The impacts of effective stress and CO 2 sorption on the matrix permeability of shale reservoir rocks [The impacts of CO 2 sorption and effective stress on the matrix permeability of shale reservoir rocks

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

Wu, Wei; Zoback, Mark D.; Kohli, Arjun H.

We assess the impacts of effective stress and CO 2 sorption on the bedding-parallel matrix permeability of the Utica shale through pressure pulse-decay experiments. We first measure permeability using argon at relatively high (14.6 MPa) and low (2.8 MPa) effective stresses to assess both pressure dependence and recoverability. We subsequently measure permeability using supercritical CO 2 and again using argon to assess changes due to CO 2 sorption. We find that injection of both argon and supercritical CO 2 reduces matrix permeability in distinct fashion. Samples with permeability higher than 10 –20 m 2 experience a large permeability reduction aftermore » treatment with argon, but a minor change after treatment with supercritical CO 2. However, samples with permeability lower than this threshold undergo a slight change after treatment with argon, but a dramatic reduction after treatment with supercritical CO 2. These results indicate that effective stress plays an important role in the evolution of relatively permeable facies, while CO 2 sorption dominates the change of ultra-low permeability facies. The permeability reduction due to CO 2 sorption varies inversely with initial permeability, which suggests that increased surface area from hydraulic stimulation with CO 2 may be counteracted by sorption effects in ultra-low permeability facies. As a result, we develop a conceptual model to explain how CO 2 sorption induces porosity reduction and volumetric expansion to constrict fluid flow pathways in shale reservoir rocks.« less

Free energy study of H2O, N2O5, SO2, and O3 gas sorption by water droplets/slabs

NASA Astrophysics Data System (ADS)

Li, Wentao; Pak, Chi Yuen; Tse, Ying-Lung Steve

2018-04-01

Understanding gas sorption by water in the atmosphere is an active research area because the gases can significantly alter the radiation and chemical properties of the atmosphere. We attempt to elucidate the molecular details of the gas sorption of water and three common atmospheric gases (N2O5, SO2, and O3) by water droplets/slabs in molecular dynamics simulations. The system size effects are investigated, and we show that the calculated solvation free energy decreases linearly as a function of the reciprocal of the number of water molecules from 1/215 to 1/1000 in both the slab and the droplet systems. By analyzing the infinitely large system size limit by extrapolation, we find that all our droplet results are more accurate than the slab results when compared to the experimental values. We also show how the choice of restraints in umbrella sampling can affect the sampling efficiency for the droplet systems. The free energy changes were decomposed into the energetic ΔU and entropic -TΔS contributions to reveal the molecular details of the gas sorption processes. By further decomposing ΔU into Lennard-Jones and Coulombic interactions, we observe that the ΔU trends are primarily determined by local effects due to the size of the gas molecule, charge distribution, and solvation structure around the gas molecule. Moreover, we find that there is a strong correlation between the change in the entropic contribution and the mean residence time of water, which is spatially nonlocal and related to the mobility of water.

Comparison of high-pressure CO 2 sorption isotherms on Eastern and Western US coals

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

Romanov, V; Hur, T -B; Fazio, J

2013-10-01

Accurate estimation of carbon dioxide (CO 2) sorption capacity of coal is important for planning the CO 2 sequestration efforts. In this work, we investigated sorption and swelling behavior of several Eastern and Western US coal samples from the Central Appalachian Basin and from San Juan Basin. The CO 2 sorption isotherms have been completed at 55°C for as received and dried samples. The role of mineral components in coal, the coal swelling, the effects of temperature and moisture, and the error propagation have been analyzed. Changes in void volume due to dewatering and other factors such as temporary cagingmore » of carbon dioxide molecules in coal matrix were identified among the main factors affecting accuracy of the carbon dioxide sorption isotherms. The (helium) void volume in the sample cells was measured before and after the sorption isotherm experiments and was used to build the volume-corrected data plots.« less

Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

USGS Publications Warehouse

Blum, A.E.; Eberl, D.D.

2004-01-01

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m2, which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Phenanthrene and 2,2',5,5'-PCB sorption by several soils from methanol-water solutions: the effect of weathering and solute structure.

PubMed

Hyun, Seunghun; Kim, Minhee; Baek, Kitae; Lee, Linda S

2010-01-01

The effect of the sorption of phenanthrene and 2,2',5,5'-polychlorinated biphenyl (PCB52) by five differently weathered soils were measured in water and low methanol volume fraction (f(c)0.5) as a function of the apparent solution pH (pH(app)). Two weathered oxisols (A2 and DRC), and moderately weathered alfisols (Toronto) and two young soils (K5 and Webster) were used. The K(m) (linear sorption coefficient) values, which log-linearly decreases with f(c), were interpreted using a cosolvency sorption model. For phenanthrene sorption at the natural pH, the empirical constant (alpha) ranged between 0.95 and 1.14, and was in the order of oxisols (A2 and DRC)sorption reduction than those predicted from the increment of the solute's activity coefficient in the solution phase. A similar trend was observed for PCB52 sorption. The K(m) values measured at the range of pH 3-7 also showed an inversely log-linear relationship. The regression slope (alphasigma) calculated from the cosolvency sorption model as a function of pH(app) only varied within <5%, with the exception for phenanthrene sorption by two highly weathered soils, which had 10% greater alphasigma values obtained at acidic pH(app). This phenomenon is a result of the greater acid enhancement effect on phenanthrene sorption by the oxisols, which is reduced with increasing f(c). These results revealed an unexplored relationship between the cosolvent effect on the sorption and the properties of the soil organic matter (a primary sorption domain) as a function of the degree of soil weathering. Copyright 2009 Elsevier Ltd. All rights reserved.

Measurement of solubility and water sorption of dental nanocomposites light cured by argon laser.

