured at different desorption temperatures from the filter, which separates the more and less refractory organic compounds. The composition of the organic aerosol is measured using an thermal-desporption Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) method (Holzinger et al, 2010) and the stable isotopic composition is measured using a thermal desorption IRMS method (Dusek et al., 2013). Source apportionment results using 14C show that the contribution of fossil fuel combustion to EC and OC is higher during day-time than during night-time. This is valid for all seasons. During night-time biomass combustion plays a bigger role as a source of carbonaceous aerosol. Even in the summer, when biomass combustion is a small source, its relative contribution increases between 19:00 and 07:00. However, the diurnal changes in source contributions are relatively moderate (e.g., the biomass burning contribution to TC increased from 31% to 43% for the winter sample with the most distinct day-night difference.) This highlights the importance of long-range transport as a source of the carbonaceous aerosol in this region. First results from chemical composition measurements on four of the samples show that the concentration of less refractory organic carbon (desorption temperature up to 200 °C) increases at night-time much more strongly than the concentration of the more refractory carbon. Similarly, the concentration of small organic compounds with m/z < 100 also increases more strongly than heavier compounds. This indicates partitioning of semi-volatile OC as a possible additional night-time source. The chemical composition will be studied in more detail, focusing on diurnal changes in O/C ratios, individual compounds and compound classes, such as hydrocarbons or organic acids. Dusek, U., Meusinger, C., Oyama, B., Ramon, W., de Wilde, P., Holzinger, R., and Röckmann, T.: A thermal desorption system for measuring δ 13 C ratios on organic aerosol, Journal of aerosol science, 66, 72-82, 2013. Holzinger, R., Williams, J., Herrmann, F., Lelieveld, J., Donahue, N., Röckmann, T., 2010. Aerosol analysis using a Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS): a new approach to study processing of organic aerosols. Atmospheric chemistry and physics 10, 2257-2267.

Phase ordering dynamics of reconstituting particles

NASA Astrophysics Data System (ADS)

Albarracín, F. A. Gómez; Rosales, H. D.; Grynberg, M. D.

2017-06-01

We consider the large-time dynamics of one-dimensional processes involving adsorption and desorption of extended hard-core particles (dimers, trimers, ..., k -mers), while interacting through their constituent monomers. Desorption can occur whether or not these latter adsorbed together, which leads to reconstitution of k -mers and the appearance of sectors of motion with nonlocal conservation laws for k ≥3 . Dynamic exponents of the sector including the empty chain are evaluated by finite-size scaling analyses of the relaxation times embodied in the spectral gaps of evolution operators. For attractive interactions it is found that in the low-temperature limit such time scales converge to those of the Glauber dynamics, thus suggesting a diffusive universality class for k ≥2 . This is also tested by simulated quenches down to T =0 , where a common scaling function emerges. By contrast, under repulsive interactions the low-temperature dynamics is characterized by metastable states which decay subdiffusively to a highly degenerate and partially jammed phase.

Ni-catalysed WO3 nanostructures grown by electron beam rapid thermal annealing for NO2 gas sensing

NASA Astrophysics Data System (ADS)

Chandrasekaran, Gopalakrishnan; Sundararaj, Anuraj; Therese, Helen Annal; Jeganathan, K.

2015-07-01

Ni-catalysed WO3 (Ni-WO3) nanowires and nanosheets were grown on Si (100) substrates using electron beam evaporation followed by electron beam-assisted rapid thermal annealing process. Gas-sensing measurements were performed for various concentrations of NO2 in dry air at a temperature range of 50-400 °C. Nanowires and nanosheets show optimum sensor response of 229 and 197 at operating temperatures of 200 and 250 °C, respectively, for 100 ppm of NO2 exposure. Nanowires demonstrated a rapid response time of 66 s, but a slow recovery time of 204 s owing to poor rate of desorption of the adsorbed NO2 gas molecules from the internal porous structure of nanowires. In contrast, the recovery time for nanosheet was 126 s due to higher desorption rate of the adhered NO2 molecules associated with low surface area and less porous structure of nanosheet. The gas-sensing mechanism of WO3 nanostructure is discussed briefly.

Detection of bacteria from biological mixtures using immunomagnetic separation combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

USGS Publications Warehouse

Madonna, A.J.; Basile, F.; Furlong, E.; Voorhees, K.J.

