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

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.

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.

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.

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

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.

Photon-Induced Thermal Desorption of CO from Small Metal-Carbonyl Clusters

NASA Astrophysics Data System (ADS)

Lüttgens, G.; Pontius, N.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

2002-02-01

Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)- and Pt2(CO)-5. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)- and Pt2(CO)-5 have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.

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.

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 kinetics of organic chemicals from albumin.

PubMed

Krause, Sophia; Ulrich, Nadin; Goss, Kai-Uwe

2018-03-01

When present in blood, most chemicals tend to bind to the plasma protein albumin. For distribution into surrounding tissues, desorption from albumin is necessary, because only the unbound form of a chemical is assumed to be able to cross cell membranes. For metabolism of chemicals, the liver is a particularly important organ. One potentially limiting step for hepatic uptake of the chemicals is desorption from albumin, because blood passes the human liver within seconds. Desorption kinetics from albumin can thus be an important parameter for our pharmacokinetic and toxicokinetic understanding of chemicals. This work presents a dataset of measured desorption rate constants and reveals a possibility for their prediction. Additionally, the obtained extraction profiles directly indicate physiological relevance of desorption kinetics, because desorption of the test chemicals is still incomplete after time frames comparable to the residence time of blood in the liver.

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.

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.

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.

The impact of soil organic matter and soil sterilisation on the bioaccessibility of 14C-azoxystrobin determined by desorption kinetics.

PubMed

Clegg, Helen; Riding, Matthew J; Oliver, Robin; Jones, Kevin C; Semple, Kirk T

2014-08-15

As soils represent a major sink for most pesticides, factors influencing pesticide degradation are essential in identifying their potential environmental risk. Desorption of (14)C-azoxystrobin was investigated over time in two soils under sterile and non-sterile conditions using exhaustive (solvent) and non-exhaustive (aqueous) methods. Desorption data were fitted to a two-compartment model, differentiating between fast and slow desorbing fractions. With increased ageing, rapid desorption (Frap) (bioaccessibility) decreased with corresponding increases in slowly desorbing fractions (F(slow)). The rapid desorption rate constant (k(fast)) was not affected by ageing, sterility or extraction solvent. The non-exhaustive extractions had similar desorption profiles; whereas exhaustive extractions in aged soils had the highest F(rap). In non-sterile soil, F(rap) was lower resulting in higher F(slow), while desorption rates remained unaffected. Organic matter (OM) reduces F(rap); but not desorption rates. Microorganisms and OM enhanced ageing effects, reducing the fraction of fast desorbing chemicals and potentially the bioaccessibility of pesticides in soil. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

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

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.

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.

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.

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.

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.

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

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

[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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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).

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

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

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

Investigation of ethyl lactate as a green solvent for desorption of total petroleum hydrocarbons (TPH) from contaminated soil.

PubMed

Jalilian Ahmadkalaei, Seyedeh Pegah; Gan, Suyin; Ng, Hoon Kiat; Abdul Talib, Suhaimi

2016-11-01

Treatment of oil-contaminated soil is a major environmental concern worldwide. The aim of this study is to examine the applicability of a green solvent, ethyl lactate (EL), in desorption of diesel aliphatic fraction within total petroleum hydrocarbons (TPH) in contaminated soil and to determine the associated desorption kinetics. Batch desorption experiments were carried out on artificially contaminated soil at different EL solvent percentages (%). In analysing the diesel range of TPH, TPH was divided into three fractions and the effect of solvent extraction on each fraction was examined. The experimental results demonstrated that EL has a high and fast desorbing power. Pseudo-second order rate equation described the experimental desorption kinetics data well with correlation coefficient values, R 2 , between 0.9219 and 0.9999. The effects of EL percentage, initial contamination level of soil and liquid to solid ratio (L/S (v/w)) on initial desorption rate have also been evaluated. The effective desorption performance of ethyl lactate shows its potential as a removal agent for remediation of TPH-contaminated soil worldwide.

Photon-stimulated desorption as a substantial source of sodium in the lunar atmosphere.

PubMed

Yakshinskiy, B V; Madey, T E

1999-08-12

Mercury and the Moon both have tenuous atmospheres that contain atomic sodium and potassium. These chemicals must be continuously resupplied, as neither body can retain the atoms for more than a few hours. The mechanisms proposed to explain the resupply include sputtering of the surface by the solar wind, micrometeorite impacts, thermal desorption and photon-stimulated desorption. But there are few data and no general agreement about which processes dominate. Here we report laboratory studies of photon-stimulated desorption of sodium from surfaces that simulate lunar silicates. We find that bombardment of such surfaces at temperatures of approximately 250 K by ultraviolet photons (wavelength lambda < 300 nm) causes very efficient desorption of sodium atoms, induced by electronic excitations rather than by thermal processes or momentum transfer. The flux at the lunar surface of ultraviolet photons from the Sun is sufficient to ensure that photon-stimulated desorption of sodium contributes substantially to the Moon's atmosphere. On Mercury, solar heating of the surface implies that thermal desorption will also be an important source of atmospheric sodium.

Evaluation of GeO desorption behavior in the metal∕GeO2∕Ge structure and its improvement of the electrical characteristics

PubMed Central

Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

2010-01-01

The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metal∕GeO2∕Ge capacitors fabricated by thermal oxidation has been investigated. In the metal∕GeO2∕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 metal∕GeO2∕Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO2∕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. PMID:20644659

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

Rotary adsorbers for continuous bulk separations

DOEpatents

Baker, Frederick S [Oak Ridge, TN

2011-11-08

A rotary adsorber for continuous bulk separations is disclosed. The rotary adsorber includes an adsorption zone in fluid communication with an influent adsorption fluid stream, and a desorption zone in fluid communication with a desorption fluid stream. The fluid streams may be gas streams or liquid streams. The rotary adsorber includes one or more adsorption blocks including adsorbent structure(s). The adsorbent structure adsorbs the target species that is to be separated from the influent fluid stream. The apparatus includes a rotary wheel for moving each adsorption block through the adsorption zone and the desorption zone. A desorption circuit passes an electrical current through the adsorbent structure in the desorption zone to desorb the species from the adsorbent structure. The adsorbent structure may include porous activated carbon fibers aligned with their longitudinal axis essentially parallel to the flow direction of the desorption fluid stream. The adsorbent structure may be an inherently electrically-conductive honeycomb structure.

Desorption kinetics of {H}/{Mo(211) }

NASA Astrophysics Data System (ADS)

Lopinski, G. P.; Prybyla, J. A.; Estrup, P. J.

1994-08-01

The desorption kinetics of the {H}/{Mo(211) } chemisorption system were studied by thermal desorption and measurement of adsorption isobars. Analysis of the steady-state measurements permits the independent determination of the desorption energy ( Ed) and prefactor ( v). These quantities are found to depend strongly on coverage, with ( Ed) varying continuously from 145 {kJ}/{mol} at low coverage to 65 {kJ}/{mol} near saturation. Three regions of hydrogen adsorption are clearly indicated by the isobars as well as the thermal desorption traces. These regions can be correlated with structural changes observed previously with HREELS and LEED. The coverage dependence of the kinetic parameters is attributed to hydrogen-induced local distortions of the substrate structure. By relating the desorption energy to the isosteric heat the partial molar entropy is also extracted from the data and indicates localized adsorption as well as significant adsorbate-induced changes in the substrate degrees of freedom.

Reduced biodegradability of desorption-resistant fractions of polycyclic aromatic hydrocarbons in soil and aquifer solids

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

White, J.C.; Alexander, M.

1996-11-01

Less of the desorption-resistant fractions of phenanthrene and naphthalene than freshly added phenanthrene and naphthalene was mineralized in columns of aquifer solids, loam, or muck. Slurrying columns of hydrocarbon-amended aquifer solids, loam, or muck enhanced the rate and extent of mineralization of desorption-resistant phenanthrene and naphthalene, but degradation was still less than in slurries amended with fresh compound. A substantial portion of the desorption-resistant compound remained undergraded in the slurry. A surfactant and methanol increased the mineralization of resistant phenanthrene in slurries of loam. A mixed culture of microorganisms enriched on desorption-resistant phenanthrene degraded twice as much of this fractionmore » of compound as a pseudomonad. The authors suggest that predictions of the environment fate of toxic chemicals require information on the biodegradability of the fraction of a compound that is resistant to desorption.« less

The impact of desorption kinetics from albumin on hepatic extraction efficiency and hepatic clearance: a model study.

PubMed

Krause, Sophia; Goss, Kai-Uwe

2018-05-23

Until now, the question whether slow desorption of compounds from transport proteins like the plasma protein albumin can affect hepatic uptake and thereby hepatic metabolism of these compounds has not yet been answered conclusively. This work now combines recently published experimental desorption rate constants with a liver model to address this question. For doing so, the used liver model differentiates the bound compound in blood, the unbound compound in blood and the compound within the hepatocytes as three well-stirred compartments. Our calculations show that slow desorption kinetics from albumin can indeed limit hepatic metabolism of a compound by decreasing hepatic extraction efficiency and hepatic clearance. The extent of this decrease, however, depends not only on the value of the desorption rate constant but also on how much of the compound is bound to albumin in blood and how fast intrinsic metabolism of the compound in the hepatocytes is. For strongly sorbing and sufficiently fast metabolized compounds, our calculations revealed a twentyfold lower hepatic extraction efficiency and hepatic clearance for the slowest known desorption rate constant compared to the case when instantaneous equilibrium between bound and unbound compound is assumed. The same desorption rate constant, however, has nearly no effect on hepatic extraction efficiency and hepatic clearance of weakly sorbing and slowly metabolized compounds. This work examines the relevance of desorption kinetics in various example scenarios and provides the general approach needed to quantify the effect of flow limitation, membrane permeability and desorption kinetics on hepatic metabolism at the same time.

Various causes behind the desorption hysteresis of carboxylic acids on mudstones.

PubMed

Rasamimanana, S; Lefèvre, G; Dagnelie, R V H

2017-02-01

Adsorption desorption is a key factor for leaching, migration and (bio)degradation of organic pollutants in soils and sediments. Desorption hysteresis of apolar organic compounds is known to be correlated with adsorption/diffusion into soil organic matter. This work focuses on the desorption hysteresis of polar organic compounds on a natural mudstone sample. Acetic, citric and ortho-phthalic acids displayed adsorption-desorption hysteresis on Callovo-Oxfordian mudstone. The non-reversible behaviours resulted from three different mechanisms. Adsorption and desorption kinetics were evaluated using 14C- and 3H-labelled tracers and an isotopic exchange method. The solid-liquid distribution ratio of acetate decreased using a NaN 3 bactericide, indicating a rapid bacterial consumption compared with negligible adsorption. The desorption hysteresis of phthalate was apparent and suppressed by the equilibration of renewal pore water with mudstone. This confirms the significant and reversible adsorption of phthalate. Finally, persistent desorption hysteresis was evidenced for citrate. In this case, a third mechanism should be considered, such as the incorporation of citrate in the solid or a chemical perturbation, leading to strong desorption resilience. The results highlighted the different pathways that polar organic pollutants might encounter in a similar environment. Data on phthalic acid is useful to predict the retarded transport of phthalate esters and amines degradation products in sediments. The behaviour of citric acid is representative of polydentate chelating agents used in ore and remediation industries. The impact of irreversible adsorption on solid/solution partitioning and transport deserves further investigation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

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

Guterl, Jerome, E-mail: jguterl@ucsd.edu; Smirnov, R. D.; Krasheninnikov, S. I.

Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samplesmore » exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.« less

USING METHANOL-WATER SYSTEMS TO INVESTIGATE PHENANTHRENE SORPTION-DESORPTION ON SEDIMENT

EPA Science Inventory

Sorption isotherm nonlinearity, sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic matter (NOM) polymers associated with soils and sediments. A conceptualizat...

APPLICATION OF THERMAL DESORPTION TECHNOLOGIES TO HAZARDOUS WASTE SITES

EPA Science Inventory

Thermal desorption is a separation process frequently used to remediate many Superfund sites. Thermal desorption technologies are recommended and used because of (1) the wide range of organic contaminants effectively treated, (2) availability and mobility of commercial systems, ...

Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

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

King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F.

2015-09-15

Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorptionmore » (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and Si–O bonding, they may still exhibit significant chemical reactivity due to the creation of surface dangling bonds resulting from H{sub 2} desorption from previously undetected silicon hydride and surface hydroxide species.« less

Desorption Product Yields Following Cl2 Adsorption on Si(111)7x7: Coverage and Temperature Dependence

DTIC Science & Technology

1991-04-12

only desorption product at approximately 950 K. At higher chloride coverages of 8/6s5 )0.t, a small’ SICl4 TrD signal -’as als:; monitored at 950 K...SiCI2 desorption along with SiCl4 descrption (20). SiCI4 desorbed from a low temperature desorption state at 400 K, whereas SiCI4 and SiCI2 both desorbed...The ratio of the S "l3 an,’ SiC]4 TPD areas suggests that the SiC]3 and SiC]4 TPD signals are both derived froin the desorption of SiCl4 . The growth

In-injection port thermal desorption for explosives trace evidence analysis.

PubMed

Sigman, M E; Ma, C Y

1999-10-01

A gas chromatographic method utilizing thermal desorption of a dry surface wipe for the analysis of explosives trace chemical evidence has been developed and validated using electron capture and negative ion chemical ionization mass spectrometric detection. Thermal desorption was performed within a split/splitless injection port with minimal instrument modification. Surface-abraded Teflon tubing provided the solid support for sample collection and desorption. Performance was characterized by desorption efficiency, reproducibility, linearity of the calibration, and method detection and quantitation limits. Method validation was performed with a series of dinitrotoluenes, trinitrotoluene, two nitroester explosives, and one nitramine explosive. The method was applied to the sampling of a single piece of debris from an explosion containing trinitrotoluene.

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.

Desorption and mobility mechanisms of co-existing polycyclic aromatic hydrocarbons and heavy metals in clays and clay minerals.

PubMed

Saeedi, Mohsen; Li, Loretta Y; Grace, John R

2018-05-15

The effects of soil components such as clay minerals and as humic acids, as well as co-existing metals and polycyclic aromatic hydrocarbons, on desorption and mobility are examined. Three types of artificially blended clay and clay mineral mixtures (pure kaolinite, kaolinite + sand and kaolinite + sand + bentonite), each with different humic acid content, were tested for desorption and mobility of acenaphthene, fluorene and fluoranthene by three extracting solutions CaCl 2 (0.01 M) and EDTA (0.01M) with non-ionic surfactants (Tween 80 and Triton X100). Heavy metals (Ni, Pb and Zn) were also studied for desorption and mobility. The influence of co-present metals on simultaneous desorption and mobility of PAHs was investigated as well. The results showed that <10% of metals in the clay mineral mixtures were mobile. Combined EDTA and non-ionic solutions can enhance the desorption and mobility of PAHs to >80% in clay mineral mixtures containing no sand, while in the same soils containing ∼40% sand, the desorption exceeded 90%. Heavy metals, as well as increasing humic acids content in the clay mineral mixtures, decreased the desorption and mobility of PAHs, especially for soils containing no sand, and for fluoranthene compared with fluorene and acenaphthene. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of Water Invasion on Outburst Predictive Index of Low Rank Coals in Dalong Mine

PubMed Central

Jiang, Jingyu; Cheng, Yuanping; Mou, Junhui; Jin, Kan; Cui, Jie

2015-01-01

To improve the coal permeability and outburst prevention, coal seam water injection and a series of outburst prevention measures were tested in outburst coal mines. These methods have become important technologies used for coal and gas outburst prevention and control by increasing the external moisture of coal or decreasing the stress of coal seam and changing the coal pore structure and gas desorption speed. In addition, techniques have had a significant impact on the gas extraction and outburst prevention indicators of coal seams. Globally, low rank coals reservoirs account for nearly half of hidden coal reserves and the most obvious feature of low rank coal is the high natural moisture content. Moisture will restrain the gas desorption and will affect the gas extraction and accuracy of the outburst prediction of coals. To study the influence of injected water on methane desorption dynamic characteristics and the outburst predictive index of coal, coal samples were collected from the Dalong Mine. The methane adsorption/desorption test was conducted on coal samples under conditions of different injected water contents. Selective analysis assessed the variations of the gas desorption quantities and the outburst prediction index (coal cutting desorption index). Adsorption tests indicated that the Langmuir volume of the Dalong coal sample is ~40.26 m3/t, indicating a strong gas adsorption ability. With the increase of injected water content, the gas desorption amount of the coal samples decreased under the same pressure and temperature. Higher moisture content lowered the accumulation desorption quantity after 120 minutes. The gas desorption volumes and moisture content conformed to a logarithmic relationship. After moisture correction, we obtained the long-flame coal outburst prediction (cutting desorption) index critical value. This value can provide a theoretical basis for outburst prediction and prevention of low rank coal mines and similar occurrence conditions of coal seams. PMID:26161959

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.

Adsorption-desorption mediated separation of low concentrated D2O from water with hydrophobic activated carbon fiber.

PubMed

Ono, Yuji; Futamura, Ryusuke; Hattori, Yoshiyuki; Sakai, Toshio; Kaneko, Katsumi

2017-12-15

The adsorption and desorption of D 2 O on hydrophobic activated carbon fiber (ACF) occurs at a smaller pressure than the adsorption and desorption of H 2 O. The behavior of the critical desorption pressure difference between D 2 O and H 2 O in the pressure range of 1.25-1.80kPa is applied to separate low concentrated D 2 O from water using the hydrophobic ACF, because the desorption branches of D 2 O and H 2 O drop almost vertically. The deuterium concentration of all desorbed water in the above pressure range is lower than that of water without adsorption-treatment on ACF. The single adsorption-desorption procedure on ACF at 1.66kPa corresponding to the maximum difference of adsorption amount between D 2 O and H 2 O reduced the deuterium concentration of desorbed water to 130.6ppm from 143.0ppm. Thus, the adsorption-desorption procedure of water on ACF is a promising separation and concentration method of low concentrated D 2 O from water. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrothermal adsorption and desorption of volatile organic compounds on activated carbon fiber cloth.

PubMed

Son, H K; Sivakumar, S; Rood, M J; Kim, B J

2016-01-15

Adsorption is an effective means to selectively remove volatile organic compounds (VOCs) from industrial gas streams and is particularly of use for gas streams that exhibit highly variable daily concentrations of VOCs. Adsorption of such gas streams by activated carbon fiber cloths (ACFCs) and subsequent controlled desorption can provide gas streams of well-defined concentration that can then be more efficiently treated by biofiltration than streams exhibiting large variability in concentration. In this study, we passed VOC-containing gas through an ACFC vessel for adsorption and then desorption in a concentration-controlled manner via electrothermal heating. Set-point concentrations (40-900 ppm(v)) and superficial gas velocity (6.3-9.9 m/s) were controlled by a data acquisition and control system. The results of the average VOC desorption, desorption factor and VOC in-and-out ratio were calculated and compared for various gas set-point concentrations and superficial gas velocities. Our results reveal that desorption is strongly dependent on the set-point concentration and that the VOC desorption rate can be successfully equalized and controlled via an electrothermal adsorption system. Copyright © 2015 Elsevier B.V. All rights reserved.

Desorption behavior of sorbed flavor compounds from packaging films with ethanol solution.

PubMed

Hwang, Y H; Matsui, T; Hanada, T; Shimoda, M; Matsumoto, K; Osajima, Y

2000-09-01

Desorption behavior of sorbed flavor compounds such as ethyl esters, n-aldehydes, and n-alcohols from LDPE and PET films was investigated in 0 to 100% (v/v) ethanol solutions at 20 degrees C, 50 degrees C, and 60 degrees C. In both films, the desorption apparently increased with increasing ethanol concentration and treatment temperature, depending on the compatibility of the flavor compound with the solvent. Namely, the partition coefficient of ethyl esters, n-aldehydes, and n-alcohols in the LDPE film turned out to be approximately zero at >/=60%, >/=80%, and >/=40% (v/v) ethanol, respectively (for PET film, >/=80%, >/=80%, and >/=40% (v/v) ethanol concentrations were required for complete desorption, respectively). As for physical properties (heat of fusion, melting point, and tensile strength and elongation at break) of LDPE and PET films, there were no significant differences between intact film and the treated film with 60% (v/v) ethanol for 30 min at 60 degrees C. These results suggest that it is possible to apply a desorption solvent such as ethanol solution for desorption of sorbed flavor compounds from packaging films with no physical change in the film properties by this desorption treatment.

Sorption and desorption of indaziflam degradates in several agricultural soils

USDA-ARS?s Scientific Manuscript database

Processes regulating pesticide fate in the environment are influenced by the physicochemical properties of pesticides and soils. Sorption-desorption are important processes as they regulate movement of pesticides in soil. Although sorption-desorption is widely studied for herbicides, studies involvi...

Innovative site remediation technology: Thermal desorption. Volume 6

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

Anderson, W.C.

1993-11-01

The monograph on thermal desorption is one of a series of eight on innovative site and waste remediation technologies that are the culmination of a multiorganization effort involving more than 100 experts over a two-year period. The thermal desorption processes addressed in this monograph use heat, either direct or indirect, ex situ, as the principal means to physically separate and transfer contaminants from soils, sediments, sludges, filter cakes, or other media. Thermal desorption is part of a treatment train; some pre- and postprocessing is necessary.

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

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

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

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

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.

Study of kinetic desorption rate constant in fish muscle and agarose gel model using solid phase microextraction coupled with liquid chromatography with tandem mass spectrometry.

PubMed

Togunde, Oluranti Paul; Oakes, Ken; Servos, Mark; Pawliszyn, Janusz

2012-09-12

This study aims to use solid phase microextraction (SPME), a simple tool to investigate diffusion rate (time) constant of selected pharmaceuticals in gel and fish muscle by comparing desorption rate of diffusion of the drugs in both agarose gel prepared with phosphate-buffered saline (PBS; pH 7.4) and fish muscle. The gel concentration (agarose gel model) that could be used to simulate tissue matrix (fish muscle) for free diffusion of drugs under in vitro and in vivo conditions was determined to model mass transfer phenomena between fibre polymer coating and environmental matrix such that partition coefficients and desorption time constant (diffusion coefficient) can be determined. SPME procedure involves preloading the extraction phase (fibre) with the standards from spiked PBS for 1h via direct extraction. Subsequently, the preloaded fibre is introduced to the sample such fish or agarose gel for specified time ranging from 0.5 to 60 h. Then, fibre is removed at specified time and desorbed in 100 μL of desorption solution (acetonitrile: water 1:1) for 90 min under agitation speed of 1000 rpm. The samples extract were immediately injected to the instrument and analysed using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The limit of detection of the method in gel and fish muscle was 0.01-0.07 ng mL(-1) and 0.07-0.34 ng g(-1), respectively, while the limit quantification was 0.10-0.20 ng mL(-1) in gel samples and 0.40-0.97 ng g(-1) in fish sample. The reproducibility of the method was good (5-15% RSD). The results suggest that kinetics of desorption of the compounds in fish tissue and different viscosity of gel can be determined using desorption time constant. In this study, desorption time constant which is directly related to desorption rate (diffusion kinetics) of selected drugs from the fibre to the gel matrix is faster as the viscosity of the gel matrix reduces from 2% (w/v) to 0.8% (w/v). As the concentration of gel reduces, viscosity of the gel will be reduced therefore allowing faster diffusion which invariably affect desorption time constant. Also, desorption time constant of model drugs in the fish muscle and 0.8-0.9% (w/v) gel model are similar based on free diffusion of studied compounds. In addition, in vitro and in vivo desorption time constant comparison shows that desorption time constant in an in vivo system (live fish muscle) is generally higher than an in vitro system (dead fish muscle) except for sertraline and nordiazepam. This study demonstrates SPME as a simple investigative tool to understand kinetics of desorption in an in vivo system with a goal to measure desorption rate of pharmaceuticals in fish. Copyright © 2011 Elsevier B.V. All rights reserved.

A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

DOE PAGES

Lillard, R. S.; Forsyth, R. T.

2015-03-14

The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared tomore » a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.« less

Efficient and surface site-selective ion desorption by positron annihilation.

PubMed

Tachibana, Takayuki; Yamashita, Takashi; Nagira, Masaru; Yabuki, Hisakuni; Nagashima, Yasuyuki

2018-05-08

We compared positron- and electron-stimulated desorption (e + SD and ESD) of positive ions from a TiO 2 (110) surface. Although desorption of O + ions was observed in both experiments, the desorption efficiency caused by positron bombardment was larger by one order of magnitude than that caused by electron bombardment at an incident energy of 500 eV. e + SD of O + ions remained highly efficient with incident positron energies between 10 eV and 600 eV. The results indicate that e + SD of O + ions is predominantly caused by pair annihilation of surface-trapped positrons with inner-shell electrons. We also tested e + SD from water chemisorbed on the TiO 2 surface and found that the desorption of specific ions was enhanced by positron annihilation, above the ion yield with electron bombardment. This finding corroborates our conclusion that annihilation-site selectivity of positrons results in site-selective ion desorption from a bombarded surface.

Characterization of a multi-metal binding biosorbent: Chemical modification and desorption studies.

PubMed

Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Zhou, John L; Du, Bin; Wei, Qin; Wang, Xiaochang C; Nguyen, Phuoc Dan

2015-10-01

This work attends to preparation and characterization of a novel multi-metal binding biosorbent after chemical modification and desorption studies. Biomass is a combination of tea waste, maple leaves and mandarin peels with a certain proportion to adsorb cadmium, copper, lead and zinc ions from aqueous solutions. The mechanism involved in metal removal was investigated by SEM, SEM/EDS and FTIR. SEM/EDS showed the presence of different chemicals and adsorbed heavy metal ions on the surface of biosorbent. FTIR of both unmodified and modified biosorbents revealed the important role of carboxylate groups in heavy metal biosorption. Desorption using different eluents and 0.1 M HCl showed the best desorption performance. The effectiveness of regeneration step by 1 M CaCl2 on five successive cycles of sorption and desorption displays this multi-metal binding biosorbent (MMBB) can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions in five cycles of sorption/desorption/regeneration. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Wei Chen; Kan, A.T.; Tomson, M.B.

Both the adsorption and the desorption processes play important roles in the transport and fate of organic contaminants in water-sediments and groundwater systems. The adsorption-desorption processes are shown to be influenced by a number of factors, including sediments organic carbon content, contaminant aqueous solubility, aqueous-phase concentration as well as some natural environmental factors such as pH, pE, ionic strength and temperature. External mechanical forces, such as sediment perturbation, and repeated dredging will also have finite effect on the microscopic interparticle forces that control bonds between large and small grain particles. The objective of this research is to study the influencesmore » of various environmental effects on the equilibrium or non-equilibrium desorption behavior of nonpolar organic pollutants in historically contaminated natural sediments of Lake Charles, LA. Differences of desorption behavior between freshly and historically contaminated sediments will be compared in order to evaluated the desorption mechanism. The influences of particle size, mineral composition, organic matter concentration, and aqueous phase matrix composition on desorption behaviour will also be evaluated.« less

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

Chen, W.; Kan, A.T.; Fu, G.

Neutral organic contaminants commonly reside on the solid portion of soils and sediments. The extent of desorption from these solids determines the fate, reactivity, and toxicity. Numerous researchers have observed that, after an initial exposure of a few days, desorption takes place in two phases, namely, an initial rapid release followed by a long-term resistant phase. Resistant desorption has been highly unpredictable. In this research, the adsorption and desorption of chlorobenzenes, hexachlorobutadiene, and naphthalene have been studied using historically and freshly contaminated bayou sediments from Lake Charles, Louisiana, USA. After an initial release period, both laboratory-spiked and historically contaminated sedimentsmore » from Lake Charles, Louisiana, USA. After an initial release period, both laboratory-spiked and historically contaminated sediments exhibit similar desorption profiles. The simulations compare favorably with previous in situ measurements. All desorption results, both laboratory and field, could reasonably be interpreted using a single irreversible isotherm. Consequences of these results in terms of sediment quality criteria (SQC) are also discussed. Finally, an index of fractional irreversible adsorption is proposed and tested.« less

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

Influence of soil properties on heavy metal sequestration by biochar amendment: 2. copper desorption isotherms

USDA-ARS?s Scientific Manuscript database

Contaminant desorption constrains the long-term effectiveness of remediation technologies, and is strongly influenced by dynamic non-equilibrium states of environmental and biological media. Information is currently lacking in the influence of biochar and activated carbon amendments on desorption of...

ON-LINE ANALYSIS OF AQUEOUS AEROSOLS BY LASER DESORPTION IONIZATION. (R823980)

EPA Science Inventory

In this work the effects of water on the laser desorption ionization mass spectra of single aerosol particles are explored. Aqueous aerosols are produced by passing dry particles through a humid environment so that they undergo deliquescent growth. Laser desorption ionization is ...

ATRAZINE DESORPTION KINETICS FROM A FRESH-WATER SEDIMENT

EPA Science Inventory

Research has shown that the sorption and desorption of neutral organic compounds to soils and sediments occurs in two stages, with an initial rapid sorption/desorption phase (usually less than an hour) followed by a slower phase that can last for several months to years for very ...

Retention of Nickel in Soils: Sorption-Desorption and Extended X-ray Absorption Fine Structure Experiments

EPA Science Inventory

Adsorption and desorption of heavy metals in soils are primary factors that influence their bioavailability and mobility in the soil profile. To examine the characteristics of nickel (Ni) adsorption-desorption in soils, kinetic batch experiments were carried out followed by Ni re...

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...

Positron-annihilation-induced ion desorption from TiO2(110)

NASA Astrophysics Data System (ADS)

Tachibana, T.; Hirayama, T.; Nagashima, Y.

2014-05-01

We have investigated the positron-stimulated desorption of ions from a TiO2(110) surface. Desorbed O+ ions were detected in coincidence with the emission of annihilation γ rays. The energy dependence of the ion yields shows that the O+ ions were detected at energies much lower than the previously reported threshold for electron impact desorption corresponding to the excitation energy of Ti(3p) core electrons. These results provide evidence that core-hole creation by positron annihilation with electrons in the core levels leads to ion desorption.

Thermal desorption of metals from tungsten single crystal surfaces

NASA Technical Reports Server (NTRS)

Bauer, E.; Bonczek, F.; Poppa, H.; Todd, G.

1975-01-01

After a short review of experimental methods used to determine desorption energies and frequencies the assumptions underlying the theoretical analysis of experimental data are discussed. Recent experimental results on the flash desorption of Cu, Ag, and Au from clean, well characterized W (110) and (100) surfaces are presented and analyzed in detail with respect to the coverage dependence. The results obtained clearly reveal the limitations of previous analytical methods and of the experimental technique per se (such as structure and phase changes below and in the temperature region in which desorption occurs).