PubMed

Mirsasaani, Seyed Shahabeddin; Ghomi, Farhad; Hemati, Mehran; Tavasoli, Tina

2013-03-01

Different parameters used for photoactivation process and also composition provide changes in the properties of dental composites. In the present work the effect of different power density of argon laser and filler loading on solubility (SL) and water sorption (WS) of light-cure dental nanocomposites was studied. The resin of nanocomposites was prepared by mixing bisphenol A glycol dimethacrylate (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) with a mass ratio of 65/35. 20 wt.% and 25 wt.% of nanosilica fillers with a primary particle size of 10 nm were added to the resin. Camphorquinone (CQ) and DMAEMA were added as photoinitiator system. The nanocomposites were cured by applying the laser beam at the wavelength of 472 nm and power densities of 260 and 340 mW/cm(2) for 40 sec. Solubility and water sorption were then measured according to ISO 4049, which in our case, the maximums were 2.2% and 4.3% at 260 mW/cm(2) and 20% filler, respectively. The minimum solubility (1.2%) and water sorption (3.8%) were achieved for the composite containing 25% filler cured at 340 mW/cm(2). The results confirmed that higher power density and filler loading decreased solubility of unreacted monomers and water sorption and improved physico-mechanical properties of nanocomposites.

Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

PubMed

Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

2017-04-01

In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

A method to simultaneously determine sorption isotherms and sorption enthalpies with a double twin microcalorimeter

NASA Astrophysics Data System (ADS)

Wadso, Lars; Markova, Natalia

2002-07-01

Sorption of vapors of water, ethanol, and other liquids on solids like pharmaceuticals, textiles and food stuffs are of both practical and theoretical importance. In this article we present a technique to simultaneously measure sorption isotherms and sorption enthalpies. The sample is contained in one end of a sorption vessel. In the other end a vaporizable liquid is introduced to start the measurement. Mass transfer from the liquid to the sample is by vapor diffusion and the rate of mass transfer is calculated from the measured thermal power of vaporization. Simultaneously, the thermal power of sorption is measured and from this one may calculate the differential enthalpy of sorption. The thermal power measurements are made by inserting the sorption vessel in an isothermal double twin microcalorimeter.

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

Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

PubMed

Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

2009-05-01

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data

USGS Publications Warehouse

Chiou, C.T.; Rutherford, D.W.; Manes, M.

1993-01-01

Vapor sorption isotherms of ethylene glycol monoethyl ether (EGME) at room temperature and isotherms of N2 gas at liquid nitrogen temperature were determined for various soils and minerals. The N2 monolayer capacities [Qm (N2)] were calculated from the BET equation and used to determine the surface areas. To examine whether EGME is an appropriate adsorbate for determination of surface areas, the apparent EGME monolayer capacities [Qm (EGME)ap] were also obtained by use of the BET equation. For sand, aluminum oxide, kaolinite, hematite, and synthetic hydrous iron oxide, which are relatively free of organic impurity and expanding/solvating minerals, the Qm (EGME)ap values are in good conformity with the corresponding Qm (N2) values and would give surface areas consistent with BET (N2) values. For other samples (Woodburn soil, a natural hydrous iron oxide, illite, and montmorillonite), the Qm (EGME)ap values overestimate the Qm (N2) values from a moderate to a large extent, depending on the sample. A high-organic-content peat shows a very small BET (N2) surface area; the EGME/ peat isotherm is linear and does not yield a calculation of the surface area. Large discrepancies between results of the two methods for some samples are attributed to the high solubility of polar EGME in soil organic matter and/ or to the cation solvation of EGME with solvating clays. The agreement for other samples is illustrative of the consistency of the BET method when different adsorbates are used, so long as they do not exhibit bulk penetration and/or cation solvation. ?? 1993 American Chemical Society.

Sorption of radionuclides by cement-based barrier materials

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

Li, Kefei, E-mail: likefei@tsinghua.edu.cn; Pang, Xiaoyun

2014-11-15

This paper investigates the sorption of radionuclide ions, {sup 137}Cs{sup +} and {sup 90}Sr{sup 2+}, by cement-based barrier materials for radioactive waste disposal. A mortar with ternary binder is prepared and powder samples are ground from the hardened material following a predetermined granulometry. After pre-equilibrium with an artificial pore solution, the sorption behaviors of powder samples are investigated through single sorption and blended sorption. The results show that: (1) no systematic difference is observed for single and blended sorptions thus the interaction between {sup 137}Cs{sup +} and {sup 90}Sr{sup 2+} sorptions must be weak; (2) the sorption kinetics is rapidmore » and all characteristic times are less than 1d; (3) the sorption capacity is enhanced by C–A–S–H hydrates and the measured K{sub d} values can be predicted from C–S–H sorption data with Ca/Si ratio equal to Ca/(Si + Al) ratio.« less

Interactions among K+-Ca2+ exchange, sorption of m-dinitrobenzene, and smectite quasicrystal dynamics.

PubMed

Chatterjee, Ritushree; Laird, David A; Thompson, Michael L

2008-12-15

The fate of organic contaminants in soils and sediments is influenced by sorption of the compounds to surfaces of soil materials. We investigated the interaction among sorption of an organic compound, cation exchange reactions, and both the size and swelling of smectite quasicrystals. Two reference smectites that vary in location and amount of layer charge, SPV (a Wyoming bentonite) and SAz-1 were initially Ca- and K-saturated and then equilibrated with mixed 0.01 M KCl and 0.005 M CaCl2 salt solutions both with and without the presence of 200 mg L(-1) m-dinitrobenzene (m-DNB). In general, sorption of m-DNB increased with the amount of K+ in the system for both clays, and the SPV sorbed more m-DNB than the SAz-1. Sorption of m-DNB increased the preference of Ca-SPV for K+ relative to Ca2+ but had little effect on K+-Ca2+ selectivity for K-SPV. Selectivity for K+ relative to Ca2+ was slightly higher for both K-SAz-1 and Ca-SAz-1 in the presence of m-DNB than in its absence. Distinct hysteresis loops were observed for the K+-Ca2+ cation exchange reactions for both clays, and the legacy of having been initially Ca- or K-saturated influenced sorption of m-DNB by SPV but had little effect for SAz-1. Suspension X-ray diffraction was used to measure changes in d-spacing and the relative thickness of smectite quasicrystals during the cation exchange and m-DNB sorption reactions. The results suggest that interactions among cation exchange and organic sorption reactions are controlled byan inherently hysteretic complex feedback process that is regulated by changes in the size and extent of swelling of smectite quasicrystals.

