Desorption

This study presents the effects of equations of state (EOSs) on methane adsorption capacity, sorption hysteresis and initial gas reserves of a medium volatile bituminous coal. The sorption experiments were performed, at temperatures of 25 • C and 40 • C and up to 7MPa pressure, using a high-pressure volumetric analyzer (HPVA-II). The measured isotherms were parameterized with the modified (three-parameter) Langmuir model. Gas compressibility factors were calculated using six popular equations of state and the results were compared with those obtained using gas compressibility factors from NIST-Refprop ® (which implies McCarty and Arp's EOS for Z-factor of helium and Setzmann and Wagner's EOS for that of methane). Significant variations were observed in the resulting isotherms and associated model parameters with EOS. Negligible hysteresis was observed with NIST-refprop at both experimental temperatures, with the desorption isotherm being slightly lower than the adsorption isotherm at 25 • C. Compared to NIST-refprop, it was observed that equations of state that gave lower values of Z-factor for methane resulted in "positive hysteresis", (one in which the desorption isotherm is above the corresponding adsorption curve) and the more negatively deviated the Z-factors are, the bigger the observed hysteresis loop. Conversely, equations of state that gave positively deviated Z-factors of methane relatively produced "negative hysteresis" loops where the desorption isotherms are lower than the corresponding adsorption isotherms. Adsorbed gas accounted for over 90% of the calculated original gas in place (OGIP) and the larger the Langmuir volume, the larger the proportion of OGIP that was adsorbed.

Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch K(d) values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10(-6) M (238 microg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption K(d) values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption K(d) values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected.

ABSTRACT A number of previous studies have reported the existence of a minimum in phosphate solubility between pH 5.5 and 7 in non-calcareous soils. Different hypotheses have been forwarded to explain this phenomenon. In this study, ten soil samples with varying textures and phosphorus status were subjected to batch experiments in which dissolved phosphate was measured as a function of pH and phosphate load. Soil samples with more than 20% clay all had a minimum phosphate solubility between pH 6 and 7, whereas for samples with <10% clay, no such minimum was observed. Further experiments involving additions of phosphate and arsenate showed an increasing adsorption of these anions with decreasing pH also below pH 6 in clay soils, suggesting that the pH dependence on adsorption and desorption in short-term experiments was not the same. Kinetic experiments showed that the increased phosphate desorption at lower pH values in non-calcareous clay soils was a quick process, which is consistent with adsorption/desorption being the most important mechanism governing the retention and release of inorganic P. Moreover, by comparing extraction results with batch experiment results for samples from a long-term fertility experiment, it was concluded that more than 60% of the accumulated phosphate was occluded, i.e. not reactive within 6 days. Additional evidence for an important role of occluded phosphate comes from an analysis of the Freundlich sorption isotherms for the studied soils. It is hypothesized that interlayered hydroxy-Al and hydroxy-Fe polymers in clay minerals may be important for P dynamics in clay soils by trapping some of the P in an occluded form. The results also suggest that improved knowledge on the speciation and dynamics of phosphorus in soils is required for consistent mechanistically based modeling of phosphate sorption/desorption reactions.

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite (α-FeOOH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller surface area analysis. Pseudo-first order (PFO) and pseudo-second order (PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption, respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics.

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite (α-FeOOH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller surface area analysis. Pseudo-first order (PFO) and pseudo-second order (PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption, respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics.

This paper describes quantitation of biodegradation kinetics in soil slurry and compacted soil systems using polycyclic aromatic hydrocarbons (PAHs) as the test contaminants. The experimental protocol, elaborated in this paper, results in the measurement of biokinetic parameters which can be used to quantitate both ex‐situ and in‐situ bioremediation rates and assess the attainable end‐points. Biodegradation studies were conducted for naphthalene

ABSTRACT a b s t r a c t The influence of contact time, temperature and particle size on lead sorption by the natural and Fe(III)-modified zeolites was investigated. Characterization of the natural and Fe(III)-modified zeolite before and after lead sorption was performed by determination of textural properties, by scanning elec-tron microscopy and X-ray spectroscopy in energy-dispersive mode (SEM–EDS), transmission electron microscopy (TEM) and X-ray powder diffraction (XRPD) analysis. Lead sorption kinetics at 303–333 K, best represented by the pseudo-second order model and activation energy (13.5 and 8.5 kJ/mol for the natural and Fe(III)-modified zeolite respectively) confirmed an activated chemical sorption. Desorption experiments indicated that lead was irreversibly sorbed on both zeolites. XRPD, TEM and SEM results showed that modification of the natural zeolite with Fe(III) ions did not change its crystal structure and iron is mainly located at the zeolite surface, likely in form of amorphous iron oxy-hydroxides. Specific surface area significantly increases after modification of the natural zeolite with Fe(III) ions (from 30.2 for the natural to 52.5 m 2 /g for Fe(III)-modified zeolite). Characterization of both lead saturated sorbents suggested that besides ion exchange, lead is both chemisorbed and precipitated at their surfaces, and presence of amorphous iron in Fe(III)-modified zeolite favors sorption of lead.