Oxygen desorption from YBa2Cu3O(7-x) and Bi2CaSr2Cu2O(8 + delta) superconductors

NASA Technical Reports Server (NTRS)

Mesarwi, A.; Levenson, L. L.; Ignatiev, A.

1991-01-01

Oxygen desorption experiments from YBa2Cu3O(7-x) (YBCO) and Bi2CaSr2Cu2O(8 + delta) (BSCCO) superconductors were carried out using a quadrupole mass spectrometer for monitoring the desorbing species and X-ray photoemission spectroscopy for surface characterization. Molecular oxygen was found to desorb from both superconductors following photoirradiation with ultraviolet/optical radiation and subsequent heating at over 150 C. Both YBCO and BSCCO were found to have similar oxygen desorption rates and similar activation energies. The desorption data as well as the X-ray photoemission data indicate that the oxygen desorption is not intrinsic to the superconductors but rather due to molecular oxygen entrapped in the material.

Laser desorption of explosives as a way to create an effective non-contact sampling device

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2015-10-01

Comparison of desorption effectiveness of Nd3+:YAG nanosecond laser sources (λ=266, 354, 532 nm) has been carried out to investigate a possibility of creating a non-contact sampling device for detectors of explosives based on principles of ion mobility spectrometry (IMS) and field asymmetric ion mobility spectrometry (FAIMS). The results of mass spectrometric study of laser desorption of nitroamine, nitrate ester and nitroaromatic compounds from a quartz substrate are presented. It is shown that irradiation of adsorbed layers of studied samples by a single pulse of non-resonant laser radiation (λ=532 nm) leads to efficient desorption at laser intensity 107 W/cm2 and above. Excitation of the first singlet state of nitro compounds by resonant radiation (λ=354 nm) provides heating of adsorbed layers and thermal desorption. A strongly non-equilibrium (non-thermal) dissociation process is developed when the second singlet state of nitroaromatic molecules is excited by radiation at λ=266 nm, along with thermal desorption. It is shown that Nd3+: YAG laser with wavelength λ=266 nm, pulse duration 5-10 ns, intensity 107-109 W/cm2 is the most effective source for creation a non-contact sampling device based on desorption of explosives from surfaces.

Effect of Subgrid Heterogeneity on Scaling Geochemical and Biogeochemical Reactions: A Case of U(VI) Desorption

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

Liu, Chongxuan; Shang, Jianying; Shan, Huimei

2014-02-04

The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the US Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relativelymore » homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly over-predicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit at a less degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.« less

Aminocyclopyrachlor sorption-desorption and leaching from three Brazilian soils.

PubMed

Francisco, Jeane G; Mendes, Kassio F; Pimpinato, Rodrigo F; Tornisielo, Valdemar L; Guimarães, Ana C D

2017-07-03

This study aimed to evaluate the sorption-desorption and leaching of aminocyclopyrachlor from three Brazilian soils. The sorption-desorption of 14 C-aminocyclopyrachlor was evaluated using the batch method and leaching was assessed in glass columns. The Freundlich model showed an adequate fit for the sorption-desorption of aminocyclopyrachlor. The Freundlich sorption coefficient [K f (sorption) ] ranged from 0.37 to 1.34 µmol (1-1/n) L 1/n kg -1 and showed a significant positive correlation with the clay content of the soil, while the K f (desorption) ranged from 3.62 to 5.36 µmol (1-1/n) L 1/n kg -1 . The K f (desorption) values were higher than their respective K f (sorption) , indicating that aminocyclopyrachlor sorption is reversible, and the fate of this herbicide in the environment can be affected by leaching. Aminocyclopyrachlor was detected at all depths (0-30 cm) in all the studied soils, where leaching was influenced by soil texture. The total herbicide leaching from the sandy clay and clay soils was <0.06%, whereas, ∼3% leached from the loamy sand soil. The results suggest that aminocyclopyrachlor has a high potential of leaching, based on its low sorption and high desorption capacities. Therefore, this herbicide can easily contaminate underground water resources.

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.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

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

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

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.

Mechanism of and relation between the sorption and desorption of nonylphenol on black carbon-inclusive sediment.

PubMed

Liping, Lou; Guanghuan, Cheng; Jingyou, Deng; Mingyang, Sun; Huanyu, Chen; Qiang, Yang; Xinhua, Xu

2014-07-01

Correlation between the sorption and desorption of nonylphenol (NP) and binary linear regression were conducted to reveal the underlying mechanism of and relation between sorption domains and desorption sites in black carbon (BC)-amended sediment. The sorption and desorption data could be fitted well using dual-mode (R(2) = 0.971-0.996) and modified two-domain model (R(2) = 0.986-0.995), respectively, and there were good correlations between these two parts of parameters (R(2) = 0.884-0.939, P < 0.01). The NP percentage in desorbable fraction was almost equal to that of the partition fraction, suggesting the desorbed NP came from linear partition domain, whereas the resistant desorption NP was segregated in nonlinear adsorption sites, which were dominated by pores in BC-amended sediment. Our investigation refined theory about the relation between sorption domains and desorption sites in sediment and could be used to predict the release risk of NP using sorption data when BC is used for NP pollution control. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of delivery condition on desorption rate of ZrCo metal hydride bed for fusion fuel cycle

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

Kang, H.G.; Yun, S.H.; Chung, D.

2015-03-15

For the safety of fusion fuel cycle, hydrogen isotope gases including tritium are stored as metal hydride form. To satisfy fueling requirement of fusion machine, rapid delivery from metal hydride bed is one of major factors for the development of tritium storage and delivery system. Desorption from metal hydride depends on the operation scenario by pressure and temperature control of the bed. The effect of operation scenario and pump performance on desorption rate of metal hydride bed was experimentally investigated using ZrCo bed. The results showed that the condition of pre-heating scenario before actual delivery of gas affected the deliverymore » performance. Different pumps were connected to desorption line from bed and the effect of pump capacity on desorption rate were also found to be significant. (authors)« less

Laser desorption mass spectrometry for biomolecule detection and its applications

NASA Astrophysics Data System (ADS)

Winston Chen, C. H.; Sammartano, L. J.; Isola, N. R.; Allman, S. L.

2001-08-01

During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications.

A new technique for Auger analysis of surface species subject to electron-induced desorption

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1973-01-01

A method is presented to observe surface species subject to electron-induced desorption by Auger electron spectroscopy. The surface to be examined is moved under the electron beam at constant velocity, establishing a time independent condition and eliminating the time response of the electron spectrometer as a limiting factor. The dependence of the Auger signal on the surface velocity, incident electron current, beam diameter, and desorption cross section are analyzed. The method is illustrated by the Auger analysis of PTFE, in which the fluorine is removed by electron induced desorption.

MOLECULAR DESORPTION OF BAKED STAINLESS STEEL FROM IRRADIATION WITH 9 GeV/NUCLEON Au79+, 10 GeV/NUCLEON Cu29+, AND 23GeV p+ UNDER PERPENDICULAR IMPACT.

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

FISCHER,W.; IRISO, U.; MUSTAFIN, E.

We report on molecular desorption of baked stainless steel from irradiation with high energy ions under perpendicular impact. Ion induced molecular desorption has affected the performance of a number of ion accelerators, in which the beam loss typically occurs under small angles. However, experimental parameters can be easier controlled in measurements with perpendicular impact. Desorption coefficients for small angle impact can be estimated from these measurements. The measurements were carried out at Brookhaven's Relativistic Heavy Ion Collider.

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.

Remediation and desorption kinetics of pyrene from kaolinite co-contaminated with heavy metals at various organic matter contents

NASA Astrophysics Data System (ADS)

Saeedi, Mohsen; Li, Loretta Y.; Grace, John R.

2017-04-01

Soils co-contaminated with polycyclic aromatic hydrocarbons (PAHs) and heavy metals are challenging for remediation. In the present study desorption of pyrene in kaolinite, co-contaminated by Ni, Pb and Zn, was examined by combinations of surfactants and chelating agents such as Triton X-100, Tween 80, Ethylene diamine tetra acetic acid (EDTA) and citric acid. Results showed that a combination of Triton X-100 (7.5 % w/w) + EDTA (0.01 M) and Tween 80 (7.5 % w/w) + EDTA (0.01 M) were effective in simultaneously desorbing both types of contaminants. Batch desorption tests were conducted using single and combined enhancing agents containing Triton X-100 and Tween 80 as non-ionic surfactants, EDTA as a chelating agent, and citric acid as an organic acid. The solution with the highest removal efficiency was the combined solution containing Triton X-100 (7.5 % w/w) + EDTA (0.01M). Triton X-100 (7.5% w/w) + EDTA (0.01M) led to removal efficiencies of 88% for pyrene in base kaolinite. Batch desorption kinetic experiments were performed using Triton X-100 (7.5% w/w) + EDTA (0.01M). During the first 24 h, desorption was rapid. Organic matter content in the kaolinite led to a reduction in the desorption rate of the contaminants. The desorption kinetic data were well fitted by a pseudo-second-order kinetic model.

Effect of short-chain organic acids on the enhanced desorption of phenanthrene by rhamnolipid biosurfactant in soil-water environment.

PubMed

An, Chun-jiang; Huang, Guo-he; Wei, Jia; Yu, Hui

2011-11-01

This study investigated the effect of short-chain organic acids on biosurfactant-enhanced mobilization of phenanthrene in soil-water system. The desorption characteristics of phenanthrene by soils were assessed in the presence of rhamnolipid and four SCOAs, including acetic acid, oxalic acid, tartaric acid and citric acid. The tests with rhamnolipid and different organic acids could attain the higher desorption of phenanthrene compared to those with only rhamnolipid. Among the different combinations, the series with rhamnolipid and citric acid exhibited more significant effect on the desorption performance. The removal of phenanthrene using rhamnolipid and SCOAs gradually increased as the SCOA concentration increased up to a concentration of 300 mmol/L. The effects of pH, soil dissolved organic matter and ionic strength were further evaluated in the presence of both biosurfactant and SCOAs. The results showed that the extent of phenanthrene desorption was more significant at pH 6 and 9. Desorption of phenanthrene was relatively lower in the DOM-removed soils with the addition of biosurfactant and SCOAs. The presence of more salt ions made phenanthrene more persistent on the solid phase and adversely affected its desorption from contaminated soil. The results from this study may have important implications for soil washing technologies used to treat PAH-contaminated soil and groundwater. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

Photoinduced Br Desorption from CsBr Thin Films Grown on Cu(100)

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

Halliday, Matthew T.; Joly, Alan G.; Hess, Wayne P.

2015-10-22

Thin films of CsBr deposited onto metals such as copper are potential photocathode materials for light sources and other applications. We investigate desorption dynamics of Br atoms from CsBr films grown on insulator (KBr, LiF) and metal (Cu) substrates induced by sub-bandgap 6.4 eV laser pulses. The experimental results demonstrate that the peak kinetic energy of Br atoms desorbed from CsBr/Cu films is much lower than that for the hyperthermal desorption from CsBr/LiF films. Kelvin probe measurements indicate negative charge at the surface following Br desorption from CsBr/Cu films. Our ab initio calculations of excitons at CsBr surfaces demonstrate thatmore » this behavior can be explained by an exciton model of desorption including electron trapping at the CsBr surface. Trapped negative charges reduce the energy of surface excitons available for Br desorption. We examine the electron-trapping characteristics of low-coordinated sites at the surface, in particular, divacancies and kink sites. We also provide a model of cation desorption caused by Franck-Hertz excitation of F centers at the surface in the course of irradiation of CsBr/Cu films. These results provide new insights into the mechanisms of photoinduced structural evolution of alkali halide films on metal substrates and activation of metal photocathodes coated with CsBr.« less

Wide-range and accurate modeling of linear alkylbenzene sulfonate (LAS) adsorption/desorption on agricultural soil.

PubMed

Oliver-Rodríguez, B; Zafra-Gómez, A; Reis, M S; Duarte, B P M; Verge, C; de Ferrer, J A; Pérez-Pascual, M; Vílchez, J L

2015-11-01

In this paper, rigorous data and adequate models about linear alkylbenzene sulfonate (LAS) adsorption/desorption on agricultural soil are presented, contributing with a substantial improvement over available adsorption works. The kinetics of the adsorption/desorption phenomenon and the adsorption/desorption equilibrium isotherms were determined through batch studies for total LAS amount and also for each homologue series: C10, C11, C12 and C13. The proposed multiple pseudo-first order kinetic model provides the best fit to the kinetic data, indicating the presence of two adsorption/desorption processes in the general phenomenon. Equilibrium adsorption and desorption data have been properly fitted by a model consisting of a Langmuir plus quadratic term, which provides a good integrated description of the experimental data over a wide range of concentrations. At low concentrations, the Langmuir term explains the adsorption of LAS on soil sites which are highly selective of the n-alkyl groups and cover a very small fraction of the soil surface area, whereas the quadratic term describes adsorption on the much larger part of the soil surface and on LAS retained at moderate to high concentrations. Since adsorption/desorption phenomenon plays a major role in the LAS behavior in soils, relevant conclusions can be drawn from the obtained results. Copyright © 2015 Elsevier Ltd. All rights reserved.

Exploration of biodegradation mechanisms of black carbon-bound nonylphenol in black carbon-amended sediment.

PubMed

Cheng, Guanghuan; Sun, Mingyang; Ge, Xinlei; Xu, Xinhua; Lin, Qi; Lou, Liping

2017-12-01

The present study aimed to investigate biodegradation mechanisms of black carbon (BC)-bound contaminants in BC-amended sediment when BC was applied to control organic pollution. The single-point Tenax desorption technique was applied to track the species changes of nonylphenol (NP) during biodegradation process in the rice straw carbon (RC)-amended sediment. And the correlation between the biodegradation and desorption of NP was analyzed. Results showed that microorganisms firstly degraded the rapid-desorbing NP (6 h Tenax desorption) in RC-amended sediment. The biodegradation facilitated the desorption of slow-desorbing NP, which was subsequently degraded as well (192 h Tenax desorption). Notably, the final amount of NP degradation was greater than that of NP desorption, indicating that absorbed NP by RC amendment can be degraded by microorganisms. Finally, the residual NP amount in RC-amended sediment was decided by RC content and its physicochemical property. Moreover, the presence of the biofilm was observed by the confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) so that microorganisms were able to overcome the mass transfer resistance and directly utilized the absorbed NP. Therefore, single-point Tenax desorption alone may not be an adequate basis for the prediction of the bioaccessibility of contaminants to microorganisms or bioremediation potential in BC-amended sediment. Copyright © 2017. Published by Elsevier Ltd.

Kinetics of tetracycline, oxytetracycline, and chlortetracycline adsorption and desorption on two acid soils.

PubMed

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

2015-01-01

The purpose of this work was to quantify retention/release of tetracycline, oxytetracycline, and chlortetracycline on two soils, paying attention to sorption kinetics and to implications of the adsorption/desorption processes on transfer of these pollutants to the various environmental compartments. We used the stirred flow chamber (SFC) procedure to achieve this goal. All three antibiotics showed high affinity for both soils, with greater adsorption intensity for soil 1, the one with the highest organic matter and Al and Fe oxides contents. Desorption was always <15%, exhibiting strong hysteresis in the adsorption/desorption processes. Adsorption was adequately modeled using a pseudo first-order equation with just one type of adsorption sites, whereas desorption was better adjusted considering both fast and slow sorption sites. The adsorption maximum (qmax) followed the sequence tetracycline > oxytetracycline > chlortetracycline in soil 1, with similar values for the three antibiotics and the sequence tetracycline > chlortetracycline > oxytetracycline in soil 2. The desorption sequences were oxytetracycline > tetracycline > chlortetracycline in soil 1 and oxytetracycline > chlortetracycline > tetracycline in soil 2. In conclusion, the SFC technique has yielded new kinetic data regarding tetracycline, oxytetracycline, and chlortetracycline adsorption/desorption on soils, indicating that it can be used to shed further light on the retention and transport processes affecting antibiotics on soils and other media, thus increasing knowledge on the behavior and evolution of these pharmaceutical residues in the environment.

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.

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2013 CFR

2013-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2012 CFR

2012-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2014 CFR

2014-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2011 CFR

2011-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. All rights reserved.

Sorbed atrazine shifts into non-desorbable sites of soil organic matter during aging.

PubMed

Park, Jeong-Hun; Feng, Yucheng; Cho, Sung Yong; Voice, Thomas C; Boyd, Stephen A

2004-11-01

Soil-chemical contact time (aging) is an important determinant of the sorption and desorption characteristics of the organic contaminants and pesticides in the environment. The effects of aging on mechanism-specific sorption and desorption of atrazine were studied in soil and clay slurries. Sorption isotherm and desorption kinetic experiments were performed, and soil-water distribution coefficients and desorption rate parameters were evaluated using linear and non-linear sorption equations and a three-site desorption model, respectively. Aging time for sorption of atrazine in sterilized soil and clay slurries ranged from 2 days to 8 months. Atrazine sorption isotherms were nearly linear (r(2)>0.97) and sorption coefficients were strongly correlated to soil organic carbon content. Sorption distribution coefficients (K(d)) increased with increase in age in all five soils studied, but not for K-montmorillonite. Sorption non-linearity did not increase with increase in age except for the Houghton muck soil. Desorption profiles were well described by the three-site desorption model. The equilibrium site fraction (f(eq)) decreased and the non-desorbable site fraction (f(nd)) increased as a function of aging time in all soils. For K-montmorillonite, f(nd) approximately 0 regardless of aging, showing that aging phenomena are sorbent/mechanism specific. In all soils, it was found that when normalized to soil organic matter content, the concentration of atrazine in desorbable sites was relatively constant, whereas that in non-desorbable site increased. This, and the lack of aging effects on desorption from montmorillonite, suggests that sorption into non-desorbable sites of soil organic matter is primary source of increased atrazine sorption in soils during aging.

Characteristics and influencing factors of tetrachloroethylene sorption-desorption on soil and its components.

PubMed

Qiu, Zhaofu; Yang, Weiwei; He, Long; Zhao, Zhexuan; Lu, Shuguang; Sui, Qian

2016-02-01

To investigate the effects of soil structure, soil organic carbon (SOC), minerals, initial tetrachloroethylene (PCE) concentration (C0), and ionic strength (Ci) on PCE sorption-desorption, six types of soil were adopted as adsorbents, including two types of natural soil and four types of soil with most of the "soft carbon" pre-treated by H2O2 or with all SOC removed from the original soil by 600 °C ignition. The results showed that all of the sorption-desorption isotherms of PCE were non-linear within the experimental range, and the H2O2-treated samples exhibited higher non-linear sorption isotherms than those of the original soils. The hysteresis index of PCE sorption to original soil is less pronounced than that of the H2O2-treated and 600 °C-heated samples due to the entrapment of sorbate molecules in the "hard carbon" domain, together with the meso- and microporous structures within the 600 °C-heated samples. Both SOC and minerals have impacts on the sorption-desorption of PCE, and the sorption-desorption contribution rate of minerals increased with decreasing SOC content. C0 has almost no influence on the sorption to minerals of the soils, but the contribution rate of minerals decreased with increasing C0 in the desorption stage. As a result of the salting-out effect, PCE sorption capacity was increased by increasing Ci, especially when Ci ≥ 0.1 M. Moreover, desorption increased and hysteresis weakened with increasing Ci, except for the 600 °C-heated samples. In addition, no significant effect of Ci on desorption of PCE and no hysteresis was observed in this experimental range for the 600 °C-heated samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Simultaneous effect of dissolved organic carbon, surfactant, and organic acid on the desorption of pesticides investigated by response surface methodology.

PubMed

Trinh, Ha Thu; Duong, Hanh Thi; Ta, Thao Thi; Van Cao, Hoang; Strobel, Bjarne W; Le, Giang Truong

2017-08-01

Desorption of pesticides (fenobucarb, endosulfan, and dichlorodiphenyltrichloroethane (DDT)) from soil to aqueous solution with the simultaneous presence of dissolved organic carbon (DOC), sodium dodecyl sulfate (SDS), and sodium oxalate (Oxa) was investigated in batch test by applying a full factorial design and the Box-Behnken response surface methodology (RSM). Five concentration levels of DOC (8 to 92 mg L -1 ), SDS (0 to 6.4 critical micelle concentration (CMC)), and Oxa (0 to 0.15 M) were used for the experiments with a rice field topsoil. The results of RSM analysis and analysis of variance (ANOVA) have shown that the experimental data could be well described by quadratic regression equations with determination coefficients (R 2 ) of 0.990, 0.976, and 0.984 for desorption of fenobucarb, endosulfan, and DDT, respectively. The individual effects and interaction of DOC, SDS, and Oxa were evaluated through quadratic regression equations. When the aqueous solution includes 50 mg L -1 DOC, 3.75 CMC SDS, and 0.1 M Oxa, the maximum desorption concentrations of fenobucarb, endosulfan, and DDT were 96, 80, and 75 μg L -1 , respectively. The lowest concentration of SDS, DOC, and Oxa caused the minimum desorption. This point at conditions of concern for flooding water is high content of organic compounds causing potentially high contamination by desorption, and the remarkably lower desorption at organic matter-free conditions. The suspended organic matter is one of the common characteristics of flooding and irrigation water in rice fields, and surfactants from pollution increase the problem with desorption of legacy pesticides in the rice fields.

Reactive Desorption of CO Hydrogenation Products under Cold Pre-stellar Core Conditions

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2018-02-01

The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as ∼10‑8–10‑9 n H, contradicts the generally accepted idea that at 10 K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO–H2CO–CH3OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H2CO and CH3OH. We find that for temperatures in the range of 10 to 14 K, an upper limit of 0.24 ± 0.02 for the overall elemental carbon loss upon CO conversion into CH3OH. This corresponds with an effective reaction desorption fraction of ≤0.07 per hydrogenation step, or ≤0.02 per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed.

Desorption induced by electronic transitions of Na from SiO2: relevance to tenuous planetary atmospheres.

NASA Astrophysics Data System (ADS)

Yakshinskiy, B. V.; Madey, T. E.

2000-04-01

The authors have studied the desorption induced by electronic transitions (DIET) of Na adsorbed on model mineral surfaces, i.e. amorphous, stoichiometric SiO2 films. They find that electron stimulated desorption (ESD) of atomic Na occurs for electron energy thresholds as low as ≡4 eV, that desorption cross-sections are high (≡1×10-19cm2 at 11 eV), and that desorbing atoms are 'hot', with suprathermal velocities. The estimated Na desorption rate from the lunar surface via ESD by solar wind electrons is a small fraction of the rate needed to sustain the Na atmosphere. However, the solar photon flux at energies ≥5 eV exceeds the solar wind electron flux by orders of magnitude; there are sufficient ultraviolet photons incident on the lunar surface to contribute substantially to the lunar Na atmosphere via PSD of Na from the surface.

A new technique for Auger analysis of surface species subject to electron-induced desorption.

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1973-01-01

A method is presented to observe surface species subject to electron-induced desorption by Auger electron spectroscopy. The surface to be examined is moved under the electron beam at constant velocity, establishing a time-independent condition and eliminating the time response of the electron spectrometer as a limiting factor. The dependence of the Auger signal on the sample velocity, incident electron current, beam diameter, and desorption cross section is analyzed. It is shown that it is advantageous to analyze the moving sample with a high beam current, in contrast to the usual practice of using a low beam current to minimize desorption from a stationary sample. The method is illustrated by the analysis of a friction transfer film of PTFE, in which the fluorine is removed by electron-induced desorption. The method is relevant to surface studies in the field of lubrication and catalysis.

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.

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.

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.

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.

Desorption of CO{sub 2} from MDEA and activated MDEA solutions

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

Xu, G.W.; Zhang, C.F.; Qin, S.J.

1995-03-01

A packed column was used for investigating the desorption rate of CO{sub 2} from aqueous methyldiethanolamine (MDEA) and activated MDEA solutions. Experiments were conducted within the temperature range 30--70 C, the concentration of MDEA was 4.28 kmol/m{sup 3}, and the concentration of piperazine (PZ) was 0.10 kmol/m{sup 3} for aqueous activated MDEA solutions. Experimental data confirmed that the kinetics model of absorption CO{sub 2} into aqueous MDEA and activated MDEA solutions can be applicable to the situations in which desorption occurs, and the desorption rate of model predictions agree well with that of experimental determination.

[Thermodynamic analysis of water adsorption and desorption process of Chinese herbal decoction pieces].

PubMed

Cheng, Lin; Luo, Xiao-Jian; Han, Xiu-Lin; Wang, Wen-Kai; Rao, Xiao-Yong; Xu, Shao-Zhong; He, Yan

2016-09-01

Based on the basic theory of thermodynamics, the thermodynamic parameters and related equations in the process of water adsorption and desorption of Chinese herbal decoction pieces were established, and their water absorption and desorption characteristics were analyzed. The physical significance of the thermodynamic parameters, such as differential adsorption enthalpy, differential adsorption entropy, integral adsorption enthalpy, integral adsorption entropy and the free energy of adsorption, were discussed in this paper to provide theoretical basis for the research on the water adsorption and desorption mechanism, optimum drying process parameters, storage conditions and packaging methods of Chinese herbal decoction pieces. Copyright© by the Chinese Pharmaceutical Association.

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.

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.

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.

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.

Regeneration of mesoporous silica aerogel for hydrocarbon adsorption and recovery.

PubMed

Zhang, Chengzhao; Dai, Chong; Zhang, Huaqin; Peng, Shitao; Wei, Xin; Hu, Yandi

2017-09-15

Silica aerogel, with mesoporous structure and high hydrophobicity, is a promising adsorbent for oil spill clean-up. To make it economic and environmental-friendly, hydrocarbon desorption and silica aerogel regeneration were investigated. After hydrocarbon desorption at 80°C, silica aerogel maintained its hydrophobicity. After toluene, petrol, and diesel desorption, shrinkage of mesopores (from 19.9 to 16.8, 13.5, and 13.4nm) of silica aerogels occurred, causing decreased adsorption capacities (from 12.4, 11.2, and 13.6 to 12.0, 6.5, and 2.3g/g). Low surface tension of petrol caused high stress on mesopores during its desorption, resulting in significant pore shrinkage. For diesel, its incomplete desorption and oxidation further hindered the regeneration. Therefore, diesel desorption was also conducted at 200°C. Severe diesel oxidation occurred under aerobic condition and destroyed the mesopores. Under anaerobic condition, no diesel oxidation occurred and the decreases in pore size (to 13.2nm) and adsorption efficiency (to 10.0g/g) of regenerated silica aerogels were much less, compared with under aerobic condition. This study provided new insights on silica aerogel regeneration for oil spill clean-up. Copyright © 2017 Elsevier Ltd. All rights reserved.

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

DOE PAGES

Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

2013-06-03

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity inmore » recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.« less

Desorption dynamics of deuterium in CuCrZr alloy

NASA Astrophysics Data System (ADS)

Thi Nguyen, Lan Anh; Lee, Sanghwa; Noh, S. J.; Lee, S. K.; Park, M. C.; Shu, Wataru; Pitcher, Spencer; Torcy, David; Guillermain, David; Kim, Jaeyong

2017-12-01

Desorption behavior of deuterium (D2) in CuCrZr alloy was investigated considering sample thickness, loading and baking temperature of deuterium followed by the ITER scopes. Cylindrical specimens of 1, 3, 5 mm thick with 4 mm diameter were exposed to deuterium at a pressure of 25 bar at 120, 240 and 350 °C for 24 h, then baked at 800 °C in a vacuum chamber maintained at a pressure lower than 10-7 Torr. Deuterium desorption characteristics such as desorption rate and amount of deuterium in the sample were estimated by analyzing the desorption peaks monitored with a residual gas analyzer (RGA), and the trapping energy of deuterium was calculated using thermal desorption spectroscopy (TDS). Secondary ion mass spectroscopy (SIMS) results showed that deuterium atoms embedded in the sample at a depth of less than 15 μm and desorbed as low as 400 °C. All absorbed deuterium atoms in the specimen were completely retrieved by dynamic pumping at 800 °C in 15 min. The desorption rate of deuterium per unit area was inversely proportional to the increment of the thickness of the sample, and was proportional to the loading temperature. Based on the assumption that a uniform distribution of interstitial sites for deuterium follows the Femi-Dirac statistics, the result of TDS demonstrated that the CuCrZr alloy has two types of trapping energies, which were estimated to be 62 and 79 kJ/mol.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

Silver-gold alloy nanoparticles as tunable substrates for systematic control of ion-desorption efficiency and heat transfer in surface-assisted laser desorption/ionization.

PubMed

Lai, Samuel Kin-Man; Cheng, Yu-Hong; Tang, Ho-Wai; Ng, Kwan-Ming

2017-08-09

Systematically controlling heat transfer in the surface-assisted laser desorption/ionization (SALDI) process and thus enhancing the analytical performance of SALDI-MS remains a challenging task. In the current study, by tuning the metal contents of Ag-Au alloy nanoparticle substrates (AgNPs, Ag55Au45NPs, Ag15Au85NPs and AuNPs, ∅: ∼2.0 nm), it was found that both SALDI ion-desorption efficiency and heat transfer can be controlled in a wide range of laser fluence (21.3 mJ cm -2 to 125.9 mJ cm -2 ). It was discovered that ion detection sensitivity can be enhanced at any laser fluence by tuning up the Ag content of the alloy nanoparticle, whereas the extent of ion fragmentation can be reduced by tuning up the Au content. The enhancement effect of Ag content on ion desorption was found to be attributable to the increase in laser absorption efficiency (at 355 nm) with Ag content. Tuning the laser absorption efficiency by changing the metal composition was also effective in controlling the heat transfer from the NPs to the analytes. The laser-induced heating of Ag-rich alloy NPs could be balanced or even overridden by increasing the Au content of NPs, resulting in the reduction of the fragmentation of analytes. In the correlation of experimental measurement with molecular dynamics simulation, the effect of metal composition on the dynamics of the ion desorption process was also elucidated. Upon increasing the Ag content, it was also found that phase transition temperatures, such as melting, vaporization and phase explosion temperature, of NPs could be reduced. This further enhanced the desorption of analyte ions via phase-transition-driven desorption processes. The significant cooling effect on the analyte ions observed at high laser fluence was also determined to be originated from the phase explosion of the NPs. This study revealed that the development of alloy nanoparticles as SALDI substrates can constitute an effective means for the systematic control of ion-desorption efficiency and the extent of heat transfer, which could potentially enhance the analytical performance of SALDI-MS.