SORPTION OF ARSENATE AND ARSENITE ON RUO2.XH2O: A SPECTROSCOPIC AND MACROSCOPIC STUDY

EPA Science Inventory

The sorption of arsenate (As(V)) and arsenite (As(III)) on RuO2 xH2O was examined using macroscopic and microscopic techniques. Constant solid:solution ratio isotherms were constructed from batch sorption experiments to study the sorption of the inorganic arsenic species on RuO2...

Sorption behavior of 17 phthalic acid esters on three soils: effects of pH and dissolved organic matter, sorption coefficient measurement and QSPR study.

PubMed

Yang, Fen; Wang, Meng; Wang, Zunyao

2013-09-01

This work studies the sorption behaviors of phthalic acid esters (PAEs) on three soils by batch equilibration experiments and quantitative structure property relationship (QSPR) methodology. Firstly, the effects of soil type, dissolved organic matter and pH on the sorption of four PAEs (DMP, DEP, DAP, DBP) are investigated. The results indicate that the soil organic carbon content has a crucial influence on sorption progress. In addition, a negative correlation between pH values and the sorption capacities was found for these four PAEs. However, the effect of DOM on PAEs sorption may be more complicated. The sorption of four PAEs was promoted by low concentrations of DOM, while, in the case of high concentrations, the influence of DOM on the sorption was complicated. Then the organic carbon content normalized sorption coefficient (logKoc) values of 17 PAEs on three soils were measured, and the mean values ranged from 1.50 to 7.57. The logKoc values showed good correlation with the corresponding logKow values. Finally, two QSPR models were developed with 13 theoretical parameters to get reliable logKoc predictions. The leave-one-out cross validation (CV-LOO) indicated that the internal predictive power of the two models was satisfactory. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Contribution of coated humic acids calculated through their surface coverage on nano iron oxides for ofloxacin and norfloxacin sorption.

PubMed

Peng, Hongbo; Liang, Ni; Li, Hao; Chen, Fangyuan; Zhang, Di; Pan, Bo; Xing, Baoshan

2015-09-01

Sorption of organic contaminants on organo-mineral complexes has been investigated extensively, but the sorption contribution of mineral particles was not properly addressed before calculating KOC, especially for ionic organic contaminants. We measured the surface coverage of a humic acid (HA) on nano iron oxides (n-Fe2O3) in a series of synthesized organo-mineral complexes. The contribution of the coated HA to ofloxacin (OFL) and norfloxacin (NOR) sorption in HA-n-Fe2O3 complexes was over 80% of the total sorption with the surface coverage of 36% and fOC of 1.6%. All the coated HA showed higher sorption to NOR and OFL in comparison to the original HA, suggesting HA fractionation and/or physical re-conformation during organo-mineral complex formation. The decreased KOC with multilayer coating may suggest the importance of site-specific interactions for OFL sorption, while the increased KOC with multilayer coating may suggest the importance of partitioning in hydrophobic region for NOR sorption. Copyright © 2015 Elsevier Ltd. All rights reserved.

Programming MOFs for water sorption: amino-functionalized MIL-125 and UiO-66 for heat transformation and heat storage applications.

PubMed

Jeremias, Felix; Lozan, Vasile; Henninger, Stefan K; Janiak, Christoph

2013-12-07

Sorption-based heat transformation and storage appliances are very promising for utilizing solar heat and waste heat in cooling or heating applications. The economic and ecological efficiency of sorption-based heat transformation depends on the availability of suitable hydrophilic and hydrothermally stable sorption materials. We investigated the feasibility of using the metal-organic frameworks UiO-66(Zr), UiO-67(Zr), H2N-UiO-66(Zr) and H2N-MIL-125(Ti) as sorption materials in heat transformations by means of volumetric water adsorption measurements, determination of the heat of adsorption and a 40-cycle ad/desorption stress test. The amino-modified compounds H2N-UiO-66 and H2N-MIL-125 feature high heat of adsorption (89.5 and 56.0 kJ mol(-1), respectively) and a very promising H2O adsorption isotherm due to their enhanced hydrophilicity. For H2N-MIL-125 the very steep rise of the H2O adsorption isotherm in the 0.1 < p/p0 < 0.2 region is especially beneficial for the intended heat pump application.

Sorption-desorption of indaziflam in selected agricultural soils.

PubMed

Alonso, Diego G; Koskinen, William C; Oliveira, Rubem S; Constantin, Jamil; Mislankar, Suresh

2011-12-28

Indaziflam, a new alkylazine herbicide that inhibits cellulose biosynthesis, is under current development for soil applications in perennial crops and nonagricultural areas. Sorption and desorption of indaziflam in six soils from Brazil and three soils from the United States, with different physical chemical properties, were investigated using the batch equilibration method. Sorption kinetics demonstrated that soil-solution equilibrium was attained in <24 h. The Freundlich equation described the sorption behavior of the herbicide for all soils (R(2) > 0.99). K(f) values of the Brazilian oxisols ranged from 4.66 to 29.3, and 1/n values were ≥ 0.95. Sorption was positively correlated to %OC and clay contents. U.S. mollisol K(f) values ranged from 6.62 to 14.3; 1/n values for sorption were ≥ 0.92. K(f) values from mollisols were also positively correlated with %OC. These results suggest that indaziflam potential mobility, based solely on its sorption coefficients, would range from moderate to low in soil. Desorption was hysteretic on all soils, further decreasing its potential mobility for offsite transport.

Short hold times in dynamic vapor sorption measurements mischaracterize the equilibrium moisture content of wood

Treesearch

Samuel V. Glass; Charles R. Boardman; Samuel L. Zelinka

2017-01-01

Recently, the dynamic vapor sorption (DVS) technique has been used to measure sorption isotherms and develop moisture-mechanics models for wood and cellulosic materials. This method typically involves measuring the time-dependent mass response of a sample following step changes in relative humidity (RH), fitting a kinetic model to the data, and extrapolating the...

Humidity sorption on natural building stone

NASA Astrophysics Data System (ADS)

Franzen, C.; Mirwald, P.