2001-01-01

A rapid method for identifying specific bacteria from complex biological mixtures using immunomagnetic separation coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been developed. The technique employs commercially available magnetic beads coated with polycolonal antibodies raised against specific bacteria and whole cell analysis by MALDI-MS. A suspension of a bacterial mixture is mixed with the immunomagnetic beads specific for the target microorganism. After a short incubation period (20 mins) the bacteria captured by the beads are washed, resuspended in deionized H2O and directly applied onto a MALDI probe. Liquid suspensions containing bacterial mixtures can be screened within 1 h total analysis time. Positive tests result in the production of a fingerprint mass spectrum primarily consisting of protein biomarkers characteristic of the targeted microorganism. Using this procedure, Salmonella choleraesuis was isolated and detected from standard bacterial mixtures and spiked samples of river water, human urine, and chicken blood. Copyright ?? 2001 John Wiley & Sons, Ltd.

Analysis and Quantitation of Glycated Hemoglobin by Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry

NASA Astrophysics Data System (ADS)

Hattan, Stephen J.; Parker, Kenneth C.; Vestal, Marvin L.; Yang, Jane Y.; Herold, David A.; Duncan, Mark W.

2016-03-01

Measurement of glycated hemoglobin is widely used for the diagnosis and monitoring of diabetes mellitus. Matrix assisted laser desorption/ionization (MALDI) time of flight (TOF) mass spectrometry (MS) analysis of patient samples is used to demonstrate a method for quantitation of total glycation on the β-subunit of hemoglobin. The approach is accurate and calibrated with commercially available reference materials. Measurements were linear (R2 > 0.99) across the clinically relevant range of 4% to 20% glycation with coefficients of variation of ≤ 2.5%. Additional and independent measurements of glycation of the α-subunit of hemoglobin are used to validate β-subunit glycation measurements and distinguish hemoglobin variants. Results obtained by MALDI-TOF MS were compared with those obtained in a clinical laboratory using validated HPLC methodology. MALDI-TOF MS sample preparation was minimal and analysis times were rapid making the method an attractive alternative to methodologies currently in practice.

Seasonal and spatial variation of arsenic in groundwater in a rhyolithic volcanic area of Lesvos Island, Greece.

PubMed

Zkeri, Eirini; Aloupi, Maria; Gaganis, Petros

2017-12-23

A survey conducted in water wells located in the rhyolithic volcanic area of Mandamados, Lesvos Island, Greece, indicated that significant seasonal variation of arsenic concentration in groundwater exists mainly in wells near the coastal zone. However, there were differences among those coastal wells with regard to the processes and factors responsible for the observed seasonal variability of the element, although they are all located in a small homogeneous area. These processes and factors include (a) a higher rate of silicate weathering and ion exchange during the dry period followed by the dilution by the recharge water during the wet period, (b) enhanced desorption promoted by higher pH in summer and subsequent dilution of As by rainwater infiltration during the wet period, and (c) reductive dissolution of Mn during the wet period and by desorption under high pH values during the dry period. On the other hand, in wells located in higher-relief regions, the concentration of As in groundwater followed a fairly constant pattern throughout the year, which is probably related to the faster flow of groundwater in this part of the area due to a higher hydraulic gradient. In general, seasonal variation of As in groundwater in the study area was found to be related to geology, recharge rate, topography-distance from coast, and well depth.

Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption.

PubMed

Fukushi, Keisuke; Sakai, Haruka; Itono, Taeko; Tamura, Akihiro; Arai, Shoji

2014-09-16

Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs(+) desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca(2+) and Mg(2+) (>0.5 mM) and high concentrations of K(+). The order of ability for Cs desorption was Na(+) = K(+) > Ca(2+) = Mg(2+) at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs(+) desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments.

Does phenomenological kinetics provide an adequate description of heterogeneous catalytic reactions?