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.

Radionuclide desorption kinetics on synthetic Zn/Ni-labeled montmorillonite nanoparticles

NASA Astrophysics Data System (ADS)

Huber, F. M.; Heck, S.; Truche, L.; Bouby, M.; Brendlé, J.; Hoess, P.; Schäfer, T.

2015-01-01

Sorption/desorption kinetics for selected radionuclides (99Tc(VII), 232Th(IV), 233U(VI), 237Np(V), 242Pu and 243Am(III)) under Grimsel (Switzerland) ground water conditions (pH 9.7 and ionic strength of ∼1 mM) in the presence of synthetic Zn or Ni containing montmorillonite nanoparticles and granodiorite fracture filling material (FFM) from Grimsel were examined in batch studies. The structurally bound Zn or Ni in the octahedral sheet of the synthetic colloids rendered them suitable as colloid markers. Only a weak interaction of the montmorillonite colloids with the fracture filling material occurs over the experimental duration of 10,000 h (∼13 months). The tri- and tetravalent radionuclides are initially strongly associated with nanoparticles in contrast to 99Tc(VII), 233U(VI) and 237Np(V) which showed no sorption to the montmorillonite colloids. Radionuclide desorption of the nanoparticles followed by sorption to the fracture filling material is observed for 232Th(IV), 242Pu and 243Am(III). Based on the conceptual model that the driving force for the kinetically controlled radionuclide desorption from nanoparticles and subsequent association to the FFM is the excess in surface area offered by the FFM, the observed desorption kinetics are related to the colloid/FFM surface area ratio. The observed decrease in concentration of the redox sensitive elements 99Tc(VII), 233U(VI) and 237Np(V) may be explained by reduction to lower oxidation states in line with Eh-pH conditions prevailing in the experiments and thermodynamic considerations leading to (i) precipitation of a sparingly soluble phase, (ii) sorption to the fracture filling material, (iii) possible formation of eigencolloids and/or (iv) sorption to the montmorillonite colloids. Subsequent to the sorption/desorption kinetics study, an additional experiment was conducted investigating the potential remobilization of radionuclides/colloids attached to the FFM used in the sorption/desorption kinetic experiments by contacting this FFM with pure Grimsel groundwater for 7 days. A positive correlation of 242Pu, 232Th(IV) and 237Np was observed with the Zn and Ni concentrations in the desorption experiments indicating a remobilization of sorbed montmorillonite colloids. The results of the study in hand highlight (i) the novel use of structural labeled colloids to decrease the uncertainties in the determination of nanoparticle attachment providing more confidence in the derived radionuclide desorption rates. Moreover, the data illustrate (ii) the importance of radionuclide colloid desorption to be considered in the analysis and application of colloid facilitated transport both in laboratory or in-situ experiments and numerical model simulations and (iii) a possible remobilization of sorbed colloids and associated radionuclides by desorption from the matrix material (FFM) under non-equilibrium conditions.

Effect of artificial root exudates on the sorption and desorption of PAHs in meadow brown soils

NASA Astrophysics Data System (ADS)

Wang, Hong

2017-10-01

The batch equilibrium experiment was conducted to investigate the effect of artificial root exudates on sorption and desorption of phenanthrene and pyrene. The result showed sorption isotherms were fitted well to the Freundlich equation with the treatment of artificial root exudates. Fructose had the most obvious effect on sorption. The artificial root exudates improved desorption of PAHs, while low molecular weight organic acids were better than serine and fructose. The capability of sorption and desorption was strengthened with the increase of organic acids concentration. And the DOM in the solution might be the most important factor of the adsorption of PAHs in solid phase.

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.)

Desorption Mass Spectrometry for Nonvolatile Compounds Using an Ultrasonic Cutter

NASA Astrophysics Data System (ADS)

Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T.; Hiraoka, Kenzo

2014-07-01

In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

Desorption mass spectrometry for nonvolatile compounds using an ultrasonic cutter.

PubMed

Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T; Hiraoka, Kenzo

2014-07-01

In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

NASA Astrophysics Data System (ADS)

Kitagawa, Yuta; Tanabe, Katsuaki

2018-05-01

Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

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.

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.

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.

Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1979-01-01

Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

The influence of dislocation and hydrogen on thermal helium desorption behavior in Fe9Cr alloys

NASA Astrophysics Data System (ADS)

Zhu, Te; Jin, Shuoxue; Gong, Yihao; Lu, Eryang; Song, Ligang; Xu, Qiu; Guo, Liping; Cao, Xingzhong; Wang, Baoyi

2017-11-01

Transmutation helium may causes serious embrittlement which is considered to be due to helium from clustering as a bubble in materials. Suppression of transmutation helium can be achieved by introducing trapping sites such as dislocations and impurities in materials. Here, effects of intentionally-induced dislocations and hydrogen on helium migrate and release behaviors were investigated using thermal desorption spectrometry (TDS) technique applied to well-annealed and cold-worked Fe9Cr alloys irradiated by energetic helium/hydrogen ions. Synchronous desorption of helium and hydrogen was observed, and the microstructure states during helium release at different temperatures were analyzed. High thermally stable HenD type complexes formed in cold-worked specimens, resulting in the retardation of helium migration and release. The existence of hydrogen will strongly affect the thermal helium desorption which could be reflected in the TDS spectrum. It was confirmed that hydrogen retained in the specimens can result in obvious delay of helium desorption.

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.

Shear-induced desorption of isolated polymer molecules from a planar wall

NASA Astrophysics Data System (ADS)

Dutta, Sarit; Dorfman, Kevin; Kumar, Satish

2014-03-01

Shear-induced desorption of isolated polymer molecules is studied using Brownian dynamics simulations. The polymer molecules are modeled as freely jointed bead-spring chains interacting with a planar wall via a short-range potential. The simulations include both intrachain and chain-wall hydrodynamic interactions. Shear flow is found to cause chain flattening, resulting at low shear rates in an increased fraction of chain segments bound to the wall. However, above a critical shear rate the chains desorb completely. The desorption process is nucleated by random protrusions in the shear gradient direction which evolve under the combined effect of drag, hydrodynamic interaction, and vorticity-induced rotation, and subsequently lead to recapture. Above the critical shear rate, these protrusions grow in length until the entire chain is peeled off the wall. For free-draining chains, the protrusions are not sustained and no desorption is observed even at shear rates much higher than the critical value. These simulations can help in interpreting experiments on shear-induced desorption of polymer films and brushes.

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

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.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

NASA Astrophysics Data System (ADS)

El-Atwani, O.; Taylor, C. N.; Frishkoff, J.; Harlow, W.; Esquivel, E.; Maloy, S. A.; Taheri, M. L.

2018-01-01

Microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed helium was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.

A Holistic Approach to Understanding the Desorption of Phosphorus in Soils.

PubMed

Menezes-Blackburn, Daniel; Zhang, Hao; Stutter, Marc; Giles, Courtney D; Darch, Tegan; George, Timothy S; Shand, Charles; Lumsdon, David; Blackwell, Martin; Wearing, Catherine; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Haygarth, Philip M

2016-04-05

The mobility and resupply of inorganic phosphorus (P) from the solid phase were studied in 32 soils from the UK. The combined use of diffusive gradients in thin films (DGT), diffusive equilibration in thin films (DET) and the "DGT-induced fluxes in sediments" model (DIFS) were adapted to explore the basic principles of solid-to-solution P desorption kinetics in previously unattainable detail. On average across soil types, the response time (Tc) was 3.6 h, the desorption rate constant (k-1) was 0.0046 h(-1), and the desorption rate was 4.71 nmol l(-1) s(-1). While the relative DGT-induced inorganic P flux responses in the first hour is mainly a function of soil water retention and % Corg, at longer times it is a function of the P resupply from the soil solid phase. Desorption rates and resupply from solid phase were fundamentally influenced by P status as reflected by their high correlation with P concentration in FeO strips, Olsen, NaOH-EDTA and water extracts. Soil pH and particle size distribution showed no significant correlation with the evaluated mobility and resupply parameters. The DGT and DET techniques, along with the DIFS model, were considered accurate and practical tools for studying parameters related to soil P desorption kinetics.

Determination of adsorption and desorption of DNA molecules on freshwater and marine sediments.

PubMed

Xue, J; Feng, Y

2018-06-01

Free DNA and its adsorption by sediment in the aquatic environment lead to ambiguity in the identification of recent faecal pollution sources. The goal of this study was to understand the mechanisms of DNA adsorption and desorption on aquatic sediment under various conditions using quantitative polymerase chain reaction (qPCR). Both raw sewage (RS) DNA and purified PCR product (PPP) were used in adsorption and desorption experiments; autoclaved freshwater and marine sediments served as sorbents. Thirty-six hours were needed for adsorption to reach equilibrium. More DNA was adsorbed on both sediments in stream water than in 5 mmol l -1 NaCl and DNA adsorption increased in the presence of Ca 2+ and Mg 2+ . Successive desorption experiments showed that between 5% and 22% of adsorbed DNA was desorbed. Organic matter and clay played a significant role in determining the DNA adsorption capacity on sediment. The data suggest the presence of multilayer adsorption. DNA molecules on sediments were mostly adsorbed through ligand binding rather than electrostatic binding. Quantitative polymerase chain reaction assays provide a better way to investigate the DNA adsorption and desorption mechanisms by sediment. DNA desorption can potentially complicate the outcomes of microbial source tracking studies. © 2018 The Society for Applied Microbiology.

Effect of land use pattern change from paddy soil to vegetable soil on the adsorption-desorption of cadmium by soil aggregates.

PubMed

Zhang, Qiu; Li, Zhongwu; Huang, Bin; Luo, Ninglin; Long, Lingzhi; Huang, Mei; Zhai, Xiuqing; Zeng, Guangming

2017-01-01

The influence of land use change from paddy soil to vegetable soil on the adsorption-desorption behavior of Cd in soil aggregates and the variation in soil properties were investigated. The vegetable soil was characterized by lower pH, organic matter content, cation exchange capacity (CEC), free iron oxides, manganese oxides, and catalase activity and higher urease activity compared with the paddy soil. In the isothermal adsorption and desorption experiments, the adsorption characteristics of Cd of the two soils could be well described by Langmuir and Freundlich equations. The adsorption capacity of vegetable soil decreased 22.72 %, and the desorption rate increased 35 % with respect to paddy soil. Therefore, conversion from paddy to vegetable field can reduce the adsorption ability to Cd of the soil to a certain extent. Both the two soils reached the maximum adsorption capacity and the minimum desorption rate in the <0.002-mm faction. The adsorption capacity of Cd in paddy and vegetable soils exhibited great reliance on the content of CEC. Desorption rate was negatively correlated with the four indicators: organic matter, CEC, free iron oxides, and manganese oxides, and specific adsorption was primarily controlled by soil organic matter and manganese oxides.

H 2 Desorption from MgH 2 Surfaces with Steps and Catalyst-Dopants

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

Reich, Jason M.; Wang, Lin-Lin; Johnson, Duane D.

2014-03-10

Light-metal hydrides, like MgH 2, remain under scrutiny as prototypes for reversible H-storage materials. For MgH 2, we assess hydrogen desorption/adsorption properties (enthalpy and kinetic barriers) for stepped, catalyst-doped surfaces occurring, e.g., from ball-milling in real samples. Employing density functional theory and simulated annealing in a slab model, we studied initial H 2 desorption from stepped surfaces with(out) titanium (Ti) catalytic dopant. Extensive simulated annealing studies were performed to find the dopant’s site preferences. For the most stable initial and final (possibly magnetic) states, nudged elastic band (NEB) calculations were performed to determine the H 2-desorption activation energy. We usedmore » a moment-transition NEB method to account for the dopant’s transition to the lowest-energy magnetic state at each image along the band. We identify a dopant-related surface-desorption mechanism that reloads via bulk H diffusion. While reproducing the observed bulk enthalpy of desorption, we find a decrease of 0.24 eV (a 14% reduction) in the activation energy on doped stepped surface; together with a 22% reduction on a doped flat surface, this brackets the assessed 18% reduction in kinetic barrier for ball-milled MgH 2 samples with low concentration of Ti from experiment.« less

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.

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold-Thiolate Bond Leading to a Tunable Molecular Template.

PubMed

Kawauchi, Takehiro; Kojima, Takahiro; Sakaguchi, Hiroshi; Iyoda, Tomokazu

2018-06-05

We investigated the adsorption and desorption behavior of self-assembled monolayers (SAMs) on gold derived from dendritic viologen-arranged molecules with an ω-mercaptodecyl group (A n, n (dendritic generation) = 0-3) at the apex of the dendritic structure in polar solvents. The adsorption of the dendritic molecules occurred quickly and saturated within a few minutes in an acetonitrile/ethanol (1/1, v/v) mixture at a concentration of 2 mM. Atomic force microscopy images of the SAMs showed flat surfaces regardless of the dendritic generation because the peripheral viologen units were closely packed at the surface of the molecular layer. Individual A3 molecules immobilized on the substrate were observed by scanning tunneling microscopy measurements of a mixed SAM with decanethiol. The desorption behaviors of dendritic molecules from the A n-SAMs in several solvents such as water were also investigated. The spontaneous desorption of the A n-SAM occurred more rapidly than that of a conventional n-alkanethiol SAM. However, the desorption was inhibited by adding electrolytes such as NaNO 3 due to the shielding effect on the electrostatic repulsion between the dendritic molecules. These results indicate that the surface density of the dendritic molecules can be controlled through the desorption.

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.

Physics of lithium bromide (LiBr) solution dewatering through vapor venting membranes

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

Isfahani, RN; Fazeli, A; Bigham, S

2014-01-01

The physics of water desorption from a lithium bromide (LiBr) solution flow through an array of microchannels capped by a porous membrane is studied. The membrane allows the vapor to exit the flow and retains the liquid. Effects of different parameters such as wall temperature, solution and vapor pressures, and solution mass flux on the desorption rate were studied. Two different mechanisms of desorption are analyzed. These mechanisms consisted of: (1) direct diffusion of water molecules out of the solution and their subsequent flow through the membrane and (2) formation of water vapor bubbles within the solution and their ventingmore » through the membrane. Direct diffusion was the dominant desorption mode at low surface temperatures and its magnitude was directly related to the vapor pressure, the solution concentration, and the heated wall temperature. Desorption at the boiling regime was predominantly controlled by the solution flow pressure and mass flux. Microscale visualization studies suggested that at a critical mass flux, some bubbles are carried out of the desorber through the solution microchannels rather than being vented through the membrane. Overall, an order of magnitude higher desorption rate compare to a previous study on a membrane-based desorber was achieved. Published by Elsevier Ltd.« less

CO adsorption on W(100) during temperature-programmed desorption: A combined density functional theory and kinetic Monte Carlo study

NASA Astrophysics Data System (ADS)

Albao, Marvin A.; Padama, Allan Abraham B.

2017-02-01

Using a combined density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations, we study the adsorption at 800 K and subsequent desorption of CO on W(100) at higher temperatures. The resulting TPD profiles are known experimentally to exhibit three desorption peaks β1, β2, and β3 at 930 K, 1070 K, and 1375 K, respectively. Unlike more recent theoretical studies that propose that all three aforementioned peaks are molecularly rather than associatively desorbed, our KMC analyses are in support of the latter, since at 800 K dissociation is facile and that CO exists as dissociation fragments C and O. We show that these peaks arise from desorption from the same adsorption site but whose binding energy varies depending on local environment, that is, the presence of CO as well as dissociation fragments C and O nearby. Furthermore we show that several key parameters, such as desorption, dissociation and recombination barriers all play a key role in the TPD spectra-these parameter effectively controls not only the location of the TPD peaks but the shape and width of the desorption peaks as well. Moreover, our KMC simulations reveal that varying the heating rate shifts the peaks but leaves their shape intact.

Desorption isotherms of heavy (AZOBE, EBONY) and light heavyweight tropical woods (IROKO, SAPELLI) of Cameroon

NASA Astrophysics Data System (ADS)

Nsouandélé, J. L.; Tamba, J. G.; Bonoma, B.

2018-04-01

This work is centered on the study of the desorption isotherms of heavy (Azobe, Ebony) and heavyweight (Iroko, Sapelli) tropical woods, which contribute in the determination of drying and storage of tropical plank woods. Desorption isotherms of tropical woods were experimentally determined under different temperatures in this study using the gravimetric method. The determination of Henderson's model isotherms parameters of desorption were obtained for temperatures of 20 °C, 30 °C, 40 °C, and 50 °C. The mean relative deviation between theoretical and experimental moisture contents was calculated and fitted well with the desorption models of tropical woods. We noticed that Henderson models fitted much better with experimental ones for 95% of relative humidity. The sigmoid shapes of results are satisfactory. Hysteresis phenomenon was observed for desorption isotherms of heavy (Azobe, Ebony) and heavyweight (Iroko, Sapelli) tropical woods. Results showed the difference between the stability and use of heavy and heavyweight tropical wood. These results help in the estimation of water content at equilibrium of tropical woods in relative humidity from experimented ones. Hygroscopic equilibrium humidity of heavy tropical woods varied between 0% and 50% while those of heavyweight varied between 0% and 25%. Therefore, these woods can be used in an opened environment; woodwork and decoration.

Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery.

PubMed

Terrón-Mejía, Ketzasmin A; López-Rendón, Roberto; Goicochea, Armando Gama

2017-08-29

The need to extract oil from wells where it is embedded on the surfaces of rocks has led to the development of new and improved enhanced oil recovery techniques. One of those is the injection of surfactants with water vapor, which promotes desorption of oil that can then be extracted using pumps, as the surfactants encapsulate the oil in foams. However, the mechanisms that lead to the optimal desorption of oil and the best type of surfactants to carry out desorption are not well known yet, which warrants the need to carry out basic research on this topic. In this work, we report non equilibrium dissipative particle dynamics simulations of model surfactants and oil molecules adsorbed on surfaces, with the purpose of studying the efficiency of the surfactants to desorb hydrocarbon chains, that are found adsorbed over flat surfaces. The model surfactants studied correspond to nonionic and cationic surfactants, and the hydrocarbon desorption is studied as a function of surfactant concentration under increasing Poiseuille flow. We obtain various hydrocarbon desorption isotherms for every model of surfactant proposed, under flow. Nonionic surfactants are found to be the most effective to desorb oil and the mechanisms that lead to this phenomenon are presented and discussed.

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.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

DOE PAGES

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James; ...

2017-11-09

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation.

PubMed

Hu, Jing; Aitken, Michael D

2012-10-01

Dermal exposure can represent a significant health risk in settings involving potential contact with soil contaminated with polycyclic aromatic hydrocarbons (PAHs). However, there is limited work on the ability of PAHs in contaminated soil to reach the skin surface via desorption from the soil. We evaluated PAH desorption from a field-contaminated soil to a two-dimensional hydrophobic surface (C18 extraction disk) as a measure of potential dermal exposure as a function of soil loading (5-100 mg dry soil cm(-2)), temperature (20-40°C), and soil moisture content (2-40%) over periods up to 16d. The efficacy of bioremediation in removing the most readily desorbable PAH fractions was also evaluated. Desorption kinetics were described well by an empirical two-compartment kinetic model. PAH mass desorbed to the C18 disk kept increasing at soil loadings well above the estimated monolayer coverage, suggesting mechanisms for PAH transport to the surface other than by direct contact. Such mechanisms were reinforced by observations that desorption occurred even with dry or moist glass microfiber filters placed between the C18 disk and the soil. Desorption of all PAHs was substantially reduced at a soil moisture content corresponding to field capacity, suggesting that transport through pore air contributed to PAH transport to the C18 disk. The lower molecular weight PAHs had greater potential to desorb from soil than higher molecular weight PAHs. Biological treatment of the soil in a slurry-phase bioreactor completely eliminated PAH desorption to the C18 disks. Copyright © 2012 Elsevier Ltd. All rights reserved.

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 of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation

PubMed Central

Hu, Jing; Aitken, Michael D.

2012-01-01

Dermal exposure can represent a significant health risk in settings involving potential contact with soil contaminated with polycyclic aromatic hydrocarbons (PAHs). However, there is limited work on the ability of PAHs in contaminated soil to reach the skin surface via desorption from the soil. We evaluated PAH desorption from a field-contaminated soil to a two-dimensional hydrophobic surface (C18 extraction disk) as a measure of potential dermal exposure as a function of soil loading (5 to 100 mg dry soil/cm2), temperature (20 °C to 40 °C), and soil moisture content (2% to 40%) over periods up to 16 d. The efficacy of bioremediation in removing the most readily desorbable PAH fractions was also evaluated. Desorption kinetics were described well by an empirical two-compartment kinetic model. PAH mass desorbed to the C18 disk kept increasing at soil loadings well above the estimated monolayer coverage, suggesting mechanisms for PAH transport to the surface other than by direct contact. Such mechanisms were reinforced by observations that desorption occurred even with dry or moist glass microfiber filters placed between the C18 disk and the soil. Desorption of all PAHs was substantially reduced at a soil moisture content corresponding to field capacity, suggesting that transport through pore air contributed to PAH transport to the C18 disk. The lower molecular weight PAHs had greater potential to desorb from soil than higher molecular weight PAHs. Biological treatment of the soil in a slurry-phase bioreactor completely eliminated PAH desorption to the C18 disks. PMID:22704210

The Adsorption and Desorption of Pb(2+) and Cd(2+) in Freeze-Thaw Treated Soils.

PubMed

Li, Linhui; Ma, Jincai; Xu, Meng; Li, Xu; Tao, Jiahui; Wang, Guanzhu; Yu, Jitong; Guo, Ping

2016-01-01

Adsorption and desorption are important processes that influence the potential toxicity and bioavailability of heavy metals in soils. However, information regarding adsorption and desorption behavior of heavy metals in soils subjected to freeze-thaw cycles is poorly understood. In the current study, the effect of freeze-thaw cycles with different freezing temperature (-15, -25, -35°C) on soil properties was investigated. Then the adsorption and desorption behavior of Pb(2+) and Cd(2+) in freeze-thaw treated soils was studied. The adsorption amounts of Pb(2+) and Cd(2+) in freeze-thaw treated soils were smaller than those in unfrozen soils (p < 0.05), due to the fact that pH, cation exchange capacity, organic matter content, free iron oxide content, and CaCO3 content in freeze-thaw treated soils were smaller than those in unfrozen soils. The adsorption amounts of Pb(2+) and Cd(2+) in soils treated with lower freezing temperatures were higher than those in soils treated with higher freezing temperatures. Desorption percentages of Pb(2+) and Cd(2+) in unfrozen soils were smaller than those in freeze-thaw treated soils (p < 0.05). The desorption percentages of Pb(2+) and Cd(2+) were smaller in soils treated with lower freezing temperatures than those in soils treated with higher freezing temperatures. The results obtained highlight the change of the adsorption and desorption behavior of typical heavy metals in freeze-thaw treated soils located in seasonal frozen soils zone in northeast China.

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.

Study of Adsorption and Desorption Performances of Zr-Based Metal-Organic Frameworks Using Paper Spray Mass Spectrometry.

PubMed

Wang, Xiaoting; Chen, Ying; Zheng, Yajun; Zhang, Zhiping

2017-07-08

The dynamic pore systems and high surface areas of flexible metal-organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal-organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal-organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH₂ and UiO-66(Zr)-2COOH] as well as ZrO₂ in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO₂ demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO₂-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin).

Impact of styrenic polymer one-step hyper-cross-linking on volatile organic compound adsorption and desorption performance.

PubMed

Ghafari, Mohsen; Atkinson, John D

2018-06-05

A novel one-step hyper-cross-linking method, using 1,2-dichloroethane (DCE) and 1,6-dichlorohexane (DCH) cross-linkers, expands the micropore volume of commercial styrenic polymers. Performance of virgin and modified polymers was evaluated by measuring hexane, toluene, and methyl-ethyl-ketone (MEK) adsorption capacity, adsorption/desorption kinetics, and desorption efficiency. Hyper-cross-linked polymers have up to 128% higher adsorption capacity than virgin polymers at P/P 0  = 0.05 due to micropore volume increases up to 330%. Improvements are most pronounced with the DCE cross-linker. Hyper-cross-linking has minimal impact on hexane adsorption kinetics, but adsorption rates for toluene and MEK decrease by 6-41%. Desorption rates decreased (3-36%) for all materials after hyper-cross-linking, with larger decreases for DCE hyper-cross-linked polymers due to smaller average pore widths. For room temperature desorption, 20-220% more adsorbate remains in hyper-cross-linked polymers after regeneration compared to virgin materials. DCE hyper-cross-linked polymers have 13-92% more residual adsorbate than DCH counterparts. Higher temperatures were required for DCE hyper-cross-linked polymers to completely desorb VOCs compared to the DCH hyper-cross-linked and virgin counterparts. Results show that the one-step hyper-cross-linking method for modifying styrenic polymers improves adsorption capacity because of added micropores, but decreases adsorption/desorption kinetics and desorption efficiency for large VOCs due to a decrease in average pore width. Copyright © 2018 Elsevier B.V. All rights reserved.

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Investigation of sorption/desorption equilibria of heavy metal ions on/from quartz using rhamnolipid biosurfactant.

PubMed

Aşçi, Yeliz; Nurbaş, Macid; Sağ Açikel, Yeşim

2010-01-01

In the present study, the sorption characteristics of Cd(II) and Zn(II) ions on quartz, a representative soil-component, and the desorption of these metal ions from quartz using rhamnolipid biosurfactant were investigated. In the first part of the studies, the effects of initial metal ion concentration and pH on sorption of Cd(II) and Zn(II) ions by a fixed amount of quartz (1.5g) were studied in laboratory batch mode. The equilibrium sorption capacity for Cd(II) and Zn(II) ions was measured and the best correlation between experimental and model predicted equilibrium uptake was obtained using the Freundlich model. Although investigations on the desorption of heavy metal ions from the main soil-components are crucial to better understand the mobility and bioavailability of metals in the environment, studies on the description of desorption equilibrium were performed rarely. In the second part, the desorption of Cd(II) and Zn(II) from quartz using rhamnolipid biosurfactant was investigated as a function of pH, rhamnolipid concentration, and the amounts of sorbed Cd(II) and Zn(II) ions by quartz. The Freundlich model was also well fitted to the obtained desorption isotherms. Several indexes were calculated based on the differences of the quantity of Cd-Zn sorbed and desorbed. A desorption hysteresis (irreversibility) index based on the Freundlich exponent, concentration-dependent metal distribution coefficients, and the irreversibility index based on the metal distribution coefficient were used to quantify hysteretic behavior observed in the systems. 2009 Elsevier Ltd. All rights reserved.

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

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

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.

Effect of pH on desorption of CO2 from alkanolamine - rich solvents

NASA Astrophysics Data System (ADS)

Du, Min

2017-08-01

Adipic acid was used as a pH regulator, which was added to 0.4 mol/L MEA, DEA and MDEA solvents during CO2 desorption process. It is found that when pH value of the solvents swing between 8-10, CO2 desorption rate enhanced, and energy consumption has declined obviously. This research may have reference significance on optimization of alkanolamine CO2 capture process.

Sequential Desorption of Nitroaromatic Compounds (NAC) from Soils

DTIC Science & Technology

2005-03-01

the soil solution . Weissmahr et al. [20] suggest an electron donor acceptor (EDA) complex between oxygens of the siloxane surface of the clays and the...release of NACs into the soil solution . At high pH values desorption is superimposed by NACs hydrolysis. Therefore, in- creasing pH values impedes the...presented demonstrate that both the cation present in the soil solution and its concentration may affect the desorption behavior of NACs in contaminated soils

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.

Plume characteristics and dynamics of UV and IR laser-desorbed oligonucleotides.

PubMed

Merrigan, Tony L; Timson, David J; Hunniford, C Adam; Catney, Martin; McCullough, Robert W

2012-05-01

Laser desorption of dye-tagged oligonucleotides was studied using laser-induced fluorescence imaging. Desorption with ultra violet (UV) and infra-red (IR) lasers resulted in forward directed plumes of molecules. In the case of UV desorption, the initial shot desorbed approximately seven-fold more material than subsequent shots. In contrast, the initial shot in IR desorption resulted in the ejection of less material compared to subsequent shots and these plumes had a component directed along the path of the laser. Thermal equilibrium of the molecules in the plume was achieved after approximately 25 μs with a spread in molecular temperature which was described by a modified Maxwell-Boltzmann equation. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Numerical comparison of hydrogen desorption behaviors of metal hydride beds based on uranium and on zirconium-cobalt

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

Kyoung, S.; Yoo, H.; Ju, H.

2015-03-15

In this paper, the hydrogen delivery capabilities of uranium (U) and zirconium-cobalt (ZrCo) are compared quantitatively in order to find the optimum getter materials for tritium storage. A three-dimensional hydrogen desorption model is applied to two identically designed cylindrical beds with the different materials, and hydrogen desorption simulations are then conducted. The simulation results show superior hydrogen delivery performance and easier thermal management capability for the U bed. This detailed analysis of the hydrogen desorption behaviors of beds with U and ZrCo will help to identify the optimal bed material, bed design, and operating conditions for the storage and deliverymore » system in ITER. (authors)« less

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.

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.

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

ε-Polylysine-based thermo-responsive adsorbents for immunoglobulin adsorption-desorption under mild conditions.

PubMed

Maruyama, Masashi; Shibuya, Keisuke

2017-08-22

Thermo-responsive adsorbents for immunoglobulin G (IgG) employing ε-polylysine (EPL) as a polymer backbone were developed. The introduction of mercaptoethylpyridine (MEP) as an IgG-binding ligand and hydrophobization of side chains afforded thermo-responsive IgG adsorbents, whose thermo-responsive IgG desorption ratio was up to 88% (EPL/MEP derivative 3m). The changes in surface densities of active MEP groups, which are caused by thermal conformational changes of the adsorbents, play key roles for IgG desorption. Although a trade-off of IgG adsorption capacity and IgG desorption ratio was observed, the present study offers a novel molecular design for thermo-responsive adsorbents with high synthetic accessibility and potentially low toxicity.

Biosorption and desorption of Cd2+ from wastewater by dehydrated shreds of Cladophora fascicularis

NASA Astrophysics Data System (ADS)

Deng, Liping; Zhu, Xiaobin; Su, Yingying; Su, Hua; Wang, Xinting

2008-02-01

The adsorption and desorption of algae Cladophora fascicularis and their relation with initial Cd2+ concentration, initial pH, and co-existing ions were studied. Adsorption equilibrium and biosorption kinetics were established from batch experiments. The adsorption equilibrium was adequately described by the Langmuir isotherm, and biosorption kinetics was in pseudo-second order model. The experiment on co-existing ions showed that the biosorption capacity of biomass decreased with an increasing concentration of competing ions. Desorption experiments indicated that EDTA was efficient desorbent for recovery from Cd2+. With high capacities of metal biosorption and desorption, the biomass of Cladophora fascicularis is promising as a cost-effective biosorbent for the removal of Cd2+ from wastewater.