2003-04-01

processes, physical, chemical or biological, depend on the presence of water. Like most porous materials building stone respond on humidity by water uptake. The sorption isotherm represents the equilibrium moisture, specific for each material. The determination of the isotherm for stone of low and small porosity like marble is difficult. With the help of a newly developed water sorption analysis chamber [2], which allows the simultaneous measurement of 11 samples, good results on stone/rock samples have been obtained. Even at marble species with pore volumes lower than 0.4 % isotherms are measured. This analytical method offers new insights in the pore behaviour of low porosity materials. The advantages of this technique which supplements other techniques (e.g. BET, Hg-porosimetry) are: i) the testing agent is identical to the weathering agent, water; ii) the atmospheric parameters at the measurement reflect the natural conditions - thus no changes to the material properties have to be considered; iii) due to the small diameter of the water molecule (~0.28 nm), smaller pores are reached than e.g. with N2 (~0.31 nm). Sorption isotherms of sandstone (Baumberg, Obernkirchen, Groeden), granite (Brixen), and marble (Sterzing, Laas) are presented. Particular as to marbles the resolution is considerably higher. A previously observed negative hysteresis [3] seems an effect due to limited data resolution. [1] Snethlage, R. (1984) Steinkonservierung, Bayer. LA Denkmalpflege, Ah. 22, 203 S. [2] Griesser, U.J., Dillenz, J. (2002) Neuartiges, vollautomatisches Feuchtesorptionsprüfgerät mit hohem Probendurchsatz, Feuchtetag 2002, Weimar, 85-93. [3] Fimmel, R. (1996) Verwitterungsverhalten der alpinen Marmore von Laas und Sterzing, Diss. Univ. Ibk, 116 S.

Sorption equilibria of ethanol on cork.

PubMed

Lequin, Sonia; Chassagne, David; Karbowiak, Thomas; Bellat, Jean-Pierre

2013-06-05

We report here for the first time a thermodynamic study of gaseous ethanol sorption on raw cork powder and plate. Our study aims at a better understanding of the reactivity of this material when used as a stopper under enological conditions, thus in close contact with a hydroethanolic solution, wine. Sorption−desorption isotherms were accurately measured by thermogravimetry at 298 K in a large range of relative pressures. Sorption enthalpies were determined by calorimetry as a function of loading. Sorption−desorption isotherms exhibit a hysteresis loop probably due to the swelling of the material and the absorption of ethanol. Surprisingly, the sorption enthalpy of ethanol becomes lower than the liquefaction enthalpy as the filling increases. This result could be attributed to the swelling of the material, which would generate endothermic effects. Sorption of SO₂ on cork containing ethanol was also studied. When the ethanol content in cork is 2 wt %, the amount of SO₂ sorbed is divided by 2. Thus, ethanol does not enhance the sorption rate for SO₂ but, on the contrary, decreases the SO₂ sorption activity onto cork, probably because of competitive sorption mechanisms.

Column Chromatography To Obtain Organic Cation Sorption Isotherms.

PubMed

Jolin, William C; Sullivan, James; Vasudevan, Dharni; MacKay, Allison A

2016-08-02

Column chromatography was evaluated as a method to obtain organic cation sorption isotherms for environmental solids while using the peak skewness to identify the linear range of the sorption isotherm. Custom packed HPLC columns and standard batch sorption techniques were used to intercompare sorption isotherms and solid-water sorption coefficients (Kd) for four organic cations (benzylamine, 2,4-dichlorobenzylamine, phenyltrimethylammonium, oxytetracycline) with two aluminosilicate clay minerals and one soil. A comparison of Freundlich isotherm parameters revealed isotherm linearity or nonlinearity was not significantly different between column chromatography and traditional batch experiments. Importantly, skewness (a metric of eluting peak symmetry) analysis of eluting peaks can establish isotherm linearity, thereby enabling a less labor intensive means to generate the extensive data sets of linear Kd values required for the development of predictive sorption models. Our findings clearly show that column chromatography can reproduce sorption measures from conventional batch experiments with the benefit of lower labor-intensity, faster analysis times, and allow for consistent sorption measures across laboratories with distinct chromatography instrumentation.

Sorption of Cu(2+) on humic acids sequentially extracted from a sediment.

PubMed

Yang, Kun; Miao, Gangfen; Wu, Wenhao; Lin, Daohui; Pan, Bo; Wu, Fengchang; Xing, Baoshan

2015-11-01

In addition to the diverse properties of humic acids (HAs) extracted from different soils or sediments, chemical compositions, functional groups and structures of HAs extracted from a single soil or sediment could also be diverse and thus significantly affect sorption of heavy metals, which is a key process controlling the transfer, transformation and fate of heavy metals in the environment. In this study, we sequentially extracted four HA fractions from a single sediment and conducted the sorption experiments of Cu(2+) on these HA fractions. Our results showed that aromaticity and acidic group content of HA fraction decreased with increasing extraction. Earlier extracted HA fraction had higher sorption capacity and affinity for Cu(2+). There were two fractions of adsorbed Cu(2+) on HAs, i.e., ion exchanged fraction and surface bonded fraction, which can be captured mechanically by the bi-Langmuir model with good isotherm fitting. The ion exchanged fraction had larger sorption capacity but lower sorption affinity, compared with the surface bonded fraction. The dissociated carboxyl groups of HAs were responsible for both fractions of Cu(2+) sorption, due to the more Cu(2+) sorption on the earlier extracted HA fraction with more carboxyl groups and at higher pH. The intensive competition between H(+) and the exchangeable Cu(2+) could result in the decrease of ion exchanged capacity and affinity for Cu(2+) on HAs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorption of thiabendazole in sub-tropical Brazilian soils.