PubMed

Temel, Burcin; Meskine, Hakim; Reuter, Karsten; Scheffler, Matthias; Metiu, Horia

2007-05-28

Phenomenological kinetics (PK) is widely used in the study of the reaction rates in heterogeneous catalysis, and it is an important aid in reactor design. PK makes simplifying assumptions: It neglects the role of fluctuations, assumes that there is no correlation between the locations of the reactants on the surface, and considers the reacting mixture to be an ideal solution. In this article we test to what extent these assumptions damage the theory. In practice the PK rate equations are used by adjusting the rate constants to fit the results of the experiments. However, there are numerous examples where a mechanism fitted the data and was shown later to be erroneous or where two mutually exclusive mechanisms fitted well the same set of data. Because of this, we compare the PK equations to "computer experiments" that use kinetic Monte Carlo (kMC) simulations. Unlike in real experiments, in kMC the structure of the surface, the reaction mechanism, and the rate constants are known. Therefore, any discrepancy between PK and kMC must be attributed to an intrinsic failure of PK. We find that the results obtained by solving the PK equations and those obtained from kMC, while using the same rate constants and the same reactions, do not agree. Moreover, when we vary the rate constants in the PK model to fit the turnover frequencies produced by kMC, we find that the fit is not adequate and that the rate constants that give the best fit are very different from the rate constants used in kMC. The discrepancy between PK and kMC for the model of CO oxidation used here is surprising since the kMC model contains no lateral interactions that would make the coverage of the reactants spatially inhomogeneous. Nevertheless, such inhomogeneities are created by the interplay between the rate of adsorption, of desorption, and of vacancy creation by the chemical reactions.

In situ polymerization synthesis of Z-scheme tungsten trioxide/polyimide photocatalyst with enhanced visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Meng, Pengcheng; Heng, Huimin; Sun, Yanhong; Liu, Xia

2018-01-01

A novel direct Z-scheme P-containing tungsten trioxide/polyimide (PWO/PI) photocatalyst was synthesized by an in-situ solid-state polymerization strategy to enhance the visible-light photocatalytic oxidation capacity of PI. The effects of polymerization temperature and PWO content on the physicochemical properties of PWO/PI composites and photocatalytic degradation efficiency of imidacloprid were investigated. The photocatalysts were characterized by X-ray powder diffraction, Fourier transformed infrared spectra, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, UV-vis diffused reflection spectra and N2 adsorption-desorption isothermals. The results showed that the photocatalysts with visible-light photocatalytic activity can already be prepared at 300 °C. The PWO/PI composites exhibited a lamellar structure and PWO was wrapped by PI. After PWO was introduced, there was a significant interaction between PWO and PI, and the visible light response of photocatalysts was also improved. The visible-light photocatalytic degradation efficiency of imidacloprid on 3% PWO/PI-300 composite was about 3.2 times of commercial P25, and the corresponding pseudo-first-order rate constant was about 2.9 times of pristine PI. The Z-scheme photocatalytic system of PWO/PI composites was confirmed by the electron spin resonance technology, terephthalic acid photoluminescence probing technique, reactive species trapping experiments, X-ray photoelectron spectroscopy and photoluminescence of PWO/PI composites and pristine photocatalysts.

MALDI-TOF mass spectrometry for quantitative gene expression analysis of acid responses in Staphylococcus aureus.

PubMed

Rode, Tone Mari; Berget, Ingunn; Langsrud, Solveig; Møretrø, Trond; Holck, Askild

2009-07-01

Microorganisms are constantly exposed to new and altered growth conditions, and respond by changing gene expression patterns. Several methods for studying gene expression exist. During the last decade, the analysis of microarrays has been one of the most common approaches applied for large scale gene expression studies. A relatively new method for gene expression analysis is MassARRAY, which combines real competitive-PCR and MALDI-TOF (matrix-assisted laser desorption/ionization time-of-flight) mass spectrometry. In contrast to microarray methods, MassARRAY technology is suitable for analysing a larger number of samples, though for a smaller set of genes. In this study we compare the results from MassARRAY with microarrays on gene expression responses of Staphylococcus aureus exposed to acid stress at pH 4.5. RNA isolated from the same stress experiments was analysed using both the MassARRAY and the microarray methods. The MassARRAY and microarray methods showed good correlation. Both MassARRAY and microarray estimated somewhat lower fold changes compared with quantitative real-time PCR (qRT-PCR). The results confirmed the up-regulation of the urease genes in acidic environments, and also indicated the importance of metal ion regulation. This study shows that the MassARRAY technology is suitable for gene expression analysis in prokaryotes, and has advantages when a set of genes is being analysed for an organism exposed to many different environmental conditions.

Continuous optical measurement system of hemolysis during a photosensitization reaction using absorption spectrum

NASA Astrophysics Data System (ADS)

Hamada, R.; Ogawa, E.; Arai, T.