Desorption and sublimation kinetics for fluorinated aluminum nitride surfaces

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

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Nemanich, Robert J.

2014-09-01

The adsorption and desorption of halogen and other gaseous species from surfaces is a key fundamental process for both wet chemical and dry plasma etch and clean processes utilized in nanoelectronic fabrication processes. Therefore, to increase the fundamental understanding of these processes with regard to aluminum nitride (AlN) surfaces, temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) have been utilized to investigate the desorption kinetics of water (H{sub 2}O), fluorine (F{sub 2}), hydrogen (H{sub 2}), hydrogen fluoride (HF), and other related species from aluminum nitride thin film surfaces treated with an aqueous solution of buffered hydrogen fluoride (BHF) dilutedmore » in methanol (CH{sub 3}OH). Pre-TPD XPS measurements of the CH{sub 3}OH:BHF treated AlN surfaces showed the presence of a variety of Al-F, N-F, Al-O, Al-OH, C-H, and C-O surfaces species in addition to Al-N bonding from the AlN thin film. The primary species observed desorbing from these same surfaces during TPD measurements included H{sub 2}, H{sub 2}O, HF, F{sub 2}, and CH{sub 3}OH with some evidence for nitrogen (N{sub 2}) and ammonia (NH{sub 3}) desorption as well. For H{sub 2}O, two desorption peaks with second order kinetics were observed at 195 and 460 °C with activation energies (E{sub d}) of 51 ± 3 and 87 ± 5 kJ/mol, respectively. Desorption of HF similarly exhibited second order kinetics with a peak temperature of 475 °C and E{sub d} of 110 ± 5 kJ/mol. The TPD spectra for F{sub 2} exhibited two peaks at 485 and 585 °C with second order kinetics and E{sub d} of 62 ± 3 and 270 ± 10 kJ/mol, respectively. These values are in excellent agreement with previous E{sub d} measurements for desorption of H{sub 2}O from SiO{sub 2} and AlF{sub x} from AlN surfaces, respectively. The F{sub 2} desorption is therefore attributed to fragmentation of AlF{sub x} species in the mass spectrometer ionizer. H{sub 2} desorption exhibited an additional high temperature peak at 910 °C with E{sub d} = 370 ± 10 kJ/mol that is consistent with both the dehydrogenation of surface AlOH species and H{sub 2} assisted sublimation of AlN. Similarly, N{sub 2} exhibited a similar higher temperature desorption peak with E{sub d} = 535 ± 40 kJ/mol that is consistent with the activation energy for direct sublimation of AlN.« less

Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

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

Li, Ming; Kang, Zhan, E-mail: zhankang@dlut.edu.cn; Huang, Xiaobo

2015-08-28

Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-networkmore » (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.« less

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.

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Study of Adsorption and Desorption Performances of Zr-Based Metal–Organic Frameworks Using Paper Spray Mass Spectrometry

PubMed Central

Wang, Xiaoting; Chen, Ying; Zheng, Yajun

2017-01-01

The dynamic pore systems and high surface areas of flexible metal–organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal–organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal–organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH2 and UiO-66(Zr)-2COOH] as well as ZrO2 in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO2 demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO2-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin). PMID:28773131

Adsorption-desorption of dimethenamid and fenarimol onto three agricultural soils as affected by treated wastewater and fresh sewage sludge-derived dissolved organic carbon.

PubMed

Rodríguez-Liébana, José Antonio; Peña, Aránzazu

2018-07-01

The use of treated wastewaters (TWW) in agriculture is widening in areas suffering drought, such as southern Europe, to preserve freshwater supply for human consumption. The composition of TWW, especially concerning their organic carbon (OC) content, has been demonstrated to influence the processes governing the behavior of non-ionic pesticides in soils. Three OC-poor agricultural soils (SV, RM1 and RM3) from the province of Granada (Spain) were chosen for the assessment of the adsorption and desorption of the herbicide dimethenamid (DIM) and the fungicide fenarimol (FEN). TWW and sewage sludge extracts at different dissolved OC (DOC) concentrations (30, 90 and 300 mg L -1 ) were considered to evaluate their effect on pesticide adsorption-desorption. As expected by their properties, DIM and FEN were weakly and moderately adsorbed to the soils, respectively. Soil OC seemed to be the major factor controlling FEN adsorption, whereas the mineral fraction played a key role in DIM adsorption, especially in RM1 with high clay:OC ratio. Although TWW did not significantly modify the adsorption of pesticides, it enhanced DIM desorption from the three soils. Adsorption of FEN to SV and RM3 was directly related to the concentration of DOC, possibly due to co-sorption phenomena. Hysteretic desorption was found in all cases, indicating partially reversible adsorption. While FEN desorption was not altered by the solutions, the use of sludge extracts at the highest DOC concentration (300 mg L -1 ) enhanced DIM desorption as occurred with TWW. Interactions with DOC in solution seemed to predominate for this less hydrophobic compound, thus increasing the risk of natural waters contamination if TWW will be used. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials

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

Chen, Mohan; Roszell, John; Scoullos, Emanuel V.

2016-03-30

Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. Here, we present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader chargemore » analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. In addition, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.« less

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

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.

Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Li, Ming; Huang, Xiaobo; Kang, Zhan

2015-08-01

Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

Photodesorption of Solid CO2 by Lyα

NASA Astrophysics Data System (ADS)

Bahr, D. A.; Baragiola, R. A.

2012-12-01

We measured desorption of atoms and molecules from films of solid carbon dioxide in an ultrahigh vacuum from 6 to 60 K under irradiation with Lyα (121.6 nm, 10.2 eV) photons, an important process in the balance between gas phase and condensed molecules in the interstellar medium. The measurements use microgravimetry and mass spectrometry during irradiation and temperature programmed desorption after irradiation. At low photon fluences, the desorption flux consists mainly of O atoms and, after ~1017 photons cm-2, it is dominated by CO with smaller amount of O2, C, and CO2, with the presence of O2 indicating solid-state chemical reactions. At high fluences (up to 1018 photons cm-2), the desorption yields saturate at values much higher than in previous studies. The yields (molecules/photon), derived assuming stoichiometric desorption, reach 0.014 at 6 K, growing to ~0.2 at 50 and 60 K. Warming the films during irradiation gives rise to pressure spikes that suggest desorption of trapped species in pores or at defects, possibly assisted by radical-induced reactions. Such an effect could be significant for radiation-processed CO2-coated interstellar grains that are heated by, i.e., cosmic ray impacts or grain-grain collisions. We discuss the experiments considering photochemical mechanisms and compare them to the results of ion irradiation.

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.

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.

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.

The regeneration characteristics of various red mud granular adsorbents (RMGA) for phosphate removal using different desorption reagents.

PubMed

Zhao, Yaqin; Yue, Qinyan; Li, Qian; Gao, Baoyu; Han, Shuxin; Yu, Hui

2010-10-15

In this research, various red mud granular adsorbents (RMGA), which were made from red mud--a kind of waste residue from the alumina industry, were manufactured under different sintering temperatures (ST). For the purpose of investigating the regeneration characteristics of them for phosphate removal, systematic experiments were carried out, including adsorption, desorption (using different desorption reagents) and resorption tests. When RMGA were desorbed by HCl solutions, the desorption efficiencies were relatively higher due to acid erosion, but the corresponding resorption capacities became small owing to extraction of effective components. Although RMGA rarely released phosphate in desorption process when being desorbed by deionised water, it performed well on resorption of phosphate afterwards. It was assumed that the lower pH in resorption process, which was caused by the reductive release of CaO into solution, contributed to a weaker competition of OH(-) on phosphate resorption. When NaOH solution was employed as the desorption reagent, resorption capacities of RMGA were relatively larger and increased with the increase of NaOH concentration, because OH(-) might ameliorate the chemical composition on the surface of RMGA potentially. In addition, several RMGA manufactured under lower ST obtained larger resorption capacities than their original adsorption capacities, because of the comparatively unstable crystal structure which led to a stronger amelioration on them. 2010 Elsevier B.V. All rights reserved.

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.

Root endophytic bacteria of a (137)Cs and Mn accumulator plant, Eleutherococcus sciadophylloides, increase (137)Cs and Mn desorption in the soil.

PubMed

Yamaji, Keiko; Nagata, Satoshi; Haruma, Toshikatsu; Ohnuki, Toshihiko; Kozaki, Tamotsu; Watanabe, Naoko; Nanba, Kenji

2016-03-01

We found that root endophytes of (137)Cs accumulator plant produce siderophores, resulting in the desorption of (137)Cs from the contaminated soil collected at Fukushima, Japan. We selected an endemic Japanese deciduous tree, Eleutherococcus sciadophylloides (Franch. et Sav), that accumulates high concentrations of (137)Cs and Mn. Root endophytic bacteria were isolated from E. sciadophylloides and microbial siderophore production was evaluated via chrome azurol S (CAS) Fe and CAS Al assays. Of the 463 strains that we isolated, 107 (23.1%) produced the siderophores. Using eight strains that showed high siderophore production in our assays, we examined desorption of (137)Cs, Mn, Fe and Al by the bacterial culture filtrates from (137)Cs-contaminated soil after decomposing the soil organic matter using hydrogen peroxide. We found (137)Cs and Mn desorption concomitant with Al and Fe desorption, as well as a decrease of pH. We also detected succinic acid, a well-known siderophore, in the bacterial culture filtrates of our two root endophytic bacteria. Our results strongly suggest that the root endophytic bacteria of E. sciadophylloides produce the siderophores that enhance (137)Cs and Mn desorption in the rhizosphere, making the resulting (137)Cs and Mn ions easier for E. sciadophylloides to absorb from the rhizosphere. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Effectiveness of laser sources for contactless sampling of explosives

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2016-05-01

A mass-spectrometric study of photo processes initiated by ultraviolet (UV) laser radiation in explosives adsorbed on metal and dielectric substrates has been performed. A calibrated quadrupole mass spectrometer was used to determine a value of activation energy of desorption and a quantity of explosives desorbed by laser radiation. A special vacuumoptical module was elaborated and integrated into a vacuum mass-spectrometric system to focus the laser beam on a sample. It has been shown that the action of nanosecond laser radiation set at q= 107 - 108 W/cm2, λ=266 nm on adsorbed layers of molecules of trinitrotoluene (TNT ) and pentaerytritoltetranitrate (PETN) leads not only to an effective desorption, but also to the non-equilibrium dissociation of molecules with the formation of nitrogen oxide NO. The cyclotrimethylenetrinitramine (RDX) dissociation products are observed only at high laser intensities (q> 109 W/cm2) thus indicating the thermal nature of dissociation, whereas desorption of RDX is observed even at q> 107 W/cm2 from all substrates. Desorption is not observed for cyclotetramethylenetetranitramine (HMX) under single pulse action: the dissociation products NO and NO2 are registered only, whereas irradiation at 10Hz is quite effective for HMX desorption. The results clearly demonstrate a high efficiency of nanosecond laser radiation with λ = 266 nm, q ~ 107 - 108 W/cm2, Epulse= 1mJ for desorption of molecules of explosives from various surfaces.

Physicochemical and thermodynamic investigation of hydrogen absorption and desorption in LaNi3.8Al1.0Mn0.2 using the statistical physics modeling

NASA Astrophysics Data System (ADS)

Bouaziz, Nadia; Ben Manaa, Marwa; Ben Lamine, Abdelmottaleb

2018-06-01

In the present work, experimental absorption and desorption isotherms of hydrogen in LaNi3.8Al1.0Mn0.2 metal at two temperatures (T = 433 K, 453 K) have been fitted using a monolayer model with two energies treated by statistical physics formalism by means of the grand canonical ensemble. Six parameters of the model are adjusted, namely the numbers of hydrogen atoms per site nα and nβ, the receptor site densities Nmα and Nmβ, and the energetic parameters Pα and Pβ. The behaviors of these parameters are discussed in relationship with temperature of absorption/desorption process. Then, a dynamic investigation of the simultaneous evolution with pressure of the two α and β phases in the absorption and desorption phenomena using the adjustment parameters. Thanks to the energetic parameters, we calculated the sorption energies which are typically ranged between 276.107 and 310.711 kJ/mol for absorption process and between 277.01 and 310.9 kJ/mol for desorption process comparable to usual chemical bond energies. The calculated thermodynamic parameters such as entropy, Gibbs free energy and internal energy from experimental data showed that the absorption/desorption of hydrogen in LaNi3.8Al1.0Mn0.2 alloy was feasible, spontaneous and exothermic in nature.

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

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

Tian, Lei; Shi, Zhenqing; Lu, Yang

Understanding the kinetics of toxic ion reactions with ferrihydrite is crucial for predicting the dynamic behavior of contaminants in soil environments. In this study, the kinetics of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite were investigated with a combination of laboratory macroscopic experiments, microscopic investigation and mechanistic modeling. The rates of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite, as systematically studied using a stirred-flow method, was highly dependent on the reaction pH and metal concentrations and varied significantly among four metals. Spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) showed, at sub-nano scales, all fourmore » metals were distributed within the ferrihydrite particle aggregates homogeneously after adsorption reactions, with no evidence of surface diffusion-controlled processes. Based on experimental results, we developed a unifying kinetics model for both cation and oxyanion adsorption/desorption on ferrihydrite based on the mechanistic-based equilibrium model CD-MUSIC. Overall, the model described the kinetic results well, and we quantitatively demonstrated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites affected the adsorption and desorption rates. Our results provided a unifying quantitative modeling method for the kinetics of both cation and oxyanion adsorption/desorption on iron minerals.« less

Measurements of VOC adsorption/desorption characteristics of typical interior building materials

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

An, Y.; Zhang, J.S.; Shaw, C.Y.

2000-07-01

The adsorption/desorption of volatile organic compounds (VOCs) on interior building material surfaces (i.e., the sink effect) can affect the VOC concentrations in a building, and thus need to be accounted for an indoor air quality (IAQ) prediction model. In this study, the VOC adsorption/desorption characteristics (sink effect) were measured for four typical interior building materials including carpet, vinyl floor tile, painted drywall, and ceiling tile. The VOCs tested were ethylbenzene, cyclohexanone, 1,4-dichlorobenzene, benzaldehyde, and dodecane. These five VOCs were selected because they are representative of hydrocarbons, aromatics, ketones, aldehydes, and chlorine substituted compounds. The first order reversible adsorption/desorption model wasmore » based on the Langmuir isotherm was used to analyze the data and to determine the equilibrium constant of each VOC-material combination. It was found that the adsorption/desorption equilibrium constant, which is a measure of the sink capacity, increased linearly with the inverse of the VOC vapor pressure. For each compound, the adsorption/desorption equilibrium constant, and the adsorption rate constant differed significantly among the four materials tested. A detailed characterization of the material structure in the micro-scale would improve the understanding and modeling of the sink effect in the future. The results of this study can be used to estimate the impact of sink effect on the VOC concentrations in buildings.« less

Reprint of: Effects of cold deformation, electron irradiation and extrusion on deuterium desorption behavior in Zr-1%Nb alloy

NASA Astrophysics Data System (ADS)

Morozov, O.; Mats, O.; Mats, V.; Zhurba, V.; Khaimovich, P.

2018-01-01

The present article introduces the data of analysis of ranges of ion-implanted deuterium desorption from Zr-1% Nb alloy. The samples studied underwent plastic deformation, low temperature extrusion and electron irradiation. Plastic rolling of the samples at temperature ∼300 K resulted in plastic deformation with the degree of ε = 3.9 and the formation of nanostructural state with the average grain size of d = 61 nm. The high degree of defectiveness is shown in thermodesorption spectrum as an additional area of the deuterium desorption in the temperature ranges 650-850 K. The further processing of the sample (that had undergone plastic deformation by plastic rolling) with electron irradiation resulted in the reduction of the average grain size (58 nm) and an increase in borders concentration. As a result the amount of deuterium desorpted increased in the temperature ranges 650-900 K. In case of Zr-1% Nb samples deformed by extrusion the extension of desorption area is observed towards the temperature reduction down to 420 K. The formation of the phase state of deuterium solid solution in zirconium was not observed. The structural state behavior is a control factor in the process of deuterium thermodesorption spectrum structure formation with a fixed implanted deuterium dose (hydrogen diagnostics). It appears as additional temperature ranges of deuterium desorption depending on the type, character and defect content.

Evaluation of active sampling strategies for the determination of 1,3-butadiene in air

NASA Astrophysics Data System (ADS)

Vallecillos, Laura; Maceira, Alba; Marcé, Rosa Maria; Borrull, Francesc

2018-03-01

Two analytical methods for determining levels of 1,3-butadiene in urban and industrial atmospheres were evaluated in this study. Both methods are extensively used for determining the concentration of volatile organic compounds in the atmosphere and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method uses activated charcoal as the sorbent and involves liquid desorption with carbon disulfide. The second involves the use of a multi-sorbent bed with two graphitised carbons and a carbon molecular sieve as the sorbent, with thermal desorption. Special attention was paid to the optimization of the sampling procedure through the study of sample volume, the stability of 1,3-butadiene once inside the sampling tube and the humidity effect. In the end, the thermal desorption method showed better repeatability and limits of detection and quantification for 1,3-butadiene than the liquid desorption method, which makes the thermal desorption method more suitable for analysing air samples from both industrial and urban atmospheres. However, sampling must be performed with a pre-tube filled with a drying agent to prevent the loss of the adsorption capacity of the solid adsorbent caused by water vapour. The thermal desorption method has successfully been applied to determine of 1,3-butadiene inside a 1,3-butadiene production plant and at three locations in the vicinity of the same plant.

Theoretical study of hydrogen absorption-desorption on LaNi3.8Al1.2-xMnx using statistical physics treatment

NASA Astrophysics Data System (ADS)

Bouaziz, Nadia; Ben Manaa, Marwa; Ben Lamine, Abdelmottaleb

2017-11-01

The hydrogen absorption-desorption isotherms on LaNi3.8Al1.2-xMnx alloy at temperature T = 433 K is studied through various theoretical models. The analytical expressions of these models were deduced exploiting the grand canonical ensemble in statistical physics by taking some simplifying hypotheses. Among these models an adequate model which presents a good correlation with the experimental curves has been selected. The physicochemical parameters intervening in the absorption-desorption processes and involved in the model expressions could be directly deduced from the experimental isotherms by numerical simulation. Six parameters of the model are adjusted, namely the numbers of hydrogen atoms per site n1 and n2, the receptor site densities N1m and N2m, and the energetic parameters P1 and P2. The behaviors of these parameters are discussed in relation with absorption and desorption processes to better understand and compare these phenomena. Thanks to the energetic parameters, we calculated the sorption energies which are typically ranged between 266 and 269.4 KJ/mol for absorption process and between 267 and 269.5 KJ/mol for desorption process comparable to usual chemical bond energies. Using the adopted model expression, the thermodynamic potential functions which govern the absorption/desorption process such as internal energy Eint, free enthalpy of Gibbs G and entropy Sa are derived.

Thermal desorption behavior of helium in aged titanium tritide films

NASA Astrophysics Data System (ADS)

Cheng, G. J.; Shi, L. Q.; Zhou, X. S.; Liang, J. H.; Wang, W. D.; Long, X. G.; Yang, B. F.; Peng, S. M.

2015-11-01

The desorption behavior of helium in TiT(1.5∼1.8)-x3Hex film samples (x = 0.0022-0.22) was investigated by thermal desorption technique in vacuum condition in this paper. The thermal helium desorption spectrometry (THDS) of aging titanium tritide films prepared by electron beam evaporation revealed that, depending on the decayed 3He concentration in the samples, there are more than four states of helium existing in the films. The divided four zones in THDS based on helium states represent respectively: (1) the mobile single helium atoms with low activation energy in all aging samples resulted from the interstitial sites or dissociated from interstitial clusters, loops and dislocations, (2) helium bubbles inside the grain lattices, (3) helium bubbles in the grain boundaries and interconnected networks of dislocations in the helium concentration of 3Hegen/Ti > 0.0094, and (4) helium bubbles near or linked to the film surface by interconnected channel for later aging stage with 3Hegen/Ti > 0.18. The proportion of helium desorption in each zone was estimated, and dissociated energies of helium for different trapping states were given.

Influence of Desorption Conditions on Analyte Sensitivity and Internal Energy in Discrete Tissue or Whole Body Imaging by IR-MALDESI

NASA Astrophysics Data System (ADS)

Rosen, Elias P.; Bokhart, Mark T.; Ghashghaei, H. Troy; Muddiman, David C.

2015-06-01

Analyte signal in a laser desorption/postionization scheme such as infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is strongly coupled to the degree of overlap between the desorbed plume of neutral material from a sample and an orthogonal electrospray. In this work, we systematically examine the effect of desorption conditions on IR-MALDESI response to pharmaceutical drugs and endogenous lipids in biological tissue using a design of experiments approach. Optimized desorption conditions have then been used to conduct an untargeted lipidomic analysis of whole body sagittal sections of neonate mouse. IR-MALDESI response to a wide range of lipid classes has been demonstrated, with enhanced lipid coverage received by varying the laser wavelength used for mass spectrometry imaging (MSI). Targeted MS2 imaging (MS2I) of an analyte, cocaine, deposited beneath whole body sections allowed determination of tissue-specific ion response factors, and CID fragments of cocaine were monitored to comment on wavelength-dependent internal energy deposition based on the "survival yield" method.

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.

The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films.

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

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

2012-02-02

Temperature programmed desorption (TPD) is utilized to determine the length distribution of cracks formed through amorphous solid water (ASW) during crystallization. This distribution is determined by monitoring how the thickness of an ASW overlayer alters desorption of an underlayer of O2. As deposited the ASW overlayer prevents desorption of O2. During crystallization, cracks form through the ASW overlayer and open a path to vacuum which allows O2 to escape in a rapid episodic release known as the 'molecular volcano'. Sufficiently thick ASW overlayers further trap O2 resulting in a second O2 desorption peak commensurate with desorption of the last ofmore » the ASW overlayer. The evolution of this trapping peak with overlayer thickness is the basis for determining the distribution of crystallization induced cracks through the ASW. Reflection adsorption infrared spectroscopy (RAIRS) and TPD of multicomponent parfait structures of ASW, O2 and Kr indicate that a preponderance of these cracks propagate down from the outer surface of the ASW.« 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.

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.

Using microwave heating to improve the desorption efficiency of high molecular weight VOC from beaded activated carbon.

PubMed

Fayaz, Mohammadreza; Shariaty, Pooya; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

2015-04-07

Incomplete regeneration of activated carbon loaded with organic compounds results in heel build-up that reduces the useful life of the adsorbent. In this study, microwave heating was tested as a regeneration method for beaded activated carbon (BAC) loaded with n-dodecane, a high molecular weight volatile organic compound. Energy consumption and desorption efficiency for microwave-heating regeneration were compared with conductive-heating regeneration. The minimum energy needed to completely regenerate the adsorbent (100% desorption efficiency) using microwave regeneration was 6% of that needed with conductive heating regeneration, owing to more rapid heating rates and lower heat loss. Analyses of adsorbent pore size distribution and surface chemistry confirmed that neither heating method altered the physical/chemical properties of the BAC. Additionally, gas chromatography (with flame ionization detector) confirmed that neither regeneration method detectably altered the adsorbate composition during desorption. By demonstrating improvements in energy consumption and desorption efficiency and showing stable adsorbate and adsorbent properties, this paper suggests that microwave heating is an attractive method for activated carbon regeneration particularly when high-affinity VOC adsorbates are present.

Adsorption/desorption characteristics of lead on various types of soil

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

Peters, R.W.; Shem, L.

1994-09-01

Laboratory studies were conducted to address the phenomena of adsorption/desorption of lead onto various types of soils, both in the absence and presence of the chelating agent, ethylenediaminetetraacetic acid (EDTA). The linear and Freundlich isotherm models provided adequate description of the adsorption/desorption behavior. Over the range of EDTA concentrations employed in the study (0.01 to 0.10M), no significant difference in the isotherm parameters was observed as a result of the applied EDTA concentration. The presence of EDTA significantly altered the adsorption/desorption behavior of lead on the soil, resulting in less of the metal being adsorbed. The soil with the highermore » silt/clay content had a greater amount of lead adsorbed onto it (as compared with the sandy soil).« less

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.

Explosive desorption of icy grain mantles in dense clouds

NASA Technical Reports Server (NTRS)

Schutte, W. A.; Greenberg, J. M.

1991-01-01

The cycling of the condensible material in dense clouds between the gas phase and the icy grain mantles is investigated. In the model studied, desorption of the ice occurs due to grain mantle explosions when photochemically stored energy is released after transient heating by a cosmic ray particle. It is shown that, depending on the grain size distribution in dense clouds, explosive desorption can maintain up to about eight percent of the carbon in the form of CO in the gas phase at typical cloud densities.

Diffusion Analysis Of Hydrogen-Desorption Measurements

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1988-01-01

Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.

Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

NASA Technical Reports Server (NTRS)

Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

1998-01-01

Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

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.

Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas.

PubMed

Benham, Kevin; Hodyss, Robert; Fernández, Facundo M; Orlando, Thomas M

2016-11-01

We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation. Graphical Abstract ᅟ.

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts.

PubMed

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J; De Los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-20

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al₂O₃ 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al₂O₃ support helped to stabilize the furfural molecule on the surface.

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

PubMed Central

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J.; De los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-01

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al2O3 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al2O3 support helped to stabilize the furfural molecule on the surface. PMID:28788472

Sorption specificity and desorption hysteresis of gibberellic acid on ferrihydrite compared to goethite, hematite, montmorillonite, and kaolinite.

PubMed

Zhang, Li; Liu, Fei; Chen, Liang

2017-08-01

The pesticide gibberellic acid (GA 3 ) is a potential endocrine disruptor and environmental toxin; therefore, research into its environmental fate is warranted. Batch studies were conducted to investigate the sorption and desorption characteristics of GA 3 on aquifer media. The results demonstrated special sorption characteristic of GA 3 on ferrihydrite compared to goethite, hematite, montmorillonite, and kaolinite, where the sorption kinetics of GA 3 on ferrihydrite was fitted well with the pseudo-second-order, Elovich, and intra-particle diffusion models. The sorption kinetics of GA 3 on ferrihydrite indicated an initial high sorption rate followed by a slow reaction process. The initial high GA 3 sorption rate may be related to electrostatic sorption and surface complexation reactions on the outer surfaces and at the macropore entrances of ferrihydrite. While the slow step was controlled by GA 3 diffusion into mesopore of ferrihydrite. Analysis of the desorption hysteresis indicated a high hysteresis index (HI) ranging from 0.68 to 17.32, and a low desorption percentage ranging from 18 to 48%. After sufficient desorption, the calculated maximum residual GA 3 quantity due to surface complexation reactions with the ferrihydrite coordinated unsaturated sites was 9.05 ± 0.12 mg g -1 . The calculated maximum quantity of GA 3 trapped within the mesopore was 16.23 ± 0.91 mg g -1 . Graphical Abstract Schematic overview of GA 3 sorption and desorption on five minerals in groundwater.

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.

Measurements on the gas desorption yield of the oxygen-free copper irradiated with low-energy Xe10+ and O+

NASA Astrophysics Data System (ADS)

Dong, Z. Q.; Li, P.; Yang, J. C.; Yuan, Y. J.; Xie, W. J.; Zheng, W. H.; Liu, X. J.; Chang, J. J.; Luo, C.; Meng, J.; Wang, J. C.; Wang, Y. M.; Yin, Y.; Chai, Z.

2017-10-01

Heavy ion beam lost on the accelerator vacuum wall will release quantity of gas molecules and make the vacuum system deteriorate seriously. This phenomenon is called dynamic vacuum effect, observed at CERN, GSI and BNL, leading to the decrease of beam lifetime when increasing beam intensity. Heavy ion-induced gas desorption, which results in dynamic vacuum effect, becomes one of the most important problems for future accelerators proposed to operate with intermediate charge state beams. In order to investigate the mechanism of this effect and find the solution method for the IMP future project High Intensity heavy-ion Accelerator Facility (HIAF), which is designed to extract 1 × 1011 uranium particles with intermediate charge state per cycle, two dedicated experiment setups have been installed at the beam line of the CSR and the 320 kV HV platform respectively. Recently, experiment was performed at the 320 kV HV platform to study effective gas desorption with oxygen-free copper target irradiated with continuous Xe10+ beam and O+ beam in low energy regime. Gas desorption yield in this energy regime was calculated and the link between gas desorption and electronic energy loss in Cu target was proved. These results will be used to support simulations about dynamic vacuum effect and optimizations about efficiency of collimators to be installed in the HIAF main synchrotron BRing, and will also provide guidance for future gas desorption measurements in high energy regime.

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.

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.

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.

Dependence of samarium-soil interaction on samarium concentration: Implications for environmental risk assessment.

PubMed

Ramírez-Guinart, Oriol; Salaberria, Aitor; Vidal, Miquel; Rigol, Anna

2018-03-01

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption K d values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Thermal Programmed Desorption of C32 H 66

NASA Astrophysics Data System (ADS)

Cisternas, M.; Del Campo, V.; Cabrera, A. L.; Volkmann, U. G.; Hansen, F. Y.; Taub, H.

2011-03-01

Alkanes are of interest as prototypes for more complex molecules and membranes. In this work we study the desorption kinetics of dotriacontane C32 adsorbed on Si O2 /Si substrate. We combine in our instrument High Resolution Ellipsometry (HRE) and Thermal Programmed Desorption (TPD). C32 monolayers were deposited in high vacuum from a Knudsen cell on the substrate, monitorizing sample thickness in situ with HRE. Film thickness was in the range of up to 100 AA, forming a parallel bilayer and perpendicular C32 layer. The Mass Spectrometer (RGA) of the TPD section was detecting the shift of the desorption peaks at different heating rates applied to the sample. The mass registered with the RGA was AMU 57 for parallel and perpendicular layers, due to the abundance of this mass value in the disintegration process of C32 in the mass spectrometers ionizer. Moreover, the AMU 57 signal does not interfere with other signals coming from residual gases in the vacuum chamber. The desorption energies obtained were ΔEdes = 11,9 kJ/mol for the perpendicular bilayer and ΔEdes = 23 ,5 kJ/mol for the parallel bilayer.