PubMed

de Oliveira Neto, Odilon França; Arenas, Alejandro Yopasa; Fostier, Anne Hélène

2017-07-01

Thiabendazole (TBZ) is an ionizable anthelmintic agent that belongs to the class of benzimidazoles. It is widely used in veterinary medicine and as a fungicide in agriculture. Sorption and desorption are important processes influencing transport, transformation, and bioavailability of xenobiotic compounds in soils; data related to sorption capacity are therefore needed for environmental risk assessments. The aim of this work was to assess the sorption potential of TBZ in four Brazilians soils (sandy, sandy-clay, and clay soils), using batch equilibrium experiments at three pH ranges (2.3-3.0, 3.8-4.2, and 5.5-5.7). The Freundlich sorption coefficient (K F ) ranged from 9.0 to 58 μg 1-1/n  (mL) 1/n  g -1 , with higher values generally observed at the lower pH ranges (2.3-3.0 and 3.8-4.2) and for clay soils. The highest organic carbon-normalized sorption coefficients (K OC ) obtained at pH 3.8-5.7 (around the natural pH range of 4.1-5.0) for both clay soils and sandy-clay soil were 3255 and 2015 mL g -1 , respectively. The highest correlations K F vs SOM (r = 0.70) and K F vs clay content (r = 0.91) were observed at pH 3.8-4.2. Our results suggest that TBZ sorption/desorption is strongly pH dependent and that its mobility could be higher in the studied soils than previously reported in soils from temperate regions.

The use of cross-linked chitosan beads for nutrients (nitrate and orthophosphate) removal from a mixture of P-PO4, N-NO2 and N-NO3.

PubMed

Jóźwiak, Tomasz; Filipkowska, Urszula; Szymczyk, Paula; Kuczajowska-Zadrożna, Małgorzata; Mielcarek, Artur

2017-11-01

A hydrogel chitosan sorbent ionically cross-linked with sodium citrate and covalently cross-linked with epichlorohydrin was used to remove nutrients from an equimolar mixture of P-PO 4 , N-NO 2 and N-NO 3 . The scope of the study included, among other things, determination of the influence of pH on nutrient sorption effectiveness, nutrient sorption kinetics as well as determination of the maximum sorption capacity of cross-linked chitosan sorbents regarding P-PO 4 (H 2 PO 4 - , HPO 4 2- ), N-NO 2 (HNO 2 , NO 2 - ), and N-NO 3 (NO 3 - ). The effect of the type of the cross-linking agent on the affinity of the modified chitosan to each nutrient was studied as well. The kinetics of nutrient sorption on the tested chitosan sorbents was best described with the pseudo-second order model. The model of intramolecular diffusion showed that P-PO 4 , N-NO 2 and N-NO3 sorption on cross-linked hydrogel chitosan beads proceeded in two phases. The best sorbent of nutrients turned out to be chitosan cross-linked covalently with epichlorohydrin; with P-PO 4 , N-NO 2 and N-NO 3 sorption capacity reaching: 1.23, 0.94 and 0.76mmol/g, respectively (total of 2.92mmol/g). For comparison, the sorption capacity of chitosan cross-linked ionically with sodium citrate was: 0.43, 0.39 and 0.39mmol/g for P-PO 4 , N-NO 2 and N-NO 3 , respectively (total of 1.21mmol/g). Copyright © 2017 Elsevier B.V. All rights reserved.

The variability of standard artificial soils: cadmium and phenanthrene sorption measured by a batch equilibrium method.

PubMed

Bielská, Lucie; Hovorková, Ivana; Kuta, Jan; Machát, Jiří; Hofman, Jakub

2017-01-01

Artificial soil (AS) is used in soil ecotoxicology as a test medium or reference matrix. AS is prepared according to standard OECD/ISO protocols and components of local sources are usually used by laboratories. This may result in significant inter-laboratory variations in AS properties and, consequently, in the fate and bioavailability of tested chemicals. In order to reveal the extent and sources of variations, the batch equilibrium method was applied to measure the sorption of 2 model compounds (phenanthrene and cadmium) to 21 artificial soils from different laboratories. The distribution coefficients (K d ) of phenanthrene and cadmium varied over one order of magnitude: from 5.3 to 61.5L/kg for phenanthrene and from 17.9 to 190L/kg for cadmium. Variations in phenanthrene sorption could not be reliably explained by measured soil properties; not even by the total organic carbon (TOC) content which was expected. Cadmium logK d values significantly correlated with cation exchange capacity (CEC), pH H2O and pH KCl , with Pearson correlation coefficients of 0.62, 0.80, and 0.79, respectively. CEC and pH H2O together were able to explain 72% of cadmium logK d variability in the following model: logK d =0.29pH H2O +0.0032 CEC -0.53. Similarly, 66% of cadmium logK d variability could be explained by CEC and pH KCl in the model: logKd=0.27pH KCl +0.0028 CEC -0.23. Variable cadmium sorption in differing ASs could be partially treated with these models. However, considering the unpredictable variability of phenanthrene sorption, a more reliable solution for reducing the variability of ASs from different laboratories would be better harmonization of AS preparation and composition. Copyright © 2016 Elsevier Inc. All rights reserved.

Application of headspace analysis to the study of sorption of hydrophobic organic chemicals to α-Al2O3

USGS Publications Warehouse

Pelinger, Judith A.; Eisenreich, Steven J.; Capel, Paul D.

1993-01-01

The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.

Sorption of selected organic compounds from water to a peat soil and its humic-acid and humin fractions: Potential sources of the sorption nonlinearity

USGS Publications Warehouse

Chiou, C.T.; Kile, D.E.; Rutherford, D.W.; Sheng, G.; Boyd, S.A.

2000-01-01

The sorption isotherms of ethylene dibromide (EDB), diuron (DUN), and 3,5-dichlorophenol (DCP) from water on the humic acid and humin fractions of a peat soil and on the humic-acid of a muck soil have been measured. The data were compared with those of the solutes with the whole peat from which the humic-acid (HA) and humin (HM) fractions were derived and on which the sorption of the solutes exhibited varying extents of nonlinear capacities at low relative concentrations (C(e)/S(w)). The HA fraction as prepared by the density-fractionated method is relatively pure and presumably free of high- surface-area carbonaceous material (HSACM) that is considered to be responsible for the observed nonlinear sorption for nonpolar solutes (e.g., EDB) on the peat; conversely, the base-insoluble HM fraction as prepared is presumed to be enriched with HSACM, as manifested by the greatly higher BET- (N2) surface area than that of the whole peat. The sorption of EDB on HA exhibits no visible nonlinear effect, whereas the sorption on HM shows an enhanced nonlinearity over that on the whole peat. The sorption of polar DUN and DCP on HA and HM display nonlinear effects comparable with those on the whole peat; the effects are much more significant than those with nonpolar EDB. These results conform to the hypothesis that adsorption onto a small amount of strongly adsorbing HSACM is largely responsible for the nonlinear sorption of nonpolar solutes on soils and that additional specific interactions with the active groups of soil organic matter are responsible for the generally higher nonlinear sorption of the polar solutes.