Lawrence Livermore National Laboratory (LLNL) has developed a mass spectrometer-based system that measures organic surface residues in situ. This system, called the Contamination Analysis Unit (CAU), can detect and quantify a variety of volatile surface residues on a range of different substrates. Residue samples are removed from the substrate using a combination of vacuum and thermal desorption, and are then ionized and quantified by a quadrupole mass spectrometer. The current effort (Phase 2) was carried out in accordance with Thiokol Project Test Plan PTP-0467. A first phase of tests was completed under PTP-0327 and the results reported in TWR-75385. The Phase 2 test plan, PTP-0467, is a follow-on to PTP-0327, and was conducted in order to more fully determine the capabilities of the CAU. This report summarizes experiments in which the CAU was evaluated for application in reusable solid rocket motor production scenarios. The report has been ordered by the tasks requested by ATK Thiokol Propulsion Testplan PTP-0467. Project tasks included the following: (1) Determine the amount of residual propellant and liner components with the CAU after coupons have been cleaned. (2) Determine if the CAU can detect solvent that has soaked into NBR. (3) Test the capabilities of the CAU for analyzing non-flat surfaces on the inside and outside of the 12-foot diameter Reusable Solid Rocket Motor (RSRM) and 5-foot diameter nozzle throat housing surfaces. (4) Determine if solvent extraction and gas chromatography (GC) approaches are able to enhance the surface analysis data available through use of the mass-spectrometer-based CAU. (5) Determine the CAU's detection limit for various soils and cleaners. (6) Determine if contact of both Viton and silicon O-rings with critical substrates will result in any visual evidence of the contact, when observed under black light. (7) Demonstrate CAU viability during routine manufacturing Thiokol manufacturing operations. This effort was originally projected to include three one-week visits to Utah in 2000 to analyze surfaces during routine FSM-9 manufacturing and three additional one-week visits to Utah in 2001 during FSM-10 PSA manufacture. These two tasks were compressed into one that was conducted at Thiokol during 2000.

The objective of this study was to test the availability of the boron from doped oxides to rape (Brassica napus L.), and the effect of the boron doped oxides on soil acidosis. The soil was treated with goethite, manganite and their boron-containing oxides including iron oxide with adsorbed boron (i.e. ad-B-goethite), iron oxide with occluded boron (i.e. oc-B-goethite), manganese oxide

ABSTRACT This work reports experimental data on the desorption of pure propane and n‐butane from refined soybean oil at low pressures. The desorption parameters investigated were the overall solvent (normally gaseous at ambient conditions) content and solution stirring rate. Solvent mass fraction ranged from 1 to 10 wt% and stirring was studied in the interval between 0 and 200 rpm (equivalent to a Reynolds number 2 × 107). Results showed a fast solvent release from the binary propane–soybean oil system, while a relatively slower liberation was noticed for soybean oil−n‐butane, due possibly to the much smaller solubility exhibited by the former solvent. The experimental information reported in this work may be of great technological relevance, since no desorption data were found in the literature for the systems investigated in this work.

ABSTRACT Surface modification of biomaterials has been adopted over the years to improve their biocompatibility. In this study, aiming to promote hydrophilicity and to introduce natural recognition sites onto poly(L-lactic acid) (PLLA) films, chitosan and its derivatives, carboxymethyl chitosan(CMC) and N-methylene phosphonic chitosan (NPC), were used to modify the surface of PLLA films by an entrapment method. Radiolabeled (125I) proteins were used to measure the amount of protein adsorbed to PLLA surfaces. Fibronectin (Fn) was used to study the protein adsorption on the modified PLLA surfaces, including isotherm adsorption and adsorption kinetics of single protein, competitive adsorption of binary proteins system and serum multi-proteins and the desorption behavior in serum solution. The results showed that in the isotherm adsorption, Fn had a larger adsorption capacity on the CS-modified surface at lower concentrations, but had a high adsorption capacity at CMC-modified surface at higher concentrations. In the study of absorption kinetics, Fn had a fastest adsorption equilibrium and a highest equilibrium adsorption capacity at the CS-modified surface, while it was opposite at the PCS-modified surface. When BSA and serum were added, it had the greatest effect on the adsorption of Fn on the PCS-modified surface. After 6 hours soaking in the desorption study, Fn had reached desorption equilibrium on all the modified surfaces, which had different effects on the desorption rate and the remaining percentage of Fn.