Retention and transport of mecoprop on acid sandy-loam soils

NASA Astrophysics Data System (ADS)

Paradelo Núñez, Remigio; Conde Cid, Manuel; Abad, Elodie Martin; Fernández Calviño, David; Nóvoa Muñoz, Juan Carlos; Arias Estévez, Manuel

2017-04-01

Interaction with soil components is one of the key processes governing the fate of agrochemicals in the environment. In this work, we have studied the adsorption/desorption and transport of mecoprop in four acid sandy-loam soils with different organic matter contents. Kinetics of adsorption and adsorption/desorption at equilibrium have been studied in batch experiments, whereas transport was studied in laboratory columns. Adsorption and desorption are linear or nearly-linear. The kinetics of mecoprop adsorption are relatively fast in all cases (less than 24 h). Adsorption and desorption were adequately described by the linear and Freundlich models, with KF values that ranged from 0.7 to 8.8 Ln µmol1-n kg-1 and KD values from 0.3 to 3.6 L kg-1. High desorption percentages (>50%) were found, indicative of a high reversibility of the adsorption process. The results of the transport experiments showed that the retention of mecoprop by soil was very low (less than 6.2%). The retention of mecoprop by the soils in all experiments increased with organic matter content. Overall, it was observed that mecoprop was weakly adsorbed by the soils, what would result in a high risk of leaching of this compound.

NH4+ ad-/desorption in sequencing batch reactors: simulation, laboratory and full-scale studies.

PubMed

Schwitalla, P; Mennerich, A; Austermann-Haun, U; Müller, A; Dorninger, C; Daims, H; Holm, N C; Rönner-Holm, S G E

2008-01-01

Significant NH4-N balance deficits were found during the measurement campaigns for the data collection for dynamic simulation studies at five full-scale sequencing batch reactor (SBR) waste water treatment plants (WWTPs), as well as during subsequent calibrations at the investigated plants. Subsequent lab scale investigations showed high evidence for dynamic, cycle-specific NH4+ ad-/desorption to the activated flocs as one reason for this balance deficit. This specific dynamic was investigated at five full-scale SBR plants for the search of the general causing mechanisms. The general mechanism found was a NH4+ desorption from the activated flocs at the end of the nitrification phase with subsequent nitrification and a chemical NH4+ adsorption at the flocs in the course of the filling phases. This NH4+ ad-/desorption corresponds to an antiparallel K+ ad/-desorption.One reasonable full-scale application was investigated at three SBR plants, a controlled filling phase at the beginning of the sedimentation phase. The results indicate that this kind of filling event must be specifically hydraulic controlled and optimised in order to prevent too high waste water break through into the clear water phase, which will subsequently be discarded. IWA Publishing 2008.

The influence of material and mesh characteristics on transmission mode desorption electrospray ionization.

PubMed

Chipuk, Joseph E; Brodbelt, Jennifer S

2009-04-01

Adaptation of desorption electrospray ionization to a transmission mode (TM-DESI) entails passing an electrospray plume through a sample that has been deposited onto a mesh substrate. A combination of mass spectrometry and fluorescence microscopy studies is used to illustrate the critical role material composition, mesh open space, and mesh fiber diameter play on the transmission, desorption, and ionization process. Substrates with open spaces less than 150 microm and accompanying minimal strand diameters produce less scattering of the plume and therefore favor transmission. Larger strand diameters typically encompass larger open spaces, but the increase in the surface area of the strand increases plume scattering as well as solvent and analyte spreading on the mesh. Polypropylene (PP), ethylene tetrafluoroethylene (ETFE), and polyetheretherketone (PEEK) materials afford much better desorption than similarly sized polyethylene terephthalate (PETE) or nylon-6,6 (PA66) substrates. Ultimately, the manner in which the electrospray plume interacts with the mesh as it is transmitted through the substrate is shown to be critical to performing and optimizing TM-DESI analyses. In addition, evidence is presented for analyte dependent variations in the desorption mechanisms of dry and solvated samples.

New insights into the electrochemical desorption of alkanethiol SAMs on gold

PubMed Central

Pensa, Evangelina; Vericat, Carolina; Grumelli, Doris; Salvarezza, Roberto C.; Park, Sung Hyun; Longo, Gabriel S.; Szleifer, Igal

2012-01-01

A combination of Polarization Modulation Infrared Reflection Absorption Spectroscopy (PMIRRAS) under electrochemical control, Electrochemical Scanning Tunneling Microscopy (ECSTM) and Molecular Dynamics (MD) simulations has been used to shed light on the reductive desorption process of dodecanethiol (C12) and octadecanethiol (C18) SAMs on gold in aqueous electrolytes. Experimental PMIRRAS, ECSTM and MD simulations data for C12 desorption are consistent with formation of randomly distributed micellar aggregates stabilized by Na+ ions, coexisting with a lying-down phase of molecules. The analysis of pit and Au island coverage before and after desorption is consistent with the thiolate-Au adatoms models. On the other hand, PMIRRAS and MD data for C18 indicate that the desorbed alkanethiolates adopt a Na+ ion-stabilized bilayer of interdigitated alkanethiolates, with no evidence of lying down molecules. MD simulations also show that both the degree of order and tilt angle of the desorbed alkanethiolates change with the surface charge on the metal, going from bilayers to micelles. These results demonstrate the complexity of the alkanethiol desorption in the presence of water and the fact that chain length and counterions play a key role in a complex structure. PMID:22870508

Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

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

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2014-05-08

We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, themore » N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.« less

Laser Infrared Desorption Spectroscopy to Detect Complex Organic Molecules on Icy Planetary Surfaces

NASA Technical Reports Server (NTRS)

Sollit, Luke S.; Beegle, Luther W.

2008-01-01

Laser Desorption-Infrared Spectroscopy (LD-IR) uses an IR laser pulse to desorb surface materials while a spectrometer measures the emission spectrum of the desorbed materials (Figure 1). In this example, laser desorption operates by having the incident laser energy absorbed by near surface material (10 microns in depth). This desorption produces a plume that exists in an excited state at elevated temperatures. A natural analog for this phenomenon can be observed when comets approach the sun and become active and individual molecular emission spectra can be observed in the IR [1,2,3,4,5]. When this occurs in comets, the same species that initially emit radiation down to the ground state are free to absorb it, reducing the amount of detectable emission features. The nature of our technique results in absorption not occurring, because the laser pulse could easily be moved away form the initial desorption plume, and still have better spatial resolution then reflectance spectroscopy. In reflectance spectroscopy, trace components have a relatively weak signal when compared to the entire active nature of the surface. With LDIR, the emission spectrum is used to identify and analyze surface materials.

Preparative Purification of Polyphenols from Aronia melanocarpa (Chokeberry) with Cellular Antioxidant and Antiproliferative Activity.

PubMed

Gao, Ningxuan; Wang, Yuehua; Jiao, Xinyao; Chou, Shurui; Li, Enhui; Li, Bin

2018-01-10

The aim of this study was the purification process of polyphenols from Aronia melanocarpa (chokeberry), and the purification parameters were optimised by adsorption and desorption tests. By comparing adsorption and desorption ability of polyphenols from chokeberry on six kinds of macroporous resin, XAD-7 resin was selected. Experiments prove that the best purification parameters of static adsorption and desorption were sample pH = 4.0 with 4 h of adsorption; and desorption solvent is 95% ethanol (pH = 7.0) with 2 h of desorption. The best dynamic parameters were 9.3 bed volume (BV) of sample loading amount at a feeding flow rate of 2 BV/h, and washing the column with 5.8 BV of water, followed by subsequent elution with an eluent volume of 5.0 mL at an elution flow rate of 2 BV/h. Next the antioxidant and antiproliferative activity of polyphenols from chokeberry, blueberries, haskap berries was studied on HepG2 human liver cancer cells. The results show that polyphenol from chokeberry has a strong antioxidant effect. Taking into account the content of polyphenols in fruit, polyphenols from chokeberry represent a very valuable natural antioxidant source with antiproliferative products.

Plasma Desorption Mass Spectrometry: Coming of Age.

ERIC Educational Resources Information Center

Cotter, Robert J.

1988-01-01

Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

Air separation with temperature and pressure swing

DOEpatents

Cassano, Anthony A.

1986-01-01

A chemical absorbent air separation process is set forth which uses a temperature swing absorption-desorption cycle in combination with a pressure swing wherein the pressure is elevated in the desorption stage of the process.

Adsorption/Desorption Measurements of Nitroglycerin and Dinitrotoluene in Camp Edwards, Massachusetts Soil

DTIC Science & Technology

2010-02-01

87 8 References...without biocide to K7 soil. ................................................ 31 Figure 8 . The 2,4-DNT concentration in the measured aqueous phase (C...28 Table 8 . Adsorption and desorption partitioning

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.

Electronic Desorption of gas from metals

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

Molvik, A W; Kollmus, H; Mahner, E

During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

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

Surfactant effects on desorption rate of nonionic organic compounds from soils to water

USGS Publications Warehouse

Cesare, David Di; Smith, James A.

1994-01-01

The widespread occurrence of organic contamination in groundwater systems has become an important environmental concern. Of particular interest are nonionic organic compounds, which sorb strongly to natural soil as a result of their characteristic low aqueous solubilities and hydrophobic nature. Consequently, the remediation of nonionic organic contamination in groundwater systems is often highly dependent on contaminant desorption from the sorbed to aqueous phase. The kinetics of desorption will significantly influence the extraction efficiency of pump-and-treat remedial methods that are capable of removing only dissolved phase contaminants.

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

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment

NASA Astrophysics Data System (ADS)

Xue, Q.; Tang, J., Sr.; Chen, H.

2017-12-01

High concentrations of ammonium sulfate, often used in the in-situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages, and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid extractable fractions. 96% of the extractable fraction in soil were desorbed into solution at pH=3.0, and the content of the reducible fraction was observed to initially increase (when pH>4.0) and then decrease (when pH<4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process.

Photothermal Desorption of Single-Walled Carbon Nanotubes and Coconut Shell-Activated Carbons Using a Continuous Light Source for Application in Air Sampling

PubMed Central

Floyd, Evan L.; Sapag, Karim; Oh, Jonghwa; Lungu, Claudiu T.

2014-01-01

Many techniques exist to measure airborne volatile organic compounds (VOCs), each with differing advantages; sorbent sampling is compact, versatile, has good sample stability, and is the preferred technique for collecting VOCs for hygienists. Development of a desorption technique that allows multiple analyses per sample (similar to chemical desorption) with enhanced sensitivity (similar to thermal desorption) would be helpful to field hygienists. In this study, activated carbon (AC) and single-walled carbon nanotubes (SWNT) were preloaded with toluene vapor and partially desorbed with light using a common 12-V DC, 50-W incandescent/halogen lamp. A series of experimental chamber configurations were explored starting with a 500-ml chamber under static conditions, then with low ventilation and high ventilation, finally a 75-ml high ventilation chamber was evaluated. When preloaded with toluene and irradiated at the highest lamp setting for 4min, AC desorbed 13.9, 18.5, 23.8, and 45.9% of the loaded VOC mass, in each chamber configuration, respectively; SWNT desorbed 25.2, 24.3, 37.4, and 70.5% of the loaded VOC mass, respectively. SWNT desorption was significantly greater than AC in all test conditions (P = 0.02–<0.0001) demonstrating a substantial difference in sorbent performance. When loaded with 0.435mg toluene and desorbed at the highest lamp setting for 4min in the final chamber design, the mean desorption for AC was 45.8% (39.7, 52.0) and SWNT was 72.6% (68.8, 76.4) (mean represented in terms of 95% confidence interval). All desorption measurements were obtained using a field grade photoionization detector; this demonstrates the potential of using this technique to perform infield prescreening of VOC samples for immediate exposure feedback and in the analytical lab to introduce sample to a gas chromatograph for detailed analysis of the sample. PMID:25016598

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.

Photothermal desorption of single-walled carbon nanotubes and coconut shell-activated carbons using a continuous light source for application in air sampling.

PubMed

Floyd, Evan L; Sapag, Karim; Oh, Jonghwa; Lungu, Claudiu T

2014-08-01

Many techniques exist to measure airborne volatile organic compounds (VOCs), each with differing advantages; sorbent sampling is compact, versatile, has good sample stability, and is the preferred technique for collecting VOCs for hygienists. Development of a desorption technique that allows multiple analyses per sample (similar to chemical desorption) with enhanced sensitivity (similar to thermal desorption) would be helpful to field hygienists. In this study, activated carbon (AC) and single-walled carbon nanotubes (SWNT) were preloaded with toluene vapor and partially desorbed with light using a common 12-V DC, 50-W incandescent/halogen lamp. A series of experimental chamber configurations were explored starting with a 500-ml chamber under static conditions, then with low ventilation and high ventilation, finally a 75-ml high ventilation chamber was evaluated. When preloaded with toluene and irradiated at the highest lamp setting for 4min, AC desorbed 13.9, 18.5, 23.8, and 45.9% of the loaded VOC mass, in each chamber configuration, respectively; SWNT desorbed 25.2, 24.3, 37.4, and 70.5% of the loaded VOC mass, respectively. SWNT desorption was significantly greater than AC in all test conditions (P = 0.02-<0.0001) demonstrating a substantial difference in sorbent performance. When loaded with 0.435mg toluene and desorbed at the highest lamp setting for 4min in the final chamber design, the mean desorption for AC was 45.8% (39.7, 52.0) and SWNT was 72.6% (68.8, 76.4) (mean represented in terms of 95% confidence interval). All desorption measurements were obtained using a field grade photoionization detector; this demonstrates the potential of using this technique to perform infield prescreening of VOC samples for immediate exposure feedback and in the analytical lab to introduce sample to a gas chromatograph for detailed analysis of the sample. © The Author 2014. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

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.

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

Modelling deuterium release during thermal desorption of D +-irradiated tungsten

NASA Astrophysics Data System (ADS)

Poon, M.; Haasz, A. A.; Davis, J. W.

2008-03-01

Thermal desorption profiles were modelled based on SIMS measurements of implantation profiles and using the multi-trap diffusion code TMAP7 [G.R. Longhurst, TMAP7: Tritium Migration Analysis Program, User Manual, Idaho National Laboratory, INEEL/EXT-04-02352 (2004)]. The thermal desorption profiles were the result of 500 eV/D + irradiations on single crystal tungsten at 300 and 500 K to fluences of 10 22-10 24 D +/m 2. SIMS depth profiling was performed after irradiation to obtain the distribution of trapped D within the top 60 nm of the surface. Thermal desorption spectroscopy (TDS) was performed subsequently to obtain desorption profiles and to extract the total trapped D inventory. The SIMS profiles were calibrated to give D concentrations. To account for the total trapped D inventory measured by TDS, SIMS depth distributions were used in the near-surface (surface to 30 nm), NRA measurements [V.Kh. Alimov, J. Roth, M. Mayer, J. Nucl. Mater. 337-339 (2005) 619] were used in the range 1-7 μm, and a linear drop in the D distribution was assumed in the intermediate sub-surface region (˜30 nm to 1 μm). Traps were assumed to be saturated so that the D distribution also represented the trap distribution. Three trap energies, 1.07 ± 0.03, 1.34 ± 0.03 and 2.1 ± 0.05 eV were required to model the 520, 640 and 900 K desorption peaks, respectively. The 1.34 and 1.07 eV traps correspond to trapping of a first and second D atom at a vacancy, respectively, while the 2.1 eV trap corresponds to atomic D trapping at a void. A fourth trap energy of 0.65 eV was used to fit the 400 K desorption peak observed by Quastel et al. [A.D. Quastel, J.W. Davis, A.A. Haasz, R.G. Macaulay-Newcombe, J. Nucl. Mater. 359 (2006) 8].

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.

COSOLVENT EFFECTS ON SORPTION ISOTHERM LINEARITY

EPA Science Inventory

Sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. In this study, aqueous and mixed solvent systems were used t...

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...

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

Rotational state modification and fast ortho-para conversion of H2 trapped within the highly anisotropic potential of Pd(210)

NASA Astrophysics Data System (ADS)

Ohno, S.; Ivanov, D.; Ogura, S.; Wilde, M.; Arguelles, E. F.; Diño, W. A.; Kasai, H.; Fukutani, K.

2018-02-01

The rotational state and ortho-para conversion of H2 on a Pd(210) surface is investigated with rotational-state-selective temperature-programmed desorption (RS-TPD) and theoretical calculations. The isotope dependence of TPD shows a higher desorption energy for D2 than that for H2, which is ascribed to the rotational and zero-point vibrational energies. The RS-TPD data show that the desorption energy of H2(J =1 ) (J : rotational quantum number) is higher than that of H2(J =0 ). This is due to the orientationally anisotropic potential confining the adsorbed H2, which is in agreement with theoretical calculations. Furthermore, the H2 desorption intensity ratio in J =1 and J =0 indicates fast ortho-para conversion in the adsorption state, which we estimate to be of the order of 1 s.

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

Desorption from interstellar grains

NASA Technical Reports Server (NTRS)

Leger, A.; Jura, M.; Omont, A.

1985-01-01

Different desorption mechanisms from interstellar grains are considered to resolve the conflict between the observed presence of gaseous species in molecular clouds and their expected depletion onto grains. The physics of desorption is discussed with particular reference to the process of grain heating and the specific heat of the dust material. Impulsive heating by X-rays and cosmic rays is addressed. Spot heating of the grains by cosmic rays and how this can lead to desorption of mantles from very large grains is considered. It is concluded that CO depletion on grains will be small in regions with A(V) less than five from the cloud surface and n(H) less than 10,000, in agreement with observations and in contrast to expectations from pure thermal equilibrium. Even in very dense and obscured regions and in the absence of internal ultraviolet sources, the classical evaporation of CO or N2 and O2-rich mantles by cosmic rays is important.

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

PubMed

Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

2015-11-28

We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

Desorption atmospheric pressure photoionization.

PubMed

Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Arvola, Ville; Kotiaho, Tapio; Ketola, Raimo A; Franssila, Sami; Kauppila, Tiina J; Kostiainen, Risto

2007-10-15

An ambient ionization technique for mass spectrometry, desorption atmospheric pressure photoionization (DAPPI), is presented, and its application to the rapid analysis of compounds of various polarities on surfaces is demonstrated. The DAPPI technique relies on a heated nebulizer microchip delivering a heated jet of vaporized solvent, e.g., toluene, and a photoionization lamp emitting 10-eV photons. The solvent jet is directed toward sample spots on a surface, causing the desorption of analytes from the surface. The photons emitted by the lamp ionize the analytes, which are then directed into the mass spectrometer. The limits of detection obtained with DAPPI were in the range of 56-670 fmol. Also, the direct analysis of pharmaceuticals from a tablet surface was successfully demonstrated. A comparison of the performance of DAPPI with that of the popular desorption electrospray ionization method was done with four standard compounds. DAPPI was shown to be equally or more sensitive especially in the case of less polar analytes.

Rapid screening of pharmaceutical drugs using thermal desorption - SALDI mass spectrometry

NASA Astrophysics Data System (ADS)

Grechnikov, A. A.; Kubasov, A. E.; Georgieva, V. B.; Borodkov, A. S.; Nikiforov, S. M.; Simanovsky, Ya O.; Alimpiev, S. S.

2012-12-01

A novel approach to the rapid screening of pharmaceutical drugs by surface assisted laser desorption-ionization (SALDI) mass spectrometry with the rotating ball interface coupled with temperature programmed thermal desorption has been developed. Analytes were thermally desorbed and deposited onto the surface of amorphous silicon substrate attached to the rotating ball. The ball was rotated and the deposited analytes were analyzed using SALDI. The effectiveness of coupling SALDI mass spectrometry with thermal desorption was evaluated by the direct and rapid analysis of tablets containing lidocaine, diphenhydramine and propranolol without any sample pretreatment. The overall duration of the screening procedure was 30÷40 sec. Real urine samples were studied for drug analysis. It is shown that with simple preparation steps, urine samples can be quantitatively analyzed using the proposed technique with the detection limits in the range of 0.2÷0.5 ng/ml.

[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, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

2014-07-17

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

Adsorption and reaction of propene on Ni(100)

NASA Astrophysics Data System (ADS)

Kleyna, R.; Borgmann, D.; Wedler, G.

1998-05-01

Photoelectron spectroscopy (UPS, XPS) and thermal desorption techniques were used to study the chemisorption and decomposition reactions of propene on Ni(100). Propene is molecularly adsorbed at temperatures below 150 K. At saturation coverage the TD spectrum shows two propene desorption peaks at 155 and 225 K and three hydrogen desorption peaks at 300, 330 and 380 K with a shoulder at 420 K. No other desorbing species could be detected. The amount of desorption of propene was determined by XPS to be 20% of the saturation coverage. The electronic structure of adsorbed propene and the chemical nature of its decomposition products were deduced from UP and XP spectra taken at saturation coverage. Adsorption at low temperatures results in a π-bonded species which is stable up to 150 K. At temperatures above 150 K the UP spectra point to a σ-bonded species which decomposes further at temperatures above 260 K.

Towards atomic-level mechanics: Adhesive forces between aromatic molecules and carbon nanotubes

NASA Astrophysics Data System (ADS)

Lechner, Christoph; Sax, Alexander F.

2017-10-01

The adhesive forces for desorption of the four aromatic compounds benzene, anthracene, pyrene, and tetracene from a (8,0) carbon nanotube (CNT) are investigated and compared to the desorption from graphene. The desorption energies are found to be proportional to the size of the contact zone in the adsorbent/adsorbate complex while maximum adhesive forces are proportional to the part of the contact zone where attractive interactions are reduced when external forces pull on the adsorbate. To assess the influence of the curvature, type of CNT, and the adsorbate's orientation, the desorption processes from six zigzag CNT and four armchair CNT are studied for pyrene and tetracene. For some properties, the results are independent of the curvature of the adsorbent, whereas for others we find marked differences. Aspects of elasticity are considered as well as the influence of the Pauli exclusion principle on the equilibrium geometries in adsorbent/adsorbate complexes.

The Effect of Platinum-coatings on Hydrogen- and Water-absorption and Desorption Characteristics of Lithium Zirconate

NASA Astrophysics Data System (ADS)

Tsuchiya, B.; Bandow, S.; Nagata, S.; Saito, K.; Tokunaga, K.; Morita, K.

Hydrogen (H)- and water (H2O)-storage and desorption characteristics of 25 nm thick Pt films onLi2ZrO3composite materials, exposed to normal air at room temperature, have been investigated by means of elastic recoil detection (ERD), Rutherford backscattering spectrometry (RBS), weight gain measurement (WGM), and thermal desorption spectroscopy (TDS) techniques. It was found by the ERD and TDS that H and H2O were absorbed into the Pt-coated Li2ZrO3 in air at room temperature and desorbed from it in vacuum at much low temperatures of approximately 317 and 309 K, respectively. In addition, the WGM and TDS spectra revealed that the absorption and desorption characters ofsome gases such as CH4, CO, and CO2including H as well as H2Ointo the Li2ZrO3 bulk were improved by Pt deposition.

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.

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.

Drawing a different picture with pencil lead as matrix-assisted laser desorption/ionization matrix for fullerene derivatives.

PubMed

Nye, Leanne C; Hungerbühler, Hartmut; Drewello, Thomas

2018-02-01

Inspired by reports on the use of pencil lead as a matrix-assisted laser desorption/ionization matrix, paving the way towards matrix-free matrix-assisted laser desorption/ionization, the present investigation evaluates its usage with organic fullerene derivatives. Currently, this class of compounds is best analysed using the electron transfer matrix trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB), which was employed as the standard here. The suitability of pencil lead was additionally compared to direct (i.e. no matrix) laser desorption/ionization-mass spectrometry. The use of (DCTB) was identified as the by far gentler method, producing spectra with abundant molecular ion signals and much reduced fragmentation. Analytically, pencil lead was found to be ineffective as a matrix, however, appears to be an extremely easy and inexpensive method for producing sodium and potassium adducts.

CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

NASA Astrophysics Data System (ADS)

Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

2002-01-01

Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

A novel experimental system of high stability and lifetime for the laser-desorption of biomolecules.

PubMed

Taherkhani, Mehran; Riese, Mikko; BenYezzar, Mohammed; Müller-Dethlefs, Klaus

2010-06-01

A novel laser desorption system, with improved signal stability and extraordinary long lifetime, is presented for the study of jet-cooled biomolecules in the gas phase using vibrationally resolved photoionization spectroscopy. As a test substance tryptophane is used to characterize this desorption source. A usable lifetime of above 1 month (for a laser desorption repetition rate of 20 Hz) has been observed by optimizing the pellets (graphite/tryptophane, 3 mm diameter and 6 mm length) from which the substance is laser-desorbed. Additionally, the stability and signal-to-noise ratio has been improved by averaging the signal over the entire sample pellet by synchronizing the data acquisition with the rotation of the sample rod. The results demonstrate how a combination of the above helps to produce stable and conclusive spectra of tryptophane using one-color and two-color resonant two-photon ionization studies.

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.

Characterization of adsorption and desorption of lawn herbicide siduron in heavy metal contaminated soils.

PubMed

Jiang, Rong; Wang, Meie; Chen, Weiping

2018-08-01

Siduron is a widely used herbicide in urban lawn and has been frequently detected in urban and suburban surface water. However, characteristics of its environmental behavior in soil are seldom reported. The combined pollution of heavy metals, especially for Cu, Pb, Cd, Zn and siduron would be common because of the widely existence of heavy metal pollution in urban soils. In this study, four soils with similar physicochemical properties but different levels of preexisting heavy metals were selected to investigate the adsorption and successive desorption of siduron using batch experiments. The results revealed a low sorption of siduron to all the tested soils. The organic carbon normalized distribution coefficient (K oc ) of siduron in the studied soils ranged from 117 to 137 L kg -1 and was not significantly correlated to heavy metal levels. No apparent desorption hysteresis was observed with the hysteresis index (HI) ranging from 0.921 to 1.11. More than 50% of the sorbed siduron was readily released into soil solution. Results suggested that siduron was highly mobile and bioavailable in the studied soils. Significant correlation was found between adsorption/desorption parameters and soil organic carbon (SOC) in four soils. soil organic matter was thus considered as the dominant factor determining the adsorption and desorption of siduron in soils. Different from most of reported studies conducted by laboratory-amended soils, the influence of preexisting heavy metals on the adsorption-desorption of siduron was not significant in this work. Copyright © 2018 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.

Kinetic and isothermal adsorption-desorption of PAEs on biochars: effect of biomass feedstock, pyrolysis temperature, and mechanism implication of desorption hysteresis.

PubMed

Jing, Fanqi; Pan, Minjun; Chen, Jiawei

2018-04-01

Biochar has the potential to sequester biomass carbon efficiently into land, simultaneously while improving soil fertility and crop production. Biochar has also attracted attention as a potential sorbent for good performance on adsorption and immobilization of many organic pollutants such as phthalic acid esters (PAEs), a typical plasticizer in plastic and presenting a current environmental issue. Due to lack of investigation on the kinetic and thermodynamic adsorption-desorption of PAEs on biochar, we systematically assessed adsorption-desorption for two typical PAEs, dimethyl phthalate (DMP) and diethyl phthalate (DEP), using biochar derived from peanut hull and wheat straw at different pyrolysis temperatures (450, 550, and 650 °C). The aromaticity and specific surface area of biochars increased with the pyrolysis temperature, whereas the total amount of surface functional groups decreased. The quasi-second-order kinetic model could better describe the adsorption of DMP/DEP, and the adsorption capacity of wheat straw biochars was higher than that of peanut hull biochars, owing to the O-bearing functional groups of organic matter on exposed minerals within the biochars. The thermodynamic analysis showed that DMP/DEP adsorption on biochar is physically spontaneous and endothermic. The isothermal desorption and thermodynamic index of irreversibility indicated that DMP/DEP is stably adsorbed. Sorption of PAEs on biochar and the mechanism of desorption hysteresis provide insights relevant not only to the mitigation of plasticizer mobility but also to inform on the effect of biochar amendment on geochemical behavior of organic pollutants in the water and soil.

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.

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).

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.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

NASA Astrophysics Data System (ADS)

Hong, Sung-Young; Xu, Pan; Camillone, Nina R.; White, Michael G.; Camillone, Nicholas

2016-07-01

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

Sorption and desorption of glyphosate in Mollisols and Ultisols soils of Argentina.

PubMed

Gómez Ortiz, Ana Maria; Okada, Elena; Bedmar, Francisco; Costa, José Luis

2017-10-01

In Argentina, glyphosate use has increased exponentially in recent years as a result of the widespread adoption of no-till management combined with genetically modified glyphosate-resistant crops. This massive use of glyphosate has created concern about its potential environmental impact. Sorption-desorption of glyphosate was studied in 3 Argentinean soils with contrasting characteristics. Glyphosate sorption isotherms were modeled using the Freundlich equation to estimate the sorption coefficient (K f ). Glyphosate sorption was high, and the K f varied from 115.6 to 1612 mg 1-1/n L 1/n /kg. Cerro Azul soil had the highest glyphosate sorption capacity as a result of a combination of factors such as higher clay content, cation exchange capacity, total iron, and aluminum oxides, and lower available phosphorus and pH. Desorption isotherms were also modeled using the Freundlich equation. In general, desorption was very low (<12%). The low values of hysteresis coefficient confirm that glyphosate strongly sorbs to the soils and that it is almost an irreversible process. Anguil soil had a significantly higher desorption coefficient (K fd ) than the other soils, associated with its lower clay content and higher pH and phosphorus. Glyphosate high sorption and low desorption to the studied soils may prevent groundwater contamination. However, it may also affect its bioavailability, increasing its persistence and favoring its accumulation in the environment. The results of the present study contribute to the knowledge and characterization of glyphosate retention in different soils. Environ Toxicol Chem 2017;36:2587-2592. © 2017 SETAC. © 2017 SETAC.

CH4 dissociation on Ru(0001): A view from both sides of the barrier

NASA Astrophysics Data System (ADS)

Mortensen, H.; Diekhöner, L.; Baurichter, A.; Luntz, A. C.