Sorption of benzimidazole anthelmintics to dissolved organic matter surrogates and sewage sludge.

PubMed

Kim, Hyo-Jung; Lee, Dong Soo; Kwon, Jung-Hwan

2010-06-01

The sorption coefficients of four rarely studied zwitterionic pharmaceuticals (benzimidazoles: fenbendazole, albendazole, thiabendazole and flubendazole) and four metabolites of fenbendazole to various dissolved organic matter surrogates (humic acid, sodium dodecyl sulfate micelle, hydroxypropyl-beta-cyclodextrin and liposomes made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and sewage sludge) were measured to extend the available sorption coefficients and eventually to evaluate their environmental fate in soil and water environment. For the entire range of dissolved organic matters, the more hydrophobic fenbendazole and albendazole had higher sorption coefficients than thiabendazole and flubendazole, indicating that the traditional hypothesis of hydrophobic interaction holds for zwitterionic benzimidazole anthelmintics. However, the sorption coefficients of a given benzimidazole to selected dissolved organic matters (DOMs) varied within an order of magnitude. The measured K(oc) values decreased in the order of fenbendazole, albendazole, thiabendazole and flubendazole for sewage sludge and hydroxypropyl-beta-cyclodextrin whereas the orders were different for the other DOM surrogates, implying the hydrophilic nature of sewage sludge. This was also supported by the (N+O)/C elemental ratio of the sewage sludge sample used in this study. The correlations between log K(oc) and log K(ow) were weak (r(2)=0.28-0.64) and the magnitude of the sorption coefficients to the hydrophilic organic matters (hydroxypropyl-beta-cyclodextrin and sewage sludge) were similar to or slightly smaller than those for the hydrophobic organic matters (humic acids and liposome). This suggests that specific hydrophilic interactions also play a significant role in the sorption of moderately hydrophobic benzimidazoles to organic matters. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Effects of N-vinylcaprolactam containing polyelectrolytes on hardness, fluoride release and water sorption of conventional glass ionomers.

PubMed

Moshaverinia, Alireza; Ansari, Sahar; Roohpour, Nima; Reshad, Mamaly; Schricker, Scott R; Chee, Winston Wl

2011-05-01

N-vinylcaprolactam (NVC) containing glass ionomers are promising dental restorative materials with improved mechanical properties; however, little information is available on other physical properties of this type of modified glass ionomer, especially their water sorption, fluoride releasing properties and microhardness. The purpose of this study was to investigate the effects of NVC-containing polyelectrolytes on microhardness, fluoride release and water sorption of conventional glass ionomer cements (GIC). The terpolymer of acrylic acid (AA), itaconic acid (IA) and N-vinylcaprolactam (NVC) with 8:1:1 and 7:1:2 (AA: IA: NVC) molar ratios was synthesized by free radical polymerization and characterized using 1H-NMR and FTIR. Experimental GIC specimens were made from a 50% solution of the synthesized terpolymer with Fuji IX powder in a 3.6:1 P/L ratio. Specimens were mixed and fabricated at room temperature. Vickers hardness was determined using a microhardness tester. Water sorption and fluoride releasing properties were also investigated. Commercial Fuji IX was used as the control group. All specimens were first conditioned in distilled water at 37°C for 1 day up to 1 month. Results for the experimental GIC were compared with the control group, using 1-way and 2-way ANOVA and the Tukey multiple range test (α=.05). The NVC-modified GIC exhibited higher mean values of Vickers hardness numbers (VHN). However, the data exhibited no statistically significant differences between the experimental and control groups. The experimental cement (TP2) absorbed significantly more water than the control group (P<.034). Additionally, NVC-containing specimens showed comparable fluoride releasing properties with almost the same fluoride burst and continued fluoride release from the bulk of the material. It was concluded that a hydrophilic monomer such as NVC might be able to increase the water sorption and decrease the amount of initial fluoride release of the glass ionomers

Arsenic Sorption on TiO2 Nanoparticles: Size And Crystallinity Effects

EPA Science Inventory

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO₂ was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and cryst...

Sorption of atrazine, acetochlor, and 2,4-D by hardwood-derived biochar

NASA Astrophysics Data System (ADS)

Gonzalez, J. M.; Shipitalo, M. J.

2016-12-01

Offsite transport of herbicides and other agricultural pesticides to streams and other bodies of water can adversely impact drinking water supplies and aquatic ecology. Atrazine, acetochlor, and 2,4-D are herbicides commonly used to control weeds in maize (Zea mays) and soybean (Glycine max), the dominant crops in the U.S. Midwest. Unfortunately, these materials are frequently detected at high concentrations in surface runoff and subsurface drainage, especially when rainstorms occur shortly after their application. Thus, edge-of-field technologies employing effective sorbents to remove pesticides in water are needed to reduce this concern. In this study, we investigated the sorption of atrazine, acetochlor, and 2,4-D by a hardwood-derived biochar. Sorption kinetics and isotherms were determined for each pesticide using concentrations ranging from 5 to 100 ug L-1. The results from the kinetic sorption studies were fitted to pseudo first- and second-order reaction models and demonstrated that sorption was fast; in less than an hour > 90% of the added pesticides were sorbed and after 24 hours up to 100% was removed. The pH of the suspensions after the sorption kinetic and isotherm studies was 8.26 ± 0.51. Thus, because of the nature of the biochar and the pesticides used in this study, hydrophobic interactions appear to be the main mechanism of sorption. Furthermore, since the sorption was fast, we hypothesize that sorption occurred on the surface of biochar. The information from this study can be used to develop agricultural best management practices to remove pesticides in water.