2018-02-01

To investigate hemolysis phenomena during a photosensitization reaction with the reaction condition continuously and simultaneously for a safety assessment of hemolysis side effect, we constructed an optical system to measure blood sample absorption spectrum during the reaction. Hemolysis degree might be under estimated in general evaluation methods because there is a constant oxygen pressure assumption in spite of oxygen depression take place. By investigating hemoglobin oxidation and oxygen desorption dynamics obtained from the contribution of the visible absorption spectrum and multiple regression analysis, both the hemolysis phenomena and its oxygen environment might be obtained with time. A 664 nm wavelength laser beam for the reaction excitation and 475-650 nm light beam for measuring the absorbance spectrum were arranged perpendicularly crossing. A quartz glass cuvette with 1×10 mm in dimensions for the spectrum measurement was located at this crossing point. A red blood cells suspension medium was arranged with low hematocrit containing 30 μg/ml talaporfin sodium. This medium was irradiated up to 40 J/cm2 . The met-hemoglobin, oxygenatedhemoglobin, and deoxygenated-hemoglobin concentrations were calculated by a multiple regression analysis from the measured spectra. We confirmed the met-hemoglobin concentration increased and oxygen saturation decreased with the irradiation time, which seems to indicate the hemolysis progression and oxygen consumption, respectively. By using our measuring system, the hemolysis progression seems to be obtained with oxygen environment information.

Wax-based sustained release matrix pellets prepared by a novel freeze pelletization technique II. In vitro drug release studies and release mechanisms.

PubMed

Cheboyina, Sreekhar; Wyandt, Christy M

2008-07-09

A novel freeze pelletization technique was evaluated for the preparation of wax-based sustained release matrix pellets. Pellets containing water-soluble drugs were successfully prepared using a variety of waxes. The drug release significantly depended on the wax type used and the aqueous drug solubility. The drug release decreased as the hydrophobicity of wax increased and the drug release increased as the aqueous drug solubility increased. In glyceryl monostearate (GMS) pellets, drug release rate decreased as the loading of theophylline increased. On the contrary, the release rate increased as the drug loading of diltiazem HCl increased in Precirol pellets. Theophylline at low drug loads existed in a dissolved state in GMS pellets and the release followed desorption kinetics. At higher loads, theophylline existed in a crystalline state and the release followed dissolution-controlled constant release for all the waxes studied. However, with the addition of increasing amounts of Brij 76, theophylline release rate increased and the release mechanism shifted to diffusion-controlled square root time kinetics. But the release of diltiazem HCl from Precirol pellets at all drug loads, followed diffusion-controlled square root time kinetics. Therefore, pellets capable of providing a variety of release profiles for different drugs can be prepared using this freeze pelletization technique by suitably modifying the pellet forming matrix compositions.

A new theoretical approach to adsorption desorption behavior of Ga on GaAs surfaces

NASA Astrophysics Data System (ADS)

Kangawa, Y.; Ito, T.; Taguchi, A.; Shiraishi, K.; Ohachi, T.

2001-11-01

We propose a new theoretical approach for studying adsorption-desorption behavior of atoms on semiconductor surfaces. The new theoretical approach based on the ab initio calculations incorporates the free energy of gas phase; therefore we can calculate how adsorption and desorption depends on growth temperature and beam equivalent pressure (BEP). The versatility of the new theoretical approach was confirmed by the calculation of Ga adsorption-desorption transition temperatures and transition BEPs on the GaAs(0 0 1)-(4×2)β2 Ga-rich surface. This new approach is feasible to predict how adsorption and desorption depend on the growth conditions.

Zero-Headspace Coal-Core Gas Desorption Canister, Revised Desorption Data Analysis Spreadsheets and a Dry Canister Heating System

USGS Publications Warehouse

Barker, Charles E.; Dallegge, Todd A.

2005-01-01

Coal desorption techniques typically use the U.S. Bureau of Mines (USBM) canister-desorption method as described by Diamond and Levine (1981), Close and Erwin (1989), Ryan and Dawson (1993), McLennan and others (1994), Mavor and Nelson (1997) and Diamond and Schatzel (1998). However, the coal desorption canister designs historically used with this method have an inherent flaw that allows a significant gas-filled headspace bubble to remain in the canister that later has to be compensated for by correcting the measured desorbed gas volume with a mathematical headspace volume correction (McLennan and others, 1994; Mavor and Nelson, 1997).