2002-04-01

This paper reports measurements of both dissociative adsorption on and associative desorption from CH4 on Ru(0001). We consider the former a view of dissociation from the front side of the barrier, while the latter is considered as a view of dissociation from the back side of the barrier. A combination of both previous and new molecular beam measurements of dissociative adsorption shows that S0 depends on all experimental variables (E, Tn, Ts and isotope) in a manner similar to other close-packed transition metals. The interpretation of this behavior in terms of a theoretical description of the dissociation is discussed critically, with special emphasis on insights from new theoretical studies. The energy-resolved desorption flux Df(E,Ts) is obtained in associative desorption experiments using the technique of laser assisted associative desorption (LAAD). Measurements at several Ts allow both a direct determination of the adiabatic barrier V*(0) and considerable insight into the dynamics of dissociation. The V*(0) obtained from Df(E,Ts) is in excellent agreement with density functional theory (DFT) calculations and with the value indirectly inferred from molecular beam experiments. The chief dynamic conclusion from an analysis of Df(E,Ts) is that both bending and stretching coordinates must be produced in associative desorption, although they are not populated statistically. The absence of an isotope effect in the shape of Df(E,Ts) argues against the importance of tunneling in the desorption/adsorption. When reactive fluxes are compared via detailed balance, both the molecular beam experiment and the LAAD experiment are in good agreement.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

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

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

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

Hong, Sung-Young; Camillone, Nina R.; Camillone, Nicholas, E-mail: nicholas@bnl.gov

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increasesmore » roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η{sub el}, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η{sub el} largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

DOE PAGES

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.; ...

2016-07-01

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Sorption and desorption of carbamazepine from water by smectite clays.

PubMed

Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

2010-11-01

Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays. Copyright © 2010 Elsevier Ltd. All rights reserved.

COSOLVENT EFFECTS ON ORGANIC CHEMICAL PARTITIONING TO SEDIMENT ORGANIC CARBON

EPA Science Inventory

Sorption-desorption hysteresis, slow desorption kinetics and resultant bioavailability, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. The objectives of this study we...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2012 CFR

2012-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2013 CFR

2013-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2011 CFR

2011-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2012 CFR

2012-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2014 CFR

2014-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2014 CFR

2014-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2013 CFR

2013-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2011 CFR

2011-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

Waste Isolation Safety Assessment Program. Task 4. Third Contractor Information Meeting. [Adsorption-desorption on geological media

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

Not Available

1980-06-01

The study subject of this meeting was the adsorption and desorption of radionuclides on geologic media under repository conditions. This volume contans eight papers. Separate abstracts were prepared for all eight papers. (DLC)

40 CFR 158.260 - Experimental use permit data requirements for environmental fate.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Leaching and adsorption/desorption R NR NR NR R NR TGAI or PAIRA 3 (d) Test notes. The following test notes... cranberry bogs and rice paddies. 3. Adsorption and desorption using a batch equilibrium method is preferred...

Comparative sorption, desorption and leaching potential of aminocyclopyrachlor and picloram

USDA-ARS?s Scientific Manuscript database

Aminocyclopyrachlor and picloram sorption, desorption and leaching potential were investigated in three soils from Minnesota and Hawaii. Aminocyclopyrachlor and picloram sorption fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram ...

40 CFR 158.260 - Experimental use permit data requirements for environmental fate.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Leaching and adsorption/desorption R NR NR NR R NR TGAI or PAIRA 3 (d) Test notes. The following test notes... cranberry bogs and rice paddies. 3. Adsorption and desorption using a batch equilibrium method is preferred...

40 CFR 158.260 - Experimental use permit data requirements for environmental fate.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Leaching and adsorption/desorption R NR NR NR R NR TGAI or PAIRA 3 (d) Test notes. The following test notes... cranberry bogs and rice paddies. 3. Adsorption and desorption using a batch equilibrium method is preferred...

40 CFR 158.260 - Experimental use permit data requirements for environmental fate.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Leaching and adsorption/desorption R NR NR NR R NR TGAI or PAIRA 3 (d) Test notes. The following test notes... cranberry bogs and rice paddies. 3. Adsorption and desorption using a batch equilibrium method is preferred...

Heavy-ion induced electronic desorption of gas from metals

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

Molvik, A W; Kollmus, H; Mahner, E

During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/d/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

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.

Comparison between different adsorption-desorption kinetics schemes in two dimensional lattice gas

NASA Astrophysics Data System (ADS)

Huespe, V. J.; Belardinelli, R. E.; Pereyra, V. D.; Manzi, S. J.

2017-12-01

Monte Carlo simulation is used to study the adsorption-desorption kinetics in the framework of the kinetic lattice-gas model. Three schemes of the so-called hard dynamics and five schemes of the so called soft dynamics were used for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and non-equilibrium observable, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and non-equilibrium observables have several problems.

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.

Anionic surfactant enhanced phosphate desorption from Mg/Al-layered double hydroxides by micelle formation.

PubMed

Shimamura, Akihiro; Jones, Mark I; Metson, James B

2013-12-01

Desorption of interlayer hydrogen phosphate (HPO4) from hydrogen phosphate intercalated Mg/Al-layered double hydroxide (LDH-HPO4) by anion exchange with surfactant anions has been investigated under controlled conditions. Three types of surfactant, Dodecylbenzenesulphonate (DBS), Dodecylsulphate (DS) and 1-Octanesulphonate (OS), anions were used for intercalation experiments over a range of concentrations, and for all solutions, it was shown that the desorption of hydrogen phosphate is enhanced at concentrations close to the critical micelle concentration (CMC). Intercalation of the surfactant anions into LDH-HPO4 was confirmed by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning electron microscopy (SEM). More than 90% removal of the hydrogen phosphate was achieved at CMC. Repeat adsorption tests to investigate recyclability showed that desorption with 0.005 M DBS improved subsequent phosphate re-adsorption, allowing around 90% of the original adsorption over three cycles. This is much higher than when desorption was conducted using either Na2CO3 or NaCl-NaOH solutions, even at much higher concentrations. This study suggests potential economic and environmental advantages in using these surfactants in improving the cycling performance of LDH materials as absorbents for clean-up of water systems. Copyright © 2013 Elsevier Inc. All rights reserved.

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

Huang, Huogen; Chen, Liang

Ti-Zr-Ni quasicrystals have been demonstrated to store a large number of hydrogen atoms, which implies strong potential application in hydrogen energy field for them. However, the desorption of hydrogen atoms in the quasicrystals is quite difficult, with the indication of high desorption temperature and slow desorption rate. The shortage limits their use in the field to a large extent. But this kind of quasicrystals might be used in nuclear fusion energy field, because tritium as a coral fuel for nuclear fusion needs tight storage. However, equilibrium pressure at room temperature of Ti-Zr-Ni quasicrystals, important for their application in fusion energymore » field, has not been clear yet. In this work, we designed a gas-solid reaction system with the pressure resolution of 10{sup −8}Pa and carried out hydrogen desorption investigation at different temperatures on Ti{sub 36}Zr{sub 40}Ni{sub 20}Pd{sub 4} icosahedral quasicrystal. Based on three Pressure-Composition-Temperature desorption curves, we speculate according to Van’t Hoff theory about hydrogen storage that its equilibrium pressure at room temperature could be at the magnitude of 10{sup −6}Pa, displaying good stability of hydrogen in the quasicrystal and also implying application prospects in fusion energy field for quasicrystals of this type.« less

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.

(100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

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

Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF

2011-05-01

Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoreticalmore » DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.« less

Sorption-desorption of antimony species onto calcined hydrotalcite: Surface structure and control of competitive anions.

PubMed

Constantino, Leonel Vinicius; Quirino, Juliana Nunes; Abrão, Taufik; Parreira, Paulo Sérgio; Urbano, Alexandre; Santos, Maria Josefa

2018-02-15

Calcined hydrotalcite can be applied to remove anionic contaminants from aqueous systems such as antimony species due to its great anion exchange capacity and high surface area. Hence, this study evaluated antimonite and antimonate sorption-desorption processes onto calcined hydrotalcite in the presence of nitrate, sulfate and phosphate. Sorption and desorption experiments of antimonite and antimonate were carried out in batch equilibrium and the post-sorption solids were analyzed by X-ray fluorescence (EDXRF). Sorption data were better fitted by dual-mode Langmuir-Freundlich model (R 2 >0.99) and desorption data by Langmuir model. High maximum sorption capacities were found for the calcined hydrotalcite, ranging from 617 to 790meqkg -1 . The competing anions strongly affected the antimony sorption. EDXRF analysis and mathematical modelling showed that sulfate and phosphate presented higher effect on antimonite and antimonate sorption, respectively. High values for sorption efficiency (SE=99%) and sorption capacity were attributed to the sorbent small particles and the large surface area. Positive hysteresis indexes and low mobilization factors (MF>3%) suggest very low desorption capacity to antimony species from LDH. These calcined hydrotalcite characteristics are desirable for sorption of antimony species from aqueous solutions. Copyright © 2017. Published by Elsevier B.V.

Surface tuning laser desorption/ionization mass spectrometry (STLDI-MS) for the analysis of small molecules using quantum dots.

PubMed

Abdelhamid, Hani Nasser; Chen, Zhen-Yu; Wu, Hui-Fen

2017-08-01

In most applications of quantum dots (QDs) for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS), one side of QDs is supported by a solid substrate (stainless - steel plate), whereas the other side is in contact with the target analytes. Therefore, the surface capping agent of QDs is a key parameter for laser desorption/ionization mass spectrometry (LDI-MS). Cadmium telluride quantum dots (CdTe QDs) modified with different capping agents are synthesized, characterized, and applied for surface tuning laser desorption/ionization mass spectrometry (STLDI-MS). Data shows that CdTe quantum dot modified cysteine (cys@CdTe QDs) has an absorption that matches with the wavelength of the N 2 laser (337 nm). The synergistic effect of large surface area and absorption of the laser irradiation of cys@CdTe QDs enhances the LDI-MS process for small - molecule analysis, including α-, β-, and γ-cyclodextrin, gramicidin D, perylene, pyrene, and triphenylphosphine. Cys@CdTe QDs are also applied using Al foils as substrates. Aluminum foil combined with cys@CdTe QDs enhances the ionization efficiency and is cheap compared to traditional matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with a stainless - steel plate.

Dimethyl Methylphosphonate Adsorption Capacities and Desorption Energies on Ordered Mesoporous Carbons.

PubMed

Huynh, Kim; Holdren, Scott; Hu, Junkai; Wang, Luning; Zachariah, Michael R; Eichhorn, Bryan W

2017-11-22

In this study, we determine effective adsorption capacities and desorption energies for DMMP with highly ordered mesoporous carbons (OMCs), 1D cylindrical FDU-15, 3D hexagonal CMK-3, 3D bicontinuous CMK-8, and as a reference, microporous BPL carbon. After exposure to DMMP vapor at room temperature for approximately 70 and 800 h, the adsorption capacity of DMMP for each OMC was generally proportional to the total surface area and pore volume, respectively. Desorption energies of DMMP were determined using a model-free isoconversional method applied to thermogravimetric analysis (TGA) data. Our experiments determined that DMMP saturated carbon will desorb any weakly bound DMMP from pores >2.4 nm at room temperature, and no DMMP will adsorb into pores smaller than 0.5 nm. The calculated desorption energies for high surface coverages, 25% DMMP desorbed from pores ≤2.4 nm, are 68-74 kJ mol -1 , which is similar to the DMMP heat of vaporization (52 kJ mol -1 ). At lower surface coverages, 80% DMMP desorbed, the DMMP desorption energies from the OMCs are 95-103 kJ mol -1 . This is overall 20-30 kJ mol -1 higher in comparison to that of BPL carbon, due to the pore size and diffusion through different porous networks.

Effect of inorganic regenerant properties on pharmaceutical adsorption and desorption performance on polymer anion exchange resin.

PubMed

Zheng, Shaokui; Li, Xiaofeng; Zhang, Xueyu; Wang, Wei; Yuan, Shengliu

2017-09-01

This study investigated the potential effect of four frequently used inorganic regenerant properties (i.e., ionic strength, cation type, anion type, and regeneration solution volume) on the desorption and adsorption performance of 14 pharmaceuticals, belonging to 12 therapeutic classes with different predominant chemical forms and hydrophobicities, using polymeric anion exchange resin (AER)-packed fixed-bed column tests. After preconditioning with NaCl, NaOH, or saline-alkaline (SA) solutions, all resulting mobile counterion types of AERs effectively adsorbed all 14 pharmaceuticals, where the preferential magnitude of OH - -type = Cl -  + OH - -type > Cl - -type. During regeneration, ionic strength (1 M versus 3 M NaCl) had no significant influence on desorption performance for any of the 14 pharmaceuticals, while no regenerant cation (HCl versus NaCl) or anion type (NaCl versus NaOH and SA) achieved higher desorption efficiencies for all pharmaceuticals. A volumetric increase in 1 M or 3 M NaCl solutions significantly improved the desorption efficiencies of most pharmaceuticals, irrespective of ionic strength. The results indicate that regeneration protocols, including regenerant cation type, anion type and volume, should be optimized to improve pharmaceutical removal by AERs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trapping and desorption of complex organic molecules in water at 20 K

NASA Astrophysics Data System (ADS)

Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

2015-10-01

The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

Ambient diode laser desorption dielectric barrier discharge ionization mass spectrometry of nonvolatile chemicals.

PubMed

Gilbert-López, Bienvenida; Schilling, Michael; Ahlmann, Norman; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan F; Franzke, Joachim

2013-03-19

In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface.

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.

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

PubMed

Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

2006-03-07

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

PubMed

Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

2017-10-03

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

Modification of the acid/base properties of γ-Al2O3 by oxide additives: An ethanol TPD investigation

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

Kwak, Ja Hun; Lee, Jaekyoung; Szanyi, Janos

2016-02-26

The electronic properties of oxide-modified γ Al2O3 surfaces were investigated by using ethanol TPD. Ethanol TPD showed remarkable sensitivity toward the surface structures and electronic properties of the aluminas modified by various transition metal oxides. Maximum desorption rates for the primary product of ethanol adsorption, ethylene, were observed at 225 °C on non-modified γ-Al2O3. Desorption temperature of ethanol over a γ Al2O3 samples with different amounts of BaO linearly increased with increasing loading. On the contrary, ethanol desorption temperature on Pt modified γ-Al2O3 after calcined at 500 oC linearly decreased with increasing Pt loading. These results clearly suggested that themore » acid/base properties of the γ-Al2O3 surface can be strongly affected by ad-atoms. For confirming these arguments, we performed ethanol TPD experiments on various oxide modified γ-Al2O3 and normalized the maximum desorption temperatures based on the same number of oxide dopants. These normalized ethanol desorption temperatures linearly correlate with the electronegativity of the metal atom in the oxide. This linear relationship clearly demonstrates that the acidic properties of alumina surfaces can be systematically changed by ad-atoms.« less

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.

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.

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...

Quantum theory of laser-stimulated desorption

NASA Technical Reports Server (NTRS)

Slutsky, M. S.; George, T. F.

1978-01-01

A quantum theory of laser-stimulated desorption (LSDE) is presented and critically analyzed. It is shown how LSDE depends on laser-pulse characteristics and surface-lattice dynamics. Predictions of the theory for a Debye model of the lattice dynamics are compared to recent experimental results.

SITE TECHNOLOGY CAPSULE: CLEAN BERKSHIRES, INC. THERMAL DESORPTION SYSTEM

EPA Science Inventory

The thermal desorption process devised by Clean Berkshires, Inc., works by vaporizing the organic contaminants from the soil with heat, isolating the contaminant! in a gas stream, and then destroying them in a high efficiency afterburner. The processed solids are either replaced ...

Rapid detection of nicotine from breath using desorption ionisation on porous silicon.

PubMed

Guinan, T M; Abdelmaksoud, H; Voelcker, N H

2017-05-04

Desorption ionisation on porous silicon (DIOS) was used for the detection of nicotine from exhaled breath. This result represents proof-of-principle of the ability of DIOS to detect small molecular analytes in breath including biomarkers and illicit drugs.

Desorption of 137Cs from Brachythecium mildeanum moss using acid solutions with pH 4.60-6.50

NASA Astrophysics Data System (ADS)

Čučulović, Ana; Veselinović, Dragan

2015-12-01

The desorption of 137Cs from the moss Brachythecium mildeanum (Schimp.) was performed using the following solutions: H2SO4 ( I), HNO3 ( II), H2SO4 + HNO3 ( III) with pH values of 4.60, 5.15, and 5.75, respectively, as well as distilled water (D) with pH 6.50. After five successive desorptions, each lasting 24 h, 20.5-37.6% 137Cs was desorbed from the moss using these solutions, while 30.7% of the starting content was desorbed using distilled water. The first desorption removed the highest percent of the original content of 137Cs in the moss (11.3-18.4%). This was determined by measuring 137Cs activity. If the current results are compared with those obtained earlier it may be concluded that 137Cs desorption from mosses is not species-dependent. The obtained results indicate the necessity of investigating the influence of acid rain, or rather, of H+ ions, on desorption of other ions from biological systems, i.e., the role of H+ ions in spreading other polluting compounds and thus producing secondary environmental pollution. From the results of this study it follows that acid rain will lead, through H+ ion action, to a similar increasing pollution of fallout waters with other ionic compounds which may not be present in the water before the contact with the plants and thus enable the pollution spreading. In the investigated system, the replacement of H+ ions from acid rains by more dangerous radioactive ions occured, increasing the concentration of the radioactive ions in the water, which demonstrates that the same process takes place in fallout water.

Growth kinetics of indium metal atoms on Si(1 1 2) surface

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

Raj, Vidur; Chauhan, Amit Kumar Singh; Gupta, Govind, E-mail: govind@nplindia.org

Graphical abstract: Controlled growth of indium atoms on Si(1 1 2) surface has been carried out systematically and the influence of substrate temperature on the kinetics is analysed under various growth conditions. Temperature induced anomalous layer-to-clusters transformation during thermal desorption has also been reported. - Highlights: • Controlled growth of indium atoms on Si(1 1 2) surface & their thermal stability. • Influence of substrate temperature on the kinetics under various growth conditions. • Temperature induced layer-to-clusters transformation during thermal desorption. - Abstract: The growth kinetics and desorption behavior of indium (In) atoms grown on high index Si(1 1 2)more » surface at different substrate temperatures has been studied. Auger electron spectroscopy analysis revealed that In growth at room temperature (RT) and high substrate temperature (HT) ∼250 °C follows Frank–van der Merve growth mode whereas at temperatures ≥450 °C, In growth evolves through Volmer–Weber growth mode. Thermal desorption studies of RT and 250 °C grown In/Si(1 1 2) systems show temperature induced rearrangement of In atoms over Si(1 1 2) surface leading to clusters to layer transformation. The monolayer and bilayer desorption energies for RT grown In/Si(1 1 2) system are calculated to be 2.5 eV and 1.52 eV, while for HT-250 °C the values are found to be 1.6 eV and 1.3 eV, respectively. This study demonstrates the effect of temperature on growth kinetics as well as on the multilayer/monolayer desorption pathway of In on Si(1 1 2) surface.« less

Interactive effects of sulfadiazine and Cu(II) on their sorption and desorption on two soils with different characteristics.

PubMed

Xu, Yonggang; Yu, Wantai; Ma, Qiang; Zhou, Hua

2015-11-01

Antibiotics and heavy metals often coexist in soils due to land application of animal wastes and other sources of inputs. The aim of this study is to evaluate the interaction of Cu(II) and sulfadiazine (SDZ) regarding to their sorption and desorption on Brown soil (BS, luvisols) and Red soil (RS, Udic Ferrosols) using batch experiments. The presence of Cu(II) significantly enhanced sorption of SDZ on BS at pH>5.0, and this trend increased with increasing pH, which was mainly ascribed to the formation of ternary complexes of Cu-SDZ-soil and/or SDZ-Cu-soil. In contrast, Cu(II) only slightly increased SDZ sorption on RS at pH<5.0 due to the decrease of equilibrium solution pH, whereas it hardly affected SDZ sorption at pH>5.0 because RS had high oxides contents and low affinity for Cu(II). In addition, Cu(II) inhibited SDZ desorption from BS but promoted SDZ desorption from RS, which was related to their different sorption mechanisms. The presence of SDZ exerted no significant effect on the sorption of Cu(II) on the two soils at pH<6.5 because of its low sorption coefficients (Kd), while slightly decreased Cu(II) sorption at pH>6.5 by forming water-soluble complexes. Furthermore, SDZ had little effect on Cu(II) desorption from the two soils at natural pH. These results indicate that soil characteristics strongly influence the interactions of Cu(II) and SDZ on their sorption and desorption on soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of Iron(II) on Arsenic Sequestration by δ-MnO 2 : Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy

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

Wu, Yun; Li, Wei; Sparks, Donald L.

2015-10-18

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO 2) in the presence of Fe(II)more » prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO 4 3–) and calcium (Ca 2+). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.« 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.

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.

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.

Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-17

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

Competitive adsorption-desorption reactions of two hazardous heavy metals in contaminated soils.

PubMed

Davari, Masoud; Rahnemaie, Rasoul; Homaee, Mehdi

2015-09-01

Investigating the interactions of heavy metals is imperative for sustaining environment and human health. Among those, Cd is toxic for organisms at any concentration. While Ni acts as a micronutrient at very low concentration but is hazardous toxic above certain threshold value. In this study, the chemical adsorption and desorption reactions of Ni and Cd in contaminated soils were investigated in both single and binary ion systems. Both Ni and Cd experimental data demonstrated Langmuir type adsorption. In the competitive systems, an antagonistic effect was observed, implying that both ions compete for same type of adsorption sites. Adverse effect of Cd on Ni adsorption was slightly stronger than that of opposite system, consistent with adsorption isotherms in single ion systems. Variation in ionic strength indicated that Ca, a much weaker adsorbate, could also compete with Cd and Ni for adsorption on soil particles. Desorption data indicated that Cd and Ni are adsorbed very tightly such that after four successive desorption steps, less than 0.5 % of initially adsorbed ions released into the soil solution. This implies that Ca, at concentration in equilibrium with calcite mineral, cannot adequately compete with and replace adsorbed Ni and Cd ions. This adsorption behavior was led to considerable hysteresis between adsorption and desorption in both single and binary ion systems. In the binary ion systems, desorption of Cd and Ni was increased by increase in both equilibrium concentration of adsorbed ion and concentration of competitor ion. The overall results obtained in this research indicate that Cd and Ni are strongly adsorbed in calcareous soil and Ca, the major dissolved ion, insignificantly influences metal ions adsorption. Consequently, the contaminated soils by Ni and Cd can simultaneously be remediated by environmentally oriented technologies such as phytoremediation.

X-RAY MICROSCOPY AND SPECTROSCOPY STUDIES ON METAL BINDING IN BIOSOLIDS

EPA Science Inventory

Sorption/desorption data from intact and different fractions of biosolids and biosolids-amended soils indicated the importance of Fe and Mn fractions on both sorption and desorption of metals in biosolids and biosolids-amended soils. Extraction procedures used to separate organi...

X-RAY MICROSCOPY AND SPECTROSCOPY STUDIES ON METAL BINDING IN BIOSOLIDS (ABSTRACT)

EPA Science Inventory

Sorption/desorption data from intact and different fractions of biosolids and biosolids-amended soils indicated the importance of Fe and Mn fractions on both sorption and desorption of metals in biosolids and biosolids-amended soils. Extraction procedures used to separate organi...

Sorption-desorption of indaziflam and its three metabolites in sandy soils

USDA-ARS?s Scientific Manuscript database

Indaziflam is a relatively new herbicide for which sorption-desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. Freundlich sorption isotherm slopes were < 1, there...

Sorption-desorption of indaziflam in selected agricultural soils

USDA-ARS?s Scientific Manuscript database

Sorption and desorption of indaziflam in 6 soils from Brazil and 3 soils from the USA, with different physical chemical properties, were investigated using the batch equilibration method. Sorption kinetics demonstrated that soil-solution equilibrium was attained in a 24-h period. The Freundlich equa...

INITIAL SCREENING OF THERMAL DESORPTION FOR SOIL REMEDIATION

EPA Science Inventory

The purpose of the paper is to present procedures for collecting and evaluating key data that affect the potential application of thermal desorption for a specific site. These data are defined as 'criticalsuccess factors'. The screening prodcedure can be used to peerform an ini...

DEMONSTRATION BULLETIN: THERMAL DESORPTION SYSTEM - CLEAN BERKSHIRES, INC.

EPA Science Inventory

A thermal desorption system (TDS) has been developed by Clean Berkshires, Inc. (CBI), Lanesboro, Massachusetts for ex-situ treatment of soils and other media contaminated with organic pollutants. The TDS uses heat as both a physical separation mechanism and as a means to destro...

MEASUREMENT OF VOCS DESORBED FROM BUILDING MATERIALS--A HIGH TEMPERATURE DYNAMIC CHAMBER METHOD

EPA Science Inventory

Mass balance is a commonly used approach for characterizing the source and sink behavior of building materials. Because the traditional sink test methods evaluate the adsorption and desorption of volatile organic compounds (VOC) at ambient temperatures, the desorption process is...

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.

Desorption of water from hydrophilic MCM-41 mesopores: positron annihilation, FTIR and MD simulation studies.

PubMed

Maheshwari, Priya; Dutta, D; Muthulakshmi, T; Chakraborty, B; Raje, N; Pujari, P K

2017-02-08

The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.

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.

Desorption of cesium from granite under various aqueous conditions.

PubMed

Wang, Tsing-Hai; Li, Ming-Hsu; Wei, Yuan-Yaw; Teng, Shi-Ping

2010-12-01

In this work the desorption of cesium ions from crushed granite in synthetic groundwater (GW) and seawater (SW) was investigated. Results were compared with those obtained in deionized water (DW) and in two kinds of extraction solutions, namely: MgCl(2) and NaOAc (sodium acetate). In general, the desorption rate of Cs from crushed granite increased proportionally with initial Cs loadings. Also, amounts of desorbed Cs ions followed the tendency in the order SW>GW>NaOAc approximately equal MgCl(2)>DW solutions. This indicated that the utilization of extraction reagents for ion exchange will underestimate the Cs desorption behavior. Fitting these experimental data by Langmuir model showed that these extraction reagents have reduced Cs uptake by more than 90%, while only less than 1% of adsorbed Cs ions are still observed in GW and SW solutions in comparison to those in DW. Further SEM/EDS mapping studies clearly demonstrate that these remaining adsorbed Cs ions are at the fracture areas of biotite. Copyright 2010 Elsevier Ltd. All rights reserved.

High Resolution Laser Mass Spectrometry Bioimaging

PubMed Central

Murray, Kermit K.; Seneviratne, Chinthaka A.; Ghorai, Suman

2016-01-01

MSI (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10 μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. PMID:26972785

Distribution and removal of organochlorine pesticides in waste clay bricks from an abandoned manufacturing plant using low-temperature thermal desorption technology.

PubMed

Cong, Xin; Li, Fasheng; Kelly, Ryan M; Xue, Nandong

2018-04-01

The distribution of pollutants in waste clay bricks from an organochlorine pesticide-contaminated site was investigated, and removal of the pollutants using a thermal desorption technology was studied. The results showed that the contents of HCHs in both the surface and the inner layer of the bricks were slightly higher than those of DDTs. The total pore volume of the bricks was 37.7 to 41.6% with an increase from external to internal surfaces. The removal efficiency by thermal treatment was within 62 to 83% for HCHs and DDTs in bricks when the temperature was raised from 200 to 250 °C after 1 h. HCHs were more easily removed than DDTs with a higher temperature. Either intraparticle or surface diffusion controls the desorption processes of pollutants in bricks. It was feasible to use the polluted bricks after removal of the pollutants by low-temperature thermal desorption technology.

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.

Nanostructured solid substrates for efficient laser desorption/ionization mass spectrometry (LDI-MS) of low molecular weight compounds.

PubMed

Silina, Yuliya E; Volmer, Dietrich A

2013-12-07

Analytical applications often require rapid measurement of compounds from complex sample mixtures. High-speed mass spectrometry approaches frequently utilize techniques based on direct ionization of the sample by laser irradiation, mostly by means of matrix-assisted laser desorption/ionization (MALDI). Compounds of low molecular weight are difficult to analyze by MALDI, however, because of severe interferences in the low m/z range from the organic matrix used for desorption/ionization. In recent years, surface-assisted laser desorption/ionization (SALDI) techniques have shown promise for small molecule analysis, due to the unique properties of nanostructured surfaces, in particular, the lack of a chemical background in the low m/z range and enhanced production of analyte ions by SALDI. This short review article presents a summary of the most promising recent developments in SALDI materials for MS analysis of low molecular weight analytes, with emphasis on nanostructured materials based on metals and semiconductors.

High resolution laser mass spectrometry bioimaging.

PubMed

Murray, Kermit K; Seneviratne, Chinthaka A; Ghorai, Suman

2016-07-15

Mass spectrometry imaging (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. Copyright © 2016 Elsevier Inc. All rights reserved.

Enrichment and Purification of Syringin, Eleutheroside E and Isofraxidin from Acanthopanax senticosus by Macroporous Resin

PubMed Central

Yang, Fengjian; Yang, Lei; Wang, Wenjie; Liu, Yang; Zhao, Chunjian; Zu, Yuangang

2012-01-01

In order to screen a suitable resin for the preparative simultaneous separation and purification of syringin, eleutheroside E and isofraxidin from Acanthopanax senticosus, the adsorption and desorption properties of 17 widely used commercial macroporous resins were evaluated. According to our results, HPD100C, which adsorbs by the molecular tiers model, was the best macroporous resin, offering higher adsorption and desorption capacities and higher adsorption speed for syringin, eleutheroside E and isofraxidin than other resins. Dynamic adsorption and desorption tests were carried out to optimize the process parameters. The optimal conditions were as follows: for adsorption, processing volume: 24 BV, flow rate: 2 BV/h; for desorption, ethanol–water solution: 60:40 (v/v), eluent volume: 4 BV, flow rate: 3 BV/h. Under the above conditions, the contents of syringin, eleutheroside E and isofraxidin increased 174-fold, 20-fold and 5-fold and their recoveries were 80.93%, 93.97% and 93.79%, respectively. PMID:22942746

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

Desorption of oxygen from alloyed Ag/Pt(111)

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

Jankowski, Maciej; Wormeester, Herbert, E-mail: h.wormeester@utwente.nl; Zandvliet, Harold J. W.

2014-06-21

We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (E{sub des})more » decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of E{sub des} with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.« less

Thermal desorption of dimethyl methylphosphonate from MoO 3

DOE PAGES

Head, Ashley R.; Tang, Xin; Hicks, Zachary; ...