Technetium Sorption By Cementitious Materials Under Reducing Conditions

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

Kaplan, Daniel I.; Estes, Shanna L.; Arai, Yuji

2013-07-18

The objective of this study was to measure Tc sorption to cementitious materials under reducing conditions to simulate Saltstone Disposal Facility conditions. Earlier studies were conducted and the experimental conditions were found not to simulate those of the facility. Through a five month subcontract with Clemson University, sorption of {sup 99}Tc to four cementitious materials was examined within an anaerobic glovebag targeting a 0.1% H{sub 2}(g)/ 99.9% N{sub 2}(g) atmosphere. Early experiments based on Tc sorption and Eh indicated that 0.1% H{sub 2}(g) (a reductant) was necessary to preclude experimental impacts from O{sub 2}(g) diffusion into the glovebag. Preliminary datamore » to date (up to 56 days) indicates that sorption of {sup 99}Tc to cementitious materials increased with increasing slag content for simulated saltstone samples. This is consistent with the conceptual model that redox active sulfide groups within the reducing slag facilitate reduction of Tc(VII) to Tc(IV). These experiments differ from previous experiments where a 2% H{sub 2}(g) atmosphere was maintained (Kaplan et al., 2011 (SRNL-STI-2010-00668)). The impact of the 2% H{sub 2}(g) reducing atmosphere on this data was examined and determined to cause the reduction of Tc in experimental samples without slag. In the present ongoing study, after 56 days, Tc sorption by the 50-year old cement samples (no slag) was undetectable, whereas Tc sorption in the cementitious materials containing slag continues to increase with contact time (measured after 1, 4, 8, 19 and 56 days). Sorption was not consistent with spike concentrations and steady state has not been demonstrated after 56 days. The average conditional K{sub d} value for the Vault 2 cementitious material was 873 mL/g (17% slag), for the TR547 Saltstone (45% slag) the conditional K{sub d} was 168 mL/g, and for TR545 (90% slag) the conditional K{sub d} was 1,619 mL/g. It is anticipated that additional samples will be collected until

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.

Enhanced O-2 Selectivity versus N-2 by Partial Metal Substitution in Cu-BTC

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

Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.

2015-03-24

Here, we describe the homogeneous substitution of Mn, Fe, and Co at various levels into a prototypical metal organic framework (MOP), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O-2/N-2 selectivities determined experimentally at 77 K and the difference in O-2 and N-2 binding energies calculated from DFTmore » modeling data: Mn > Fe Co >> Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273-298 K) as compared to all other metals studied, indicative of favorable interactions between N-2 and coordinatively unsaturated Fe metal centers. Interestingly, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

Enhanced O 2 selectivity versus N 2 by partial metal substitution in Cu-BTC

DOE PAGES

Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; ...

2015-03-05

Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O 2/N 2 selectivities determined experimentally at 77 K and the difference in O 2 and N 2 binding energiesmore » calculated from DFT modeling data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N 2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

Ammonia-nitrogen sorptional properties of banana peels.

PubMed

Chen, Yunnen; Ding, Lichao; Fan, Jingbiao

2011-04-01

Using modified banana peel as a biosorbent to treat water containing ammonia-nitrogen (NH4(+)-N) was studied. Related parameters in the sorptional process, such as chemical modification, pH, and contact time were investigated. The experimental results showed that banana peel modified by 30% sodium hydroxide (NaOH) and mesothermal microwaves (NMBPs) can greatly improve the sorption removal for NH4(+)-N. The kinetics study revealed that the sorption behavior better fit the pseudo-second-order equation than the Lagergren first-order equation. Fourier transform infrared absorption spectrum analysis of banana peels and NMBPs before and after NH4(+)-N sorption revealed that the activity of hydroxyl groups at the surface of the banana peels was strengthened after modification, and nitrogenous groups appeared after biosorpting the NH4(+)-N. In the end, metallurgical wastewater containing a low concentration of NH4(+)-N was treated by NMBPs. The initial NH4(+)-N concentration of 138 mg/L was reduced to 13 mg/L in 25 minutes by 4 g/L NMBPs at pH 10.

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

PubMed

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

2016-07-02

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

Effect of Temperature on the Kinetics of Sorption of Co2+ and Ni2+ Ions by a Sorbent Based on an Inositol Hexaphosphoric Acid Derivative

NASA Astrophysics Data System (ADS)

Yarusova, S. B.; Makarenko, N. V.; Gordienko, P. S.; Karpenko, M. A.; Novikova, E. S.

2018-03-01

Data on the effect temperature has on the kinetics of the removal of Co2+ and Ni2+ ions under static conditions by a sorbent based on a derivative of phytic acid fabricated from rice production waste are presented. It is shown that when the temperature is raised from 20 to 60°C, the sorption capacity of the sorbent based on phytic acid increases over the period of sorption and within 180 min reaches values of 1.4 mmol g-1 for Co2+ ions and 1.3 mmol g-1 for Ni2+ ions. It is established that for the investigated range of temperatures, order n of the sorption of Co2+ and Ni2+ ions is <1, which characterizes the reactions accompanied by diffusion processes. It is found that the process of removal of Co2+ and Ni2+ ions is characterized with low activation energy (20.74 kJ mol-1 for Co2+ ions and 14.2 kJ mol-1 for Ni2+ ions). It is also demonstrated that the sorption process in the considered time frame is best described by a kinetic model of a pseudo-second order, as is indicated by respective correlation coefficients.

The Comparison of Sorption and Solubility Behavior of Four Different Resin Luting Cements in Different Storage Media.

PubMed

Giti, Rashin; Vojdani, Mahroo; Abduo, Jaafar; Bagheri, Rafat

2016-06-01

Structural integrity and dimensional stability are the key factors that determine the clinical success and durability of luting cements in the oral cavity. Sorption and solubility of self-adhesive resin luting cements in food-simulating solutions has not been studied sufficiently. This study aimed to compare the sorption and solubility of 2 conventional and 2 self-adhesive resin-based luting cements immersed in four different storage media. A total of 32 disc-shaped specimens were prepared from each of four resin luting cements; seT (SDI), Panavia F (Kuraray), Clearfil SA Cement (Kuraray), and Choice 2 (Bisco). Eight specimens of each material were immersed in all tested solutions including n-heptane 97%, distilled water, apple juice, or Listerine mouth wash. Sorption and solubility were measured by weighing the specimens before and after immersion and desiccation. Data were analyzed by SPSS version 18, using two-way ANOVA and Tukey's HSD test with p≤ 0.05 set as the level of significance. There was a statistically significant interaction between the materials and solutions. The effect of media on the sorption and solubility was material-dependent. While seT showed the highest values of the sorption in almost all solutions, Choice 2 showed the least values of sorption and solubility. Immersion in apple juice caused more sorption than other solutions (p≤ 0.05). The sorption and solubility behavior of the studied cements were significantly affected by their composition and the storage media. The more hydrophobic materials with higher filler content like Choice 2 resin cement showed the least sorption and solubility. Due to their lower sorption and solubility, these types of resin-based luting cements are recommended to be used clinically.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.