2017-03-03

Organophosphonates are used as chemical warfare agents, pesticides, and corrosion inhibitors. New materials for the sorption, detection, and decomposition of these compounds are urgently needed. To facilitate materials and application innovation, a better understanding of the interactions between organophosphonates and surfaces is required. To this end, we have used diffuse reflectance infrared Fourier transform spectroscopy to investigate the adsorption geometry of dimethyl methylphosphonate (DMMP) on MoO 3, a material used in chemical warfare agent filtration devices. We further applied ambient pressure X-ray photoelectron spectroscopy and temperature programmed desorption to study the adsorption and desorption of DMMP. While DMMP adsorbs intactmore » on MoO 3, desorption depends on coverage and partial pressure. At low coverages under UHV conditions, the intact adsorption is reversible. Decomposition occurs with higher coverages, as evidenced by PCH x and PO x decomposition products on the MoO 3 surface. Heating under mTorr partial pressures of DMMP results in product accumulation.« less

Determination of residual solvents in pharmaceuticals by thermal desorption-GC/MS.

PubMed

Hashimoto, K; Urakami, K; Fujiwara, Y; Terada, S; Watanabe, C

2001-05-01

A novel method for the determination of residual solvents in pharmaceuticals by thermal desorption (TD)-GC/MS has been established. A programmed temperature pyrolyzer (double shot pyrolyzer) is applied for the TD. This method does not require any sample pretreatment and allows very small amounts of the sample. Directly desorbed solvents from intact pharmaceuticals (ca. 1 mg) in the desorption cup (5 mm x 3.8 mm i.d.) were cryofocused at the head of a capillary column prior to a GC/MS analysis. The desorption temperature was set at a point about 20 degrees C higher than the melting point of each sample individually, and held for 3 min. The analytical results using 7 different pharmaceuticals were in agreement with those obtained by direct injection (DI) of the solution, followed by USP XXIII. This proposed TD-GC/MS method was demonstrated to be very useful for the identification and quantification of residual solvents. Furthermore, this method was simple, allowed rapid analysis and gave good repeatability.

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

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Temperature and pH influence adsorption of cellobiohydrolase onto lignin by changing the protein properties.

PubMed

Lu, Xianqin; Wang, Can; Li, Xuezhi; Zhao, Jian

2017-12-01

Non-productive adsorption of cellulase onto lignin restricted the movement of cellulase and also hindered the cellulase recycling in bioconversion of lignocellulose. In this study, effect of temperature and pH on adsorption and desorption of cellobiohydrolase (CBH) on lignin and its possible mechanism were discussed. It found that pH value and temperature influenced the adsorption and desorption behaviors of CBH on lignin. Different thermodynamic models suggested that the action between lignin and CBH was physical action. More CBH was adsorbed onto lignin, but lower initial adsorption velocity was detected at 50°C comparing with 4°C. Elevating pH value could improve desorption of cellulase from lignin. The changes of hydrophobicity and electric potential on protein surface may partially explain the impact of environmental conditions on the adsorption and desorption behaviors of CBH on lignin, and comparing to electrical interaction, the hydrophobicity may be the dominating factor influencing the behaviors. Copyright © 2017 Elsevier Ltd. All rights reserved.

A green strategy for desorption of trihalomethanes adsorbed by humin and reuse of the fixed bed column.

PubMed

Cunha, G C; Romão, L P C; Santos, M C; Costa, A S; Alexandre, M R

2012-03-30

The objective of the present work was to develop a thermal desorption method for the removal of trihalomethanes (THM) adsorbed by humin, followed by multiple recycling of the fixed bed column in order to avoid excessive consumption of materials and reduce operating costs. The results obtained for adsorption on a fixed bed column confirmed the effectiveness of humin as an adsorbent, extracting between 45.9% and 90.1% of the total THM (TTHM). In none of the tests was the column fully saturated after 10h. Experiments involving thermal desorption were used to evaluate the potential of the technique for column regeneration. The adsorptive capacity of the humin bed increased significantly (p<0.05) between the first and fifth desorption cycle, by 18.9%, 18.1%, 24.2%, 20.2% and 24.2% for CHBr(3), CHBr(2)Cl, CHBrCl(2), CHCl(3) and TTHM, respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

PubMed Central

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.

2017-01-01

Ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)–water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface. PMID:28598428

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.

Investigating desorption during ethanol elution to improve the quality and antioxidant activity of xylo-oligosaccharides from corn stalk.

PubMed

Zhang, Jie; Wang, Yue-Hai; Wei, Quan-Yuan; Du, Xiao-Jia; Qu, Yong-Shui

2018-02-01

As the most representative of lignocellulosic materials, corn stalk (CS) will be a great candidate to produce xylo-oligosaccharides (XOS). Owing to the high impurity content of the XOS produced by directly enzymatic hydrolysis of xylan extracted from CS, subsequent refining steps are essential. The present study was aimed to investigate desorption during ethanol elution to improve the quality and antioxidant activity of XOS from CS. The desorption was systematically investigated after optimizing the elution conditions. The results showed that it had an elution watershed when the volume ratio was 2:1. More interestingly, XOS had a obvious priorities of desorption during ethanol gradient elution. The highest purity of XOS was 98.12% from 30% ethanol eluate. Antioxidant activity assay showed that the highest radical scavenging activity of XOS was 89.89% obtained from 70% ethanol eluate at a concentration of 3 mg/mL, which could be used in antioxidant food, feed additives. Copyright © 2017 Elsevier Ltd. All rights reserved.

Boron nitride nanotubes matrix for signal enhancement in infrared laser desorption postionization mass spectrometry.

PubMed

Lu, Qiao; Hu, Yongjun; Chen, Jiaxin; Li, Yujian; Song, Wentao; Jin, Shan; Liu, Fuyi; Sheng, Liusi

2018-09-01

The nanomaterials function as the substrate to trap analytes, absorb energy from the laser irradiation and transfer energy to the analytes to facilitate the laser desorption process. In this work, the signal intensity and reproducibility of analytes with nanomaterials as matrices were explored by laser desorption postionization mass spectrometry (LDPI-MS). Herein, the desorbed neutral species were further ionized by vacuum ultraviolet (VUV, 118 nm) and analyzed by mass spectrometer. Compared with other nanomaterial matrices such as graphene and carbon nanotubes (CNTs), boron nitride nanotubes (BNNTs) exhibited much higher desorption efficiency under infrared (IR) light and produced no background signal in the whole mass range by LDPI-MS. Additionally, this method was successfully and firstly exploited to in situ detection and imaging for drugs of low concentration in intact tissues, which proved the utility, facility and convenience of this method applied in drug discovery and biomedical research. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of volatiles in fire debris by combination of activated charcoal strips (ACS) and automated thermal desorption-gas chromatography-mass spectrometry (ATD/GC-MS).

PubMed

Martin Fabritius, Marie; Broillet, Alain; König, Stefan; Weinmann, Wolfgang

2018-06-04

Adsorption of volatiles in gaseous phase to activated charcoal strip (ACS) is one possibility for the extraction and concentration of ignitable liquid residues (ILRs) from fire debris in arson investigations. Besides liquid extraction using carbon dioxide or hexane, automated thermo-desorption can be used to transfer adsorbed residues to direct analysis by gas chromatography-mass spectrometry (GC-MS). We present a fire debris analysis work-flow with headspace adsorption of volatiles onto ACS and subsequent automated thermo-desorption (ATD) GC-MS analysis. Only a small portion of the ACS is inserted in the ATD tube for thermal desorption coupled to GC-MS, allowing for subsequent confirmation analysis with another portion of the same ACS. This approach is a promising alternative to the routinely used ACS method with solvent extraction of retained volatiles, and the application to fire debris analysis is demonstrated. Copyright © 2018 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.

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment.

PubMed

Tang, Jie; Xue, Qiang; Chen, Honghan; Li, Wenting

2017-05-01

High concentrations of ammonium sulfate, often used in the in situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid-extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid-extractable fractions. Ninety-six percent of the extractable fraction in soil was desorbed into solution at pH = 3.0, and the content of the reducible fraction was observed to initially increase (when pH >4.0) and then decrease (when pH <4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid-extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid-extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process. Graphical abstract ᅟ.

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

Study of residual oil in Bay Jimmy sediment 5 years after the Deepwater Horizon oil spill: Persistence of sediment retained oil hydrocarbons and effect of dispersants on desorption.

PubMed

Duan, Jun; Liu, Wen; Zhao, Xiao; Han, Yuling; O'Reilly, S E; Zhao, Dongye

2018-03-15

The 2010 Deepwater Horizon (DwH) oil spill contaminated ~1,773km of the Gulf of Mexico shorelines. Yet, few field data are available on the long-term fate and persistency of sediment-retained oil. While an unprecedented amount of oil dispersants was applied, the effects of oil dispersants on desorption of field aged oil remain unknown. This study aimed to investigate the abundance, distributions and physico-chemical availability of the oil retained in Bay Jimmy sediment, Louisiana, five years after the DwH oil spill, and to determine the effects of two model oil dispersants on the desorption potential of the residual oil. Total petroleum hydrocarbons (TPHs), n-alkanes and polycyclic aromatic hydrocarbons (PAHs) in the sediment were analyzed and compared with those in the crude oil and the pre-DwH levels, and batch desorption kinetic tests were carried out to quantify the dispersant effects on the desorption rate and extent. The biomarker hopanes profile and diagnostic ratio were analyzed, which confirmed the origin and persistence of the sediment-retained oil. After five-year natural weathering, the oil level in the sediment remained orders of magnitude higher than the pre-spill level. Nearly all low-molecular-weight n-alkanes and 2-ring PAHs had been degraded. Oil dispersants, SPC 1000 and Corexit EC9500A, were able to enhance solubilization of the sediment-retained oil upon resuspension of the sediment. Successive desorption experiments indicated that 71.6% of TPHs, 74.8% of n-alkanes, and 91.9% of PAHs in the sediment remained highly stable and hardly desorbable by seawater; yet, addition of 18mg/L of SPC 1000 enhanced the desorption and lowered these fractions to 57.3%, 68.1%, and 81.4%, respectively. The findings are important for understanding the natural weathering rate and persistence of oil residual and the effects of dispersants on the physical and biological availabilities of aged oil in coastal sediments. Copyright © 2017 Elsevier B.V. All rights reserved.

Sample Desorption/Onization From Mesoporous Silica

DOEpatents

Iyer, Srinivas; Dattelbaum, Andrew M.

2005-10-25

Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry: Mechanistic Studies and Methods for Improving the Structural Identification of Carbohydrates

PubMed Central

Lai, Yin-Hung; Wang, Yi-Sheng

2017-01-01

Although matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is one of the most widely used soft ionization methods for biomolecules, the lack of detailed understanding of ionization mechanisms restricts its application in the analysis of carbohydrates. Structural identification of carbohydrates achieved by MALDI mass spectrometry helps us to gain insights into biological functions and pathogenesis of disease. In this review, we highlight mechanistic details of MALDI, including both ionization and desorption. Strategies to improve the ion yield of carbohydrates are also reviewed. Furthermore, commonly used fragmentation methods to identify the structure are discussed. PMID:28959517

Simulated moving bed system for CO.sub.2 separation, and method of same

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

Elliott, Jeannine Elizabeth; Copeland, Robert James; Lind, Jeff

A system and method for separating and/or purification of CO.sub.2 gas from a CO.sub.2 feed stream is described. The system and method include a plurality of fixed sorbent beds, adsorption zones and desorption zones, where the sorbent beds are connected via valve and lines to create a simulated moving bed system, where the sorbent beds move from one adsorption position to another adsorption position, and then into one regeneration position to another regeneration position, and optionally back to an adsorption position. The system and method operate by concentration swing adsorption/desorption and by adsorptive/desorptive displacement.

ADSORPTION, DESORPTION AND OXIDATION OF ARSENIC AFFECTED BY CLAY MINERALS AND AGING PROCESS

EPA Science Inventory

Adsorption/desorption and oxidation/reduction of arsenic at clay surfaces are very important to the natural attenuation of arsenic in the subsurface environment. Although numerous studies have concluded that iron oxides have high affinities for the adsorption of As(V), very litt...

Glyphosate sorption/desorption on biochars – Interactions of physical and chemical processes

USDA-ARS?s Scientific Manuscript database

BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350°C t...

LASER DESORPTION/IONIZATION OF SINGLE ULTRAFINE MULTICOMPONENT AEROSOLS. (R823980)

EPA Science Inventory

Laser desorption/ionization characteristics of single
ultrafine multicomponent aerosols have been investigated.
The results confirm earlier findings that (a) the negative
ion spectra are dominated by free electrons and (b) the ion
yield-to-mass ratio is higher for ...

Split-flow regeneration in absorptive air separation

DOEpatents

Weimer, Robert F.

1987-01-01

A chemical absorptive separation of air in multiple stage of absorption and desorption is performed with partial recycle of absorbent between stages of desorption necessary to match equilibrium conditions in the various stages of absorption. This allows reduced absorbent flow, reduced energy demand and reduced capital costs.

PARTITIONING, DESORPTION, AND DECHLORINATION OF A PCB CONGENER IN SEDIMENT SLURRY SUPERNATANTS

EPA Science Inventory

Partitioning and desorption played specific roles in the dechlorination of 2-chlorobiphenyl (2-ClBP) in sediment slurry supernatants, which are suspensions of disssolved organic matter(DOM). In short-term experiments, the partition coefficient (K_p) was related to the a...

Indaziflam sorption-desorption in diverse soils

USDA-ARS?s Scientific Manuscript database

Indaziflam is a new preemergence-herbicide active ingredient, classified as a member of the new chemical class “alkylazine”. There is no published information on its fate and behavior in soil. This study is aimed at characterizing the adsorption and desorption of indaziflam in soils with different p...

COSOLVENT EFFECTS ON PHENANTHRENE SORPTION-DESORPTION ON A FRESH-WATER SEDIMENT

EPA Science Inventory

This study evaluated the effects of the water-miscible cosolvent methanol on the sorption-desorption of phenanthrene by the natural organic matter (NOM) of a fresh-water sediment. A biphasic pattern was observed in the relationship between the log of the carbon-normalized sorpti...

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

PubMed

Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

2017-06-01

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg 2 NiH 4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg 2 NiH 4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol -1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

The effects of intra-particle concentration gradient on consecutive adsorption-desorption of oryzanol from rice bran oil in packed-column

NASA Astrophysics Data System (ADS)

Susanti, Ari Diana; Sediawan, Wahyudi Budi; Wirawan, Sang Kompiang; Budhijanto

2017-05-01

Utilization of valuable trace components in agriculture by product such as rice bran oil is interesting to be explored. Among the valuables, oryzanol, a healthy nutrition for cardiovascular prevention, is the most promising one. Literature studies suggest that adsorption-desorption is a prospective method for oryzanol isolation. Design of commercial scale adsorption-desorption system for oryzanol needs a quantitative description of the phenomena involved. In this study, quantitative modeling of the consecutive adsorption-desorption in packed column has been proposed and verified through experimental data. The offered model takes into account the intra-particle concentration gradient in the adsorbent particle. In this model, the rate of mass transfer from the bulk of the liquid to the surface of the adsorbent particle or vice versa is expressed by film theory. The mass transfer of oryzanol from the liquid in the pore of the particle to the adjacent pore surface is assumed to be instantaneous, so solid-liquid equilibrium on the surface of the pores is always attained. For simplicity, the adsorption equilibrium model applied was coefficient distribution approach. The values of the parameters implicated in the model were obtained by curve fitting to the experimental data. It verified that the model proposed works well to quantitatively describe the consecutive adsorption-desorption of oryzanol from rice bran oil in packed column.

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

Influence of surface coverage on the chemical desorption process

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

Minissale, M.; Dulieu, F., E-mail: francois.dulieu@obspm.fr

2014-07-07

In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorptionmore » efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.« less

Enhanced desorption of cesium from collapsed interlayer regions in vermiculite by hydrothermal treatment with divalent cations.

PubMed

Yin, Xiangbiao; Wang, Xinpeng; Wu, Hao; Ohnuki, Toshihiko; Takeshita, Kenji

2017-03-15

Adsorption of cesium (Cs) on phyllosilicates has been intensively investigated because natural soils have strong ability of immobilizing Cs within clay minerals resulting in difficulty of decontamination. The objectives of present study are to clarify how Cs fixation on vermiculite is influenced by structure change caused by Cs sorption at different loading levels and how Cs desorption is affected by various replacing cations induced at different treating temperature. As a result, more than 80% of Cs was readily desorbed from vermiculite with loading amount of 2% saturated Cs (5.49×10 -3 mmolg -1 ) after four cycles of treatment of 0.01M Mg 2+ /Ca 2+ at room temperature, but less than 20% of Cs was desorbed from saturated vermiculite. These distinct desorption patterns were attributed to inhibition of Cs desorption by interlayer collapse of vermiculite, especially at high Cs loadings. In contrast, elevated temperature significantly facilitated divalent cations to efficiently desorb Cs from collapsed regions. After five cycles of treatment at 250°C with 0.01M Mg 2+ , ∼100% removal of saturated Cs was achieved. X-ray diffraction analysis results suggested that Cs desorption was completed through enhanced diffusion of Mg 2+ cations into collapsed interlayer space under hydrothermal condition resulting in subsequent interlayer decollapse and readily release of Cs + . Copyright © 2016 Elsevier B.V. All rights reserved.

Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

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

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

2014-01-01

A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertaintiesmore » with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.« less

Microemulsion-enhanced remediation of soils contaminated with organochlorine pesticides.

PubMed

Zhang, Yanlin; Wong, Jonathan W C; Zhao, Zhenyong; Selvam, Ammaiyappan

2011-12-01

Soil contaminated by organic pollutants, especially chlorinated aromatic compounds such as DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane), is an environmental concern because of the strong sorption of organochlorine pesticide onto the soil matrix and persistence in the environment. The remediation of organochlorine pesticide contaminated soils through microemulsion is an innovative technology to expedite this process. The remediation efficiency was evaluated by batch experiments through studying the desorption of DDT and hexachlorocyclohexane (y-HCH) and sorption of microemulsion composed of Triton X-100, 1-pentanol and linseed oil in the soil-surfactant-water suspension system. The reduction of desorption efficiency caused by the sorption loss of microemulsion components onto the soil could be corrected by the appropriate adjustment of C/S (Cosurfactant/Surfactant) and O/S (Oil/Surfactant) ratio. The C/S and O/S ratios of 1:2 and 3:20 were suitable to desorb DDT and gamma-HCH from the studied soils because of the lower sorption of Triton X-100 onto the soil. Inorganic salts added in microemulsion increased the pesticides desorption efficiency of pesticides and calcium chloride has a stronger ability to enhance the desorption of DDT than sodium chloride. From the remediation perspective, the balance of surfactant or cosurfactant sorbed to soil and desorption efficiency should be taken into consideration to enhance the remediation of soils contaminated by organochlorine pesticides.

Fraction of organic carbon predicts labile desorption rates of chlorinated organic pollutants in laboratory-spiked geosorbents.

PubMed

Ginsbach, Jake W; Killops, Kato L; Olsen, Robert M; Peterson, Brittney; Dunnivant, Frank M

2010-05-01

The resuspension of large volumes of sediments that are contaminated with chlorinated pollutants continues to threaten environmental quality and human health. Whereas kinetic models are more accurate for estimating the environmental impact of these events, their widespread use is substantially hampered by the need for costly, time-consuming, site-specific kinetics experiments. The present study investigated the development of a predictive model for desorption rates from easily measurable sorbent and pollutant properties by examining the relationship between the fraction of organic carbon (fOC) and labile release rates. Duplicate desorption measurements were performed on 46 unique combinations of pollutants and sorbents with fOC values ranging from 0.001 to 0.150. Labile desorption rate constants indicate that release rates predominantly depend upon the fOC in the geosorbent. Previous theoretical models, such as the macro-mesopore and organic matter (MOM) diffusion model, have predicted such a relationship but could not accurately predict the experimental rate constants collected in the present study. An empirical model was successfully developed to correlate the labile desorption rate constant (krap) to the fraction of organic material where log(krap)=0.291-0.785 . log(fOC). These results provide the first experimental evidence that kinetic pollution releases during resuspension events are governed by the fOC content in natural geosorbents. Copyright (c) 2010 SETAC.

Adsorption and desorption of carbaryl on hexadecyl trimethyl ammonium bromide modified zeolite NaY using RGB portable photometer

NASA Astrophysics Data System (ADS)

Patdhanagul, Nopbhasinthu; Chanpaka, Saiphon; Intharaksa, Orapan; Sirival, Rujikarn; Thanomsith, Kannikar; Wongkwanklom, Sarayuth

2018-04-01

The carbaryl adsorption-desorption isotherms of zeolite NaY and hexadecyl trimethyl ammonium bromide (HTAB) modified zeolite NaY were investigated. Zeolite NaY was synthesized and modified by HTAB in the concentration range 0.1 - 10.0 mM. The adsorption isotherms indicated that zeolite modified with HTAB could significantly enhance the carbaryl adsorption capacity. Zeolite NaY modified with 5.0 mM HTAB gave great carbaryl adsorption because of hydrophilic surface. The 5.0 mM HTAB could adsorb up to 145.75 ppm g-1 of carbaryl which was equivalent to a 36.7% increase. The Surface area characterization showed the remaining of pore volume and pore size diameter and external surface area whereas the BET surface area and micropore surface area of modified zeolite slightly decreased. The XRD results indicate that modification of zeolite NaY with HTAB does not change the crystallinity of the starting zeolite. The elemental analysis indicated that the Si/Al ratio of synthesized zeolite NaY was close to 2.43. Desorption of carbaryl was tested by organic solvents such as methanol, ethanol, tetrahydrofuran, hexane and Deionized water. The results demonstrated that the percentage desorption of methanol is the highest. Carbaryl was quantitatively desorbed with percentage desorption of 82-100 %. It indicated sorption mechanism of carbaryl on the modified sorbent which was principally driven by hydrophobic forces.

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.

Study of the photon-induced formation and subsequent desorption of CH3OH and H2CO in interstellar ice analogs

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Muñoz Caro, G. M.; Cruz-Díaz, G. A.

2016-05-01

Context. Methanol and formaldehyde are two simple organic molecules that are ubiquitously detected in the interstellar medium, in both the solid and gaseous phases. An origin in the solid phase and a subsequent nonthermal desorption into the gas phase is often invoked to explain their abundances in some of the environments where they are found. Experimental simulations under astrophysically relevant conditions have been carried out in the past four decades in order to find a suitable mechanism for that process. Aims: In particular, photodesorption from pure methanol ice (and presumably from pure formaldehyde ice) has been found to be negligible in previous works, probably because both molecules are very readily dissociated by vacuum-UV photons. Therefore, we explore the in situ formation and subsequent photon-induced desorption of these species, studying the UV photoprocessing of pure ethanol ice, and a more realistic binary H2O:CH4 ice analog. Methods: Experimental simulations were performed in an ultra-high vacuum chamber. Pure ethanol and binary H2O:CH4 ice samples deposited onto an infrared transparent window at 8 K were UV-irradiated using a microwave-discharged hydrogen flow lamp. Evidence of photochemical production of these two species and subsequent UV-photon-induced desorption into the gas phase were searched for by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer, respectively. After irradiation, ice samples were warmed up to room temperature until complete sublimation was attained for detection of volatile products. Results: Formation of CH3OH was only observed during photoprocessing of the H2O:CH4 ice analog, accounting for ~4% of the initial CH4 ice column density, but no photon-induced desorption was detected. Photochemical production of H2CO was observed in both series of experiments. Formation of formaldehyde accounted for ≤45% conversion of the initial ethanol ice, but it could not be quantified during irradiation of the binary H2O:CH4 ice analogs. Photochemidesorption of formaldehyde, I.e., photon-induced formation on the ice surface and inmediate desorption, was observed, with a yield of ~6 × 10-5 (molecules/incident photon) in the case of the pure ethanol ice experiments, and ~4.4 × 10-5 (molecules/incident photon) when the H2O:CH4 ice analogs were photoprocessed. Photoprocessing of the ice analogs lead to formation of other species. Some of them were also found to desorb upon UV irradiation. Conclusions: While certain C-bearing species, in particular H2CO, were found to desorb upon irradiation, nonthermal desorption of CH3OH was not observed. So far, there is no experimental evidence of any efficient CH3OH desorption induced by UV photons. On the other hand, the observed photon-induced desorption of H2CO could account for the total formaldehyde abundance observed in the Horsehead photodissociation-dominated region.

Influence of soil properties and test conditions on sorption and desorption of testosterone

USDA-ARS?s Scientific Manuscript database

In this study, batch sorption and desorption experiments were conducted for testosterone using four agricultural soils and five clay minerals. Significant differences in sorption behavior were observed between abiotic and biotic systems. The Freundlich sorption coefficient Kf (µg per g)/(µg per mL) ...

Desorption of Arsenic from Drinking Water Distribution System Solids

EPA Science Inventory

Given the limited knowledge regarding the soluble release of arsenic from DWDS solids, the objectives of this research were to: 1) investigate the effect of pH on the dissolution/desorption of arsenic from DWDS solids, and 2) examine the effect of orthophosphate on the soluble re...

Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.

ERIC Educational Resources Information Center

Cooks, R. G.; Busch, K. L.

1982-01-01

Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

Split-flow regeneration in absorptive air separation

DOEpatents

Weimer, R.F.

1987-11-24

A chemical absorptive separation of air in multiple stage of absorption and desorption is performed with partial recycle of absorbent between stages of desorption necessary to match equilibrium conditions in the various stages of absorption. This allows reduced absorbent flow, reduced energy demand and reduced capital costs. 4 figs.

Re-analysis of experiments to quantify irreversibility of pesticide sorption-desorption in soil

USDA-ARS?s Scientific Manuscript database

Previously published research has used an isotope-exchange technique to measure irreversibility of pesticide adsorption-desorption in soil. Results have indicated significant irreversibility (6-51%) in the sorption in five pesticide-soil systems measured over 72 hours. Here, we propose a three-site ...

Sorption-desorption of rimsulfuron, nicosulfuron, and their metabolites in soils from Argentina and USA

USDA-ARS?s Scientific Manuscript database

For many pesticides, sorption coefficients increase with residence time in the soil, becoming constant after weeks of aging in the soil. Pesticide sorption is often slowly reversible with some fraction being recalcitrant to desorption. Dissipation in soil often follows a biphasic trend, in which the...

Direct analysis of triterpenes from high-salt fermented cucumbers using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI)

USDA-ARS?s Scientific Manuscript database

High-salt samples present a challenge to mass spectrometry (MS) analysis, particularly when electrospray ionization (ESI) is used, requiring extensive sample preparation steps such as desalting, extraction, and purification. In this study, infrared matrix-assisted laser desorption electrospray ioniz...

Reply to Comment on Light-induced atomic desorption and diffusion of Rb from porous alumina

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

Villalba, S.; Failache, H.; Lezama, A.

We argue that the model used in our paper [Phys. Rev. A 81, 032901 (2010)] for the analysis of the experimental study of light-induced atomic desorption in porous alumina is the simplest consistent approach to a previously unexplored physical system.

ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

EPA Science Inventory

ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R822721C697)

EPA Science Inventory

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R826694C697)

EPA Science Inventory

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

MATRIX-ASSISTED LASER DESORPTION IONIZATION OF SIZE AND COMPOSITION SELECTED AEROSOL PARTICLES. (R823980)

EPA Science Inventory

Matrix-assisted laser desorption/ionization (MALDI) was performed on individual,
size-selected aerosol particles in the 2-8 mu m diameter range, Monodisperse aerosol droplets
containing matrix, analyte, and solvent were generated and entrained in a dry stream of air, The dr...

DEMONSTRATION BULLETIN: X*TRAX MODEL 200 THERMAL DESORPTION SYSTEMS - CHEMICAL WASTE MANAGEMENT, INC.

EPA Science Inventory

The X*TRAX™ Mode! 200 Thermal Desorption System developed by Chemical Waste Management, Inc. (CWM), is a low-temperature process designed to separate organic contaminants from soils, sludges, and other solid media. The X*TRAX™ Model 200 is fully transportable and consists of thre...

ROLE OF REDUCTANTS IN THE ENHANCED DESORPTION AND TRANSFORMATION OF CHOROALIPHATIC COMPOUNDS BY MODIFIED FENTON'S REACTIONS. (R826163)

EPA Science Inventory

The mechanism for enhanced desorption of chloroaliphatic compounds from a
silty loam soil by modified Fenton's reagent was investigated using a series of
probe compounds of varying hydrophobicities. Hexachloroethane, which has
negligible reactivity with hydroxyl ra...

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...

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

Hanyu, Yuichiro, E-mail: y-hanyu@lucid.msl.titech.ac.jp; Domen, Kay; Nomura, Kenji

We report an experimental evidence that some hydrogens passivate electron traps in an amorphous oxide semiconductor, a-In-Ga-Zn-O (a-IGZO). The a-IGZO thin-film transistors (TFTs) annealed at 300 °C exhibit good operation characteristics; while those annealed at ≥400 °C show deteriorated ones. Thermal desorption spectra (TDS) of H{sub 2}O indicate that this threshold annealing temperature corresponds to depletion of H{sub 2}O desorption from the a-IGZO layer. Hydrogen re-doping by wet oxygen annealing recovers the good TFT characteristic. The hydrogens responsible for this passivation have specific binding energies corresponding to the desorption temperatures of 300–430 °C. A plausible structural model is suggested.

Nitrate sorption and desorption in biochars from fast pyrolysis

USDA-ARS?s Scientific Manuscript database

Increasing the nitrate (NO3-) sorption capacity of Midwestern US soils has the potential to reduce nitrate leaching to ground water and reduce the extent of the hypoxia zone in the Gulf of Mexico. The objective of this study was to determine the sorption and desorption capacity of non-activated and ...

THE USE OF MATRIX-ASSISTED LASER DESORPTION/IONIZATION-MASS SPECTROMETRY FOR THE IDENTIFICATION OF AEROMONAS ISOLATES OBTAINED FROM WATER DISTRIBUTION SYSTEMS

EPA Science Inventory

Matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) has long been established as a tool by which microorganisms can be characterized and identified. EPA is investigating the potential of using this technology as a way to rapidly identify Aeromonas species fo...

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...

THE IMPORTANCE OF ORGANIC MATTER DISTRIBUTION AND EXTRACT SOIL:SOLUTION RATIO ON THE DESORPTION OF HEAVY METALS FROM SOILS

EPA Science Inventory

The lability (mobility and bioavailability) of metals varies significantly with soil properties for similar total soil metal concentrations. We studied desorption of Cu, Ni and Zn, from 15 diverse, unamended soils. These studies included evaluation of the effects of soil:solution...

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…

Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

USDA-ARS?s Scientific Manuscript database

A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...

SUPERFUND TREATABILITY CLEARINGHOUSE: TECHNOLOGY DEMONSTRATION OF A THERMAL DESORPTION/UV PHOTOLYSIS PROCESS FOR DECONTAMINATING SOILS CONTAINING HERBICIDE ORANGE

EPA Science Inventory

This treatability study report presents the results of laboratory and field tests on the effectiveness of a new decontamination process for soils containing 2,4-D/2,4,5-T and traces of dioxin. The process employs three operations, thermal desorption, condensation and absorp...

The effects of different substrates on the electron stimulated desorption dynamics of O - from physisorbed O2

NASA Astrophysics Data System (ADS)

Hedhili, M. N.; Parenteau, L.; Huels, M. A.; Azria, R.; Tronc, M.; Sanche, L.

1997-11-01

We report condensed phase measurements of kinetic energy (Ek) distributions of O-, produced by dissociative electron attachment (DEA) at 6 eV incident electron energy; they are obtained under identical experimental conditions from submonolayer quantities of 16O2 deposited on disordered multilayer substrates of 18O2, Ar, Kr, Xe, CH4, and C2H6, all condensed at 20 K on polycrystalline platinum (Pt). The results suggest that the desorption dynamics of O- DEA fragments is, in part, determined by large angle elastic scattering of O- prior to desorption, as well as the net image charge potential (Ep) induced in the condensed dielectric solid and the Pt metal. The measurements also indicate that, particularly at small Kr substrate thicknesses, the Ep may not necessarily be uniform across the surface, but may fluctuate due to surface roughness. Thus, in addition to energy losses in the substrate prior to, and during, DEA, these effects may influence the dissociation dynamics of the O2- resonance itself, as well as the desorption of the DEA O- fragment.

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.

Controlling the surface density of DNA on gold by electrically induced desorption.

PubMed

Arinaga, Kenji; Rant, Ulrich; Knezević, Jelena; Pringsheim, Erika; Tornow, Marc; Fujita, Shozo; Abstreiter, Gerhard; Yokoyama, Naoki

2007-10-31

We report on a method to control the packing density of sulfur-bound oligonucleotide layers on metal electrodes by electrical means. In a first step, a dense nucleic acid layer is deposited by self-assembly from solution; in a second step, defined fractions of DNA molecules are released from the surface by applying a series of negative voltage cycles. Systematic investigations of the influence of the applied electrode potentials and oligonucleotide length allow us to identify a sharp desorption onset at -0.65 V versus Ag/AgCl, which is independent of the DNA length. Moreover, our results clearly show the pronounced influence of competitive adsorbents in solution on the desorption behavior, which can prevent the re-adsorption of released DNA molecules, thereby enhancing the desorption efficiency. The method is fully bio-compatible and can be employed to improve the functionality of DNA layers. This is demonstrated in hybridization experiments revealing almost perfect yields for electrically "diluted" DNA layers. The proposed control method is extremely beneficial to the field of DNA-based sensors.

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.

Sorption-desorption of selenite and selenate on Mg-Al layered double hydroxide in competition with nitrate, sulfate and phosphate.

PubMed

Constantino, Leonel Vinicius; Quirino, Juliana Nunes; Monteiro, Alessandra Maffei; Abrão, Taufik; Parreira, Paulo Sérgio; Urbano, Alexandre; Santos, Maria Josefa

2017-08-01

Selenate and selenite are considered emerging contaminants and pose a risk to living organisms. Since selenium anion species are at low concentration in aquatic environments, materials for its retention are required to enable monitoring. Herein, hydrotalcite was calcined and characterised to investigate sorption and desorption of selenite and selenate in competition with nitrate, sulfate and phosphate. Sorption experiments were carried out in batch system and desorption by sequential dilution. Selenite and selenate concentration remaining after N desorption steps was determined by mass balance. The isotherms were adjusted to the dual-mode Langmuir-Freundlich model (R 2  > 0.99). Maximum sorption capacity ranged from 494 to 563 meq kg -1 for selenite and from 609 to 659 meq kg -1 for selenate. Sulfate and phosphate ions showed greater competitive effect on the sorption of selenate and selenite, respectively. Low mobilization factors and high sorption efficiency (MF<3%; SE ≈ 100%) indicated that calcined hydrotalcite has the wanted characteristics for retention of relevant selenium anion species in aqueous media. Copyright © 2017 Elsevier Ltd. All rights reserved.

UV-responsive nano-sponge for oil absorption and desorption

PubMed Central

Kim, Do Hyun; Jung, Min Chan; Cho, So-Hye; Kim, Sang Hoon; Kim, Ho-Young; Lee, Heon Ju; Oh, Kyu Hwan; Moon, Myoung-Woon

2015-01-01

Controlled surface wettability for oil has been intensively studied to remove industrial oil waste or oil spill pollution from seas or rivers. In particular, external stimuli-induced special wetting materials, such as photo-responsive TiO2, have attracted considerable attention for oil-water separation. In this study, a novel method is reported to fabricate a nano-sponge which is composed of hydrophobic hydrocarbon and hydrophilic TiO2 nanoparticles for oil absorption or desorption that are responsive to UV irradiation. The hydrocarbon in the nano-sponge could selectively absorb oil from water, whereas the absorbed oil is released into the water by TiO2 in response to UV irradiation. The nano-sponge functionalized porous polydimethylsiloxane released more than 98% of the absorbed crude oil with UV irradiation and air-bubbling. It could be continuously reused while maintaining a high absorption capacity and desorption efficiency without incurring secondary air or water pollution. This smart oil absorption/desorption methodology with excellent selectivity and recyclability with almost perfect removal of absorbed oil can be applied for oil-water separation, oil spill cleanup and reuse of spilled oil. PMID:26260470

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

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.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

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

Smith, R. Scott; Li, Zhenjun; Chen, Long

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« 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.

The use of nanomaterials for mass spectrometry can be uplifting for analyte detection

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

Li, J.; Lipson, R. H.

2014-03-31

Surface-Assisted Laser Desorption Ionization (SALDI) involves desorbing and ionizing analyte molecules from a nanoporous substrate by laser irradiation for detection in a mass spectrometer. In this work experiments were designed to better understand the mechanisms governing desorption and ionization for Desorption Ionization On Silicon (DIOS), a variant of SALDI which uses porous silicon (pSi) as a substrate. Experiments are also reported for other nanoporous semiconducting materials (WO{sub 3}, TiO{sub 2}) which exhibit very similar behaviors; specifically, that both protonated analyte ions and analyte radical cations can be generated with relative intensities that depend on the position of the incident lasermore » focus relative to substrate surface. While thermal desorption appears to be important, preliminary evidence suggests that the ionization mechanism leading to protonated analytes involves in part electrons and holes formed when photoexciting the substrate above its electronic band gap, and the presence of defect states within the band gap. Radical cation formation appears to be driven in part by electron transfer due to the large electron affinity of each substrate used in this work.« less

CEC-normalized clay-water sorption isotherm

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.

2011-11-01

A normalized clay-water isotherm model based on BET theory and describing the sorption and desorption of the bound water in clays, sand-clay mixtures, and shales is presented. Clay-water sorption isotherms (sorption and desorption) of clayey materials are normalized by their cation exchange capacity (CEC) accounting for a correction factor depending on the type of counterion sorbed on the mineral surface in the so-called Stern layer. With such normalizations, all the data collapse into two master curves, one for sorption and one for desorption, independent of the clay mineralogy, crystallographic considerations, and bound cation type; therefore, neglecting the true heterogeneity of water sorption/desorption in smectite. The two master curves show the general hysteretic behavior of the capillary pressure curve at low relative humidity (below 70%). The model is validated against several data sets obtained from the literature comprising a broad range of clay types and clay mineralogies. The CEC values, derived by inverting the sorption/adsorption curves using a Markov chain Monte Carlo approach, are consistent with the CEC associated with the clay mineralogy.

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.

Weak interactions between water and clathrate-forming gases at low pressures

DOE PAGES

Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; ...

2015-07-17

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10 –1 mbar methane or 10 –5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 10 7 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10 –5 mbar methane does not alter their morphology, suggestingmore » that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

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.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

DOE PAGES

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; ...

2017-06-09

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

PCDD/F formation during thermal desorption of p,p'-DDT contaminated soil.

PubMed

Zhao, Zhonghua; Ni, Mingjiang; Li, Xiaodong; Buekens, Alfons; Yan, Jianhua

2017-05-01

Thermal treatment of polychlorinated biphenyls (PCB) contaminated soil was shown in earlier work to generate polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). In this study, the PCDD/F were studied arising during the remediation of p,p'-DDT contaminated soil by thermal desorption. Three kinds of soil (sandy, clayey and lateritic soil) were tested to investigate the effect of soil texture on PCDD/F formation. Those soils were artificially polluted with p,p'-DDT, obtaining a concentration level of 100 mg/kg. Thermal desorption experiments were conducted for 10 min at 300 °C in an air atmosphere. The total concentration of PCDD/F generated for three soils were 331, 803 and 865 ng/kg, respectively, and TeCDD and TeCDF were dominant among all PCDD/F congeners. After thermal desorption, the total amount of PCDD/F generated both in soil and in off-gas correlated positively with the amount of DDT added to soil. In addition, a possible pathway of the formation of PCDD/F was presented.

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.

Bench-scale evaluation of in situ bioremediation strategies for soil at a former manufactured gas plant site.

PubMed

Li, Jun; Pignatello, Joseph J; Smets, Barth F; Grasso, Domenico; Monserrate, Esteban

2005-03-01

We examined the biodegradation and desorption of a set of 15 polycyclic aromatic hydrocarbon (PAH) compounds in coal tar-contaminated soil at a former manufactured gas plant site to evaluate the feasibility of in situ bioremediation. Experiments were conducted in well-mixed aerobic soil suspensions containing various additives over a 93- to 106-d period. In general, both biotransformation and desorption decreased with PAH ring size, becoming negligible for the six-ring PAH compounds. Biodegradation by indigenous microorganisms was strongly accelerated by addition of inorganic nutrients (N, P, K, and trace metals). The rates of biotransformation of PAH compounds by indigenous microorganisms in nutrient-amended flasks outpaced their maximum (i.e., chelate-enhanced) rates of desorption to an infinite sink (Tenax) in sterilized systems run in parallel, suggesting that indigenous organisms facilitated desorption. Biodegradation by indigenous organisms in nutrient-amended flasks appeared to be unaffected by the addition of a site-derived bacterial enrichment culture, resulting in approximately 100-fold higher aromatic dioxygenase levels, and by the addition of 0.01 M chelating agent (citrate or pyrophosphate), although such chelating agents greatly enhanced desorption in microbially inactivated flasks. The strong ability of nutrients to enhance degradation of the bioavailable PAHs indicates that their persistence for many decades at this site likely results from nutrient-limited natural biodegradation, and it also suggests that an effective strategy for their bioremediation could consist simply of adding inorganic nutrients.

Diamine-Functionalization of a Metal-Organic Framework Adsorbent for Superb Carbon Dioxide Adsorption and Desorption Properties.

PubMed

Lee, Woo Ram; Kim, Jeong Eun; Lee, Sung Jin; Kang, Minjung; Kang, Dong Won; Lee, Hwa Young; Hiremath, Vishwanath; Seo, Jeong Gil; Jin, Hailian; Moon, Dohyun; Cho, Moses; Jung, Yousung; Hong, Chang Seop

2018-05-25

For real-world postcombustion applications in the mitigation of CO 2 emissions using dry sorbents, adsorption and desorption behaviors should be controlled to design and fabricate prospective materials with optimal CO 2 performances. Herein, we prepared diamine-functionalized Mg 2 (dobpdc) (H 4 dobpdc=4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic acid). (1-diamine) with ethylenediamine (en), primary-secondary (N-ethylethylenediamine-een and N-isopropylethylenediamine-ipen), primary-tertiary, and secondary-secondary diamines. A slight alteration of the number of alkyl substituents on the diamines and their alkyl chain length dictates the desorption temperature (T des ) at 100 % CO 2 , desorption characteristics, and ΔT systematically to result in the tuning of the working capacity. The existence of bulky substituents on the diamines improves the framework stability upon exposure to O 2 , SO 2 , and water vapor, relevant to real flue-gas conditions. Bulky substituents are also responsible for an interesting two-step behavior observed for the ipen case, as revealed by DFT calculations. Among the diamine-appended metal-organic frameworks, 1-een, which has the required adsorption and desorption properties, is a promising material for sorbent-based CO 2 capture processes. Hence, CO 2 performance and framework durability can be tailored by the judicial selection of the diamine structure, which enables property design at will and facilitates the development of desirable CO 2 -capture materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Helium self-trapping and diffusion behaviors in deformed 316L stainless steel exposed to high flux and low energy helium plasma

NASA Astrophysics Data System (ADS)

Gong, Yihao; Jin, Shuoxue; Zhu, Te; Cheng, Long; Cao, Xingzhong; You, Li; Lu, Guanghong; Guo, Liping; Wang, Baoyi

2018-04-01

A large number of dislocation networks were introduced in to 316L stainless steel by cold rolling. Subsequently, low energy (40 eV) helium ions were implanted by exposing the steel to helium plasma. Thermal desorption and positron annihilation spectroscopy were used to study the behavior of helium in the presence of dislocations, with emphasis on helium self-trapping and migration behaviors. Helium desorption behaviour from different helium trapping states was measured by the thermal desorption spectroscopy. Most of the helium desorbed from the He m V n clusters, and the corresponding desorption peak is located at ~650 K. The desorption peak from helium-dislocation clusters (He m D) is at approximately 805 K. The effect of annealing on the defect evolution was investigated by positron annihilation spectroscopy. For the specimen exposed to helium plasma without displacement damage, the increment of S parameter meant the existence of helium self-trapping behavior (He m V n ). Helium atoms could diffuse two to three orders of magnitude deeper than the implantation depth calculated by SRIM. The diffusing helium atoms were gradually trapped by dislocation lines and formed He m D. Elevated temperatures enhance the self-trapping behavior and cause helium atoms to dissociate/desorb from the He m V n clusters, increasing the S parameters at 473-673 K. The gradual recovery of vacancies in the He m V n clusters decreased the S parameter above 673 K.

Adsorption, Desorption, and Diffusion of Nitrogen in a Model Nanoporous Material: II. Diffusion Limited Kinetics in Amorphous Solid Water

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

Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.

2007-11-14

Tykhon Zubkov, R. Scott Smith, Todd R. Engstrom, and Bruce D. Kay The adsorption, desorption, and diffusion kinetics of N2 on thick (up to ~9 mm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption (TPD). Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 mm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films, (>1 mm), N2 adsorption at 27 Kmore » results in a non-uniform distribution where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is ~7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Blocking adsorption sites near the film surface facilitates transport into the film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor-mediated and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed 2nd layer N2 species on top of the 1st layer chemisorbed layer.« less

Natural and surfactant modified zeolites: A review of their applications for water remediation with a focus on surfactant desorption and toxicity towards microorganisms.

PubMed

Reeve, Peter J; Fallowfield, Howard J

2018-01-01

The objective of this review is to highlight the need for further investigation of microbial toxicity caused by desorption of surfactant from Surfactant Modified Zeolite (SMZ). SMZ is a low cost, versatile permeable reactive media which has the potential to treat multiple classes of contaminants. With this combination of characteristics, SMZ has significant potential to enhance water and wastewater treatment processes. Surfactant desorption has been identified as a potential issue for the ongoing usability of SMZ. Few studies have investigated the toxicity of surfactants used in zeolite modification towards microorganisms and fewer have drawn linkages between surfactant desorption and surfactant toxicity. This review provides an overview of natural zeolite chemistry, characteristics and practical applications. The chemistry of commonly used surfactants is outlined, along with the kinetics that drive their adsorption to the zeolite surface. Methodologies to characterise this surfactant loading are also described. Applications of SMZ in water remediation are highlighted, giving focus to applications which deal with biological pollutants and where microorganisms play a role in the remediation process. Studies that have identified surfactant desorption from SMZ are outlined. Finally, the toxicity of a commonly used cationic surfactant towards microorganisms is discussed. This review highlights the potential for surfactant to desorb from the zeolite surface and the need for further research into the toxicity of this desorbed surfactant towards microorganisms, including pathogens and environmental microbes. Copyright © 2017 Elsevier Ltd. All rights reserved.

In situ surface transfer process of Cry1Ac protein on SiO2： The effect of biosurfactants for desorption.

PubMed

Miao, Shuzhou; Yuan, Xingzhong; Liang, Yunshan; Wang, Hou; Leng, Lijian; Wu, Zhibin; Jiang, Longbo; Li, Yifu; Mo, Dan; Zeng, Guangming

2018-01-05

Genetically modified Bacillus thuringiensis (Bt) crops, which have been widely used in agricultural transgenic plants, express insecticidal Cry proteins and release the toxin into soils. Taking into consideration the environmental risk of Cry proteins, biosurfactant-rhamnolipids were applied to desorb Cry proteins from soil environment, which has not been elucidated before. Quartz crystal microbalance with dissipation (QCM-D) was used in this article to investigate the adsorption and desorption behaviors of Cry1Ac on SiO 2 surface (model soil). Results showed that patch-controlled electrostatic attraction (PCEA) governed Cry1Ac adsorption to SiO 2, and the solution pH or ionic strength can affect PCEA. The adsorption kinetics could be fitted by the pseudo-second-order model, and the adsorption isotherm was fitted to Langmuir model with correlation coefficients higher than 0.999. The desorption characteristics of Cry1Ac from SiO 2 were assessed in the presence of mono-rhamnolipid, di-rhamnolipid or complex-rhamnolipid. Mono-rhamnolipid exhibited the most significant positive effect on desorption performance. With a complete removal of Cry1Ac reached when mono-rhamnolipid concentration was up to 50mgL -1 . Additionally, the desorption was enhanced at alkaline pH range, and Cry1Ac can be completely and rapidly desorbed by rhamnolipids from SiO 2 at ionic strength of 5×10 -2 M. Copyright © 2017 Elsevier B.V. All rights reserved.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Effects of the amendment of biochars and carbon nanotubes on the bioavailability of hexabromocyclododecanes (HBCDs) in soil to ecologically different species of earthworms.

PubMed

Li, Bing; Zhu, Hongkai; Sun, Hongwen; Xu, Jiayao

2017-03-01

Biochar is a promising material used in soil amendment and carbon nanotubes may enter soil due to its increasing application. These carbonaceous materials may change the bioavailability of pollutants in soil. In this concern, 0.5% w/w multi-walled carbon nanotubes (MWCNTs) and 3 corn-straw biochars acquired at different pyrolyzing temperatures were used in soil amendment and their influences on the bioavailability of hexabromocyclododecanes (HBCDs), a brominated flame retardant, to 2 ecologically different earthworm species were studied. The amendment of 4 carbonaceous materials all reduced the bioaccumulation of HBCDs in earthworms by 18.2%-67.3%, which varied depending on the type of carbonaceous materials and the pyrolyzing temperature of biochars. The reduction in HBCDs uptake by Eisenia fetida (an epigeic species) was greater than by Metaphire guillelmi (an anecic species). The 2 earthworm species both showed bioaccumulative selectivity on certain HBCD diastereoisomer and enantiomer in the amended soils, which was similar to that in the control soil. Moreover, Tenax-assisted HBCDs desorption test was carried out for the simulation of their bioavailability. The rapid desorption fraction (F rap ), total desorption (15 d), and 24 h desorption all correlated well with the uptake of HBCDs in the earthworms, suggesting that the 24 h-desorption, due to its easy availability, can be a good proxy to predict the bioavailability of HBCDs to earthworms in soil. Copyright © 2016. Published by Elsevier Ltd.

Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

PubMed

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution 'Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10(-9) M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

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.

Phosphorus sorption-desorption and effects of temperature, pH and salinity on phosphorus sorption in marsh soils from coastal wetlands with different flooding conditions.

PubMed

Bai, Junhong; Ye, Xiaofei; Jia, Jia; Zhang, Guangliang; Zhao, Qingqing; Cui, Baoshan; Liu, Xinhui

2017-12-01

Wetland soils act as a sink or source of phosphorus (P) to the overlaying water due to phosphorus sorption-desorption processes. Litter information is available on sorption and desorption behaviors of phosphorus in coastal wetlands with different flooding conditions. Laboratory experiments were conducted to investigate phosphorus sorption-desorption processes, fractions of adsorbed phosphorus, and the effects of salinity, pH and temperature on phosphorus sorption on soils in tidal-flooding wetlands (TW), freshwater-flooding wetlands (FW) and seasonal-flooding wetlands (SW) in the Yellow River Delta. Our results showed that the freshly adsorbed phosphorus dominantly exists in Occluded-P and Fe/AlP and their percentages increased with increasing phosphorus adsorbed. Phosphorus sorption isotherms could be better described by the modified Langmuir model than by the modified Freundlich model. A binomial equation could be properly used to describe the effects of salinity, pH, and temperature on phosphorus sorption. Phosphorus sorption generally increased with increasing salinity, pH, and temperature at lower ranges, while decreased in excess of some threshold values. The maximum phosphorus sorption capacity (Q max ) was larger for FW soils (256 mg/kg) compared with TW (218 mg/kg) and SW soils (235 mg/kg) (p < 0.05). The percentage of phosphorus desorption (P des ) in the FW soils (7.5-63.5%) was much lower than those in TW (27.7-124.9%) and SW soils (19.2-108.5%). The initial soil organic matter, pH and the exchangeable Al, Fe and Cd contents were important factors influencing P sorption and desorption. The findings of this study indicate that freshwater restoration can contribute to controlling the eutrophication status of water bodies through increasing P sorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reversible hydrogen storage by NaAlH4 confined within a titanium-functionalized MOF-74(Mg) nanoreactor.

PubMed

Stavila, Vitalie; Bhakta, Raghunandan K; Alam, Todd M; Majzoub, Eric H; Allendorf, Mark D

2012-11-27

We demonstrate that NaAlH(4) confined within the nanopores of a titanium-functionalized metal-organic framework (MOF) template MOF-74(Mg) can reversibly store hydrogen with minimal loss of capacity. Hydride-infiltrated samples were synthesized by melt infiltration, achieving loadings up to 21 wt %. MOF-74(Mg) possesses one-dimensional, 12 Å channels lined with Mg atoms having open coordination sites, which can serve as sites for Ti catalyst stabilization. MOF-74(Mg) is stable under repeated hydrogen desorption and hydride regeneration cycles, allowing it to serve as a "nanoreactor". Confining NaAlH(4) within these pores alters the decomposition pathway by eliminating the stable intermediate Na(3)AlH(6) phase observed during bulk decomposition and proceeding directly to NaH, Al, and H(2), in agreement with theory. The onset of hydrogen desorption for both Ti-doped and undoped nano-NaAlH(4)@MOF-74(Mg) is ∼50 °C, nearly 100 °C lower than bulk NaAlH(4). However, the presence of titanium is not necessary for this increase in desorption kinetics but enables rehydriding to be almost fully reversible. Isothermal kinetic studies indicate that the activation energy for H(2) desorption is reduced from 79.5 kJ mol(-1) in bulk Ti-doped NaAlH(4) to 57.4 kJ mol(-1) for nanoconfined NaAlH(4). The structural properties of nano-NaAlH(4)@MOF-74(Mg) were probed using (23)Na and (27)Al solid-state MAS NMR, which indicates that the hydride is not decomposed during infiltration and that Al is present as tetrahedral AlH(4)(-) anions prior to desorption and as Al metal after desorption. Because of the highly ordered MOF structure and monodisperse pore dimensions, our results allow key template features to be identified to ensure reversible, low-temperature hydrogen storage.

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

NASA Astrophysics Data System (ADS)

Dupuy, R.; Bertin, M.; Féraud, G.; Michaut, X.; Jeseck, P.; Doronin, M.; Philippe, L.; Romanzin, C.; Fillion, J.-H.

2017-07-01

Context. Methane is among the main components of the ice mantles of interstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims: This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules are monitored and quantified. Methods: Tunable monochromatic vacuum ultraviolet light (VUV) light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7-13.6 eV (177-91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry, and absolute photodesorption yields of intact CH4 are deduced. Results: CH4 photodesorbs for photon energies higher than 9.1 eV ( 136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions: The photodesorption of CH4 from pure ice in various interstellar environments is around 2.0 ± 1.0 × 10-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles.

Interaction of cholesterol with sphingomyelins and acyl-chain-matched phosphatidylcholines: a comparative study of the effect of the chain length.

PubMed Central

Ramstedt, B; Slotte, J P

1999-01-01

In this study we have synthesized sphingomyelins (SM) and phosphatidylcholines (PC) with amide-linked or sn-2 linked acyl chains with lengths from 14 to 24 carbons. The purpose was to examine how the chain length and degree of unsaturation affected the interaction of cholesterol with these phospholipids in model membrane systems. Monolayers of saturated SMs and PCs with acyl chain lengths above 14 carbons were condensed and displayed a high collapse pressure ( approximately 70 mN/m). Monolayers of N-14:0-SM and 1(16:0)-2(14:0)-PC had a much lower collapse pressure (58-60 mN/m) and monounsaturated SMs collapsed at approximately 50 mN/m. The relative interaction of cholesterol with these phospholipids was determined at 22 degreesC by measuring the rate of cholesterol desorption from mixed monolayers (50 mol % cholesterol; 20 mN/m) to beta-cyclodextrin in the subphase (1.7 mM). The rate of cholesterol desorption was lower from saturated SM monolayers than from chain-matched PC monolayers. In SM monolayers, the rate of cholesterol desorption was very slow for all N-linked chains, whereas for PC monolayers we could observe higher desorption rates from monolayers of longer PCs. These results show that cholesterol interacts favorably with SMs (low rate of desorption), whereas its interaction (or miscibility) with long chain PCs is weaker. Introduction of a single cis-unsaturation in the N-linked acyl chain of SMs led to faster rates of cholesterol desorption as compared with saturated SMs. The exception was monolayers of N-22:1-SM and N-24:1-SM from which cholesterol desorbed almost as slowly as from the corresponding saturated SM monolayers. The results of this study suggest that cholesterol is most likely capable of interacting with all physiologically relevant (including long-chain) SMs present in the plasma membrane of cells. PMID:9929492

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.

EFFECTS OF TEMPERATURE ON TRICHLOROETHYLENE DESORPTION FROM SILICA GEL AND NATURAL SEDIMENTS. 1. ISOTHERMS. (R822626)

EPA Science Inventory

Aqueous phase isotherms were calculated from vapor phase desorption isotherms
measured at 15, 30, and 60 C for
trichloroethylene on a silica gel, an aquifer sediment, a soil, a sand fraction,
and a clay and silt fraction, all at...

DEMONSTRATION BULLETIN: THE ECO LOGIC THERMAL DESORPTION UNIT - MIDDLEGROUND LANDFILL - BAY CITY, MI - ELI ECO LOGIC INTERNATIONAL, INC.

EPA Science Inventory

ECO Logic has developed a thermal desorption unit 0"DU) for the treatment of soils contaminated with hazardous organic contaminants. This TDU has been designed to be used in conjunction with Eco Logic's patented gas-phase chemical reduction reactor. The Eco Logic reactor is the s...

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...

EFFECTS OF TEMPERATURE ON TRICHLOROETHYLENE DESORPTION FROM SILICA GEL AND NATURAL SEDIMENTS. 2. KINETICS. (R822626)

EPA Science Inventory

Isothermal desorption rates were measured at 15, 30, and 60 src="/ncer/pubs/images/deg.gif">C for trichloroethylene (TCE) on a silica gel,
an aquifer sediment, a soil, a sand fraction, and a clay and silt fraction, all
at 100% relative humidity. Temperature-st...

Laser desorption mass spectrometry for molecular diagnosis

NASA Astrophysics Data System (ADS)

Chen, C. H. Winston; Taranenko, N. I.; Zhu, Y. F.; Allman, S. L.; Tang, K.; Matteson, K. J.; Chang, L. Y.; Chung, C. N.; Martin, Steve; Haff, Lawrence

1996-04-01

Laser desorption mass spectrometry has been used for molecular diagnosis of cystic fibrosis. Both 3-base deletion and single-base point mutation have been successfully detected by clinical samples. This new detection method can possibly speed up the diagnosis by one order of magnitude in the future. It may become a new biotechnology technique for population screening of genetic disease.

POLYCYCLIC AROMATIC HYDROCARBON (PAH) SIZE DISTRIBUTIONS IN AEROSOLS FROM APPLIANCES OF RESIDENTIAL WOOD COMBUSTION AS DETERMINED BY DIRECT THERMAL DESORPTION - GC/MS

EPA Science Inventory

The paper describesd a direct thermal desorption (TDS) approach to determine the PAH composition (MW = 202-302 amu) in size-segregated aerosols from residential wood combustion (RWC). Six combustion tests are performed with two highly available wood fuel varieties, Douglas-fir (P...

[Mass-spectrometric analysis of an anti-microbial preparation decamethoxine].

PubMed

Sukhodub, L F; Kosevich, M V; Shelkovskiĭ, V S; Volianskiĭ, Iu L

1989-11-01

I. I. Mechnikov Kharkov Research Institute of Microbiology, Vaccines and Sera, Ministry of Public Health of the Ukrainian SSR. The results of mass spectrometric investigation of decamethoxine++, an antimicrobial chemotherapeutic drug, are presented. It was shown that desorption-field mass spectrometry provided recording decamethoxine++ intensive quasimolecular ions [M.Cl]+ and [M]++ forming under conditions of high electric intensity only from the intact parent molecule. Hence, the presence of the peaks in the desorption field mass spectra made it possible to definitively determine decamethoxine++ in the samples. Therefore, the procedure of desorption-field mass spectrometry proved reliable in identification of bisquaternary ammonium compounds. Ways for thermal decomposition and mass spectrometric fragmentation of the decamethoxine++ molecule under various ionization conditions are also discussed.

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.

From Laser Desorption to Laser Ablation of Biopolymers

NASA Astrophysics Data System (ADS)

Franz, Hillenkamp

1998-03-01

For selected indications laser ablation and cutting of biological tissues is clinical practice. Preferentially lasers with emission wavelengths in the far UV and the mid IR are used, for which tissue absorption is very high. Morphologically the ablation sites look surprisingly similar for the two wavelength ranges, despite of the very different prim y putative interaction mechanisms. Ablation depth as a function of fluence follows a sigmoidal curve. Even factors below the nominal ablation threshold superficial layers of material get removed from the surface. This is the fluence range for Matrix-Assisted Laser Desorption/Ionization (MALDI). Evidence will be presented which suggest that strong similarities exist between the desorption and ablation processes both for UV- as well as for IR-wavelengths.