[Equilibrium sorption isotherm for Cu2+ onto Hydrilla verticillata Royle and Myriophyllum spicatum].

PubMed

Yan, Chang-zhou; Zeng, A-yan; Jin, Xiang-can; Wang, Sheng-rui; Xu, Qiu-jin; Zhao, Jing-zhu

2006-06-01

Equilibrium sorption isotherms for Cu2+ onto Hydrilla verticillata Royle and Myriophyllum spicatum were studied. Both methods of linear and non-linear fitting were applied to describe the sorption isotherms, and their applicability were analyzed and compared. The results were: (1) The applicability of simulated equation can't be compared only by R2 and chi2 when equilibrium sorption model was used to quantify and contrast the performance of different biosorbents. Both methods of linear and non-linear fitting can be applied in different fitting equations to describe the equilibrium sorption isotherms respectively in order to obtain the actual and credible fitting results, and the fitting equation best accorded with experimental data can be selected; (2) In this experiment, the Langmuir model is more suitable to describe the sorption isotherm of Cu2+ biosorption by H. verticillata and M. spicatum, and there is greater difference between the experimental data and the calculated value of Freundlich model, especially for the linear form of Freundlich model; (3) The content of crude cellulose in dry matter is one of the main factor affecting the biosorption capacity of a submerged aquatic plant, and -OH and -CONH2 groups of polysaccharides on cell wall maybe are active center of biosorption; (4) According to the coefficients qm of the linear form of Langmuir model, the maximum sorption capacity of Cu2+ was found to be 21.55 mg/g and 10.80mg/g for H. verticillata and M. spicatum, respectively. The maximum specific surface area for H. verticillata for binding Cu2+ was 3.23m2/g, and it was 1.62m2/g for M. spicatum.

Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution.

PubMed

Zhang, Lei; Liu, Na; Yang, Lijun; Lin, Qing

2009-10-30

Titanium dioxide nanoparticles were employed for the sorption of selenium ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption was found to be fast, and to reach equilibrium basically within 5.0 min. The sorption has been optimized with respect to the pH, maximum sorption has been achieved from solution of pH 2-6. Sorbed Se(IV) and Se(VI) were desorbed with 2.0 mL 0.1 mol L(-1) NaOH. The kinetics and thermodynamics of the sorption of Se(IV) onto nano-TiO2 have been studied. The kinetic experimental data properly correlate with the second-order kinetic model (k(2)=0.69 g mg(-1) min(-1), 293 K). The overall rate process appears to be influenced by both boundary layer diffusion and intraparticle diffusion. The sorption data could be well interpreted by the Langmuir sorption isotherm. The mean energy of adsorption (14.46 kJ mol(-1)) was calculated from the Dubinin-Radushkevich (D-R) adsorption isotherm at room temperature. The thermodynamic parameters for the sorption were also determined, and the DeltaH(0) and DeltaG(0) values indicate exothermic behavior.

Sorption properties of the activated carbon-zeolite composite prepared from coal fly ash for Ni(2+), Cu(2+), Cd(2+) and Pb(2+).

PubMed

Jha, Vinay Kumar; Matsuda, Motohide; Miyake, Michihiro

2008-12-15

Composite materials of activated carbon and zeolite have been prepared successfully by activating coal fly ash (CFA) by fusion with NaOH at 750 degrees C in N(2) followed by hydrothermal treatments under various conditions. Uptake experiments for Ni(2+), Cu(2+), Cd(2+) and Pb(2+) were performed with the materials thus obtained from CFA. Of the various composite materials, that were obtained by hydrothermal treatment with NaOH solution (ca. 4M) at 80 degrees C (a composite of activated carbon and zeolite X/faujasite) proved to be the most suitable for the uptake of toxic metal ions. The relative selectivity of the present sorbents for the various ions was Pb(2+)>Cu(2+)>Cd(2+)>Ni(2+), with equilibrium uptake capacities of 2.65, 1.72, 1.44 and 1.20mmol/g, respectively. The sorption isotherm was a good fit to the Langmuir isotherm and the sorption is thought to progress mainly by ion exchange with Na(+). The overall reaction is pseudo-second order with rate constants of 0.14, 0.17, 0.21 and 0.20Lg/mmol min for the uptake of Pb(2+), Cu(2+), Cd(2+) and Ni(2+), respectively.

Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd(ii) and Pb(ii) sorption by δ-MnO2 and ferrihydrite.

PubMed

van Genuchten, Case M; Peña, Jasquelin

2016-08-10

Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(ii) and Pb(ii) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that of the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(ii) and Pb(ii) both bind to birnessite layer vacancies, only Pb(ii) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(ii) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(ii) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(ii) < Cd(ii) < Ni(ii) < Zn(ii) < Cu(ii) < Pb(ii).

Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite

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

van Genuchten, Case M.; Peña, Jasquelin

2016-01-01

Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(II) and Pb(II) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that ofmore » the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(II) and Pb(II) both bind to birnessite layer vacancies, only Pb(II) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(II) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(II) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(II) < Cd(II) < Ni(II) < Zn(II) < Cu(II) < Pb(II).« less

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

PubMed Central

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-01-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η − γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment. PMID:27682811

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

NASA Astrophysics Data System (ADS)

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-09-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η - γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment.

Selective O 2 Sorption at Ambient Temperatures via Node Distortions in Sc-MIL-100

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

Sava Gallis, Dorina F.; Chapman, Karena W.; Rodriguez, Mark A.

2016-05-24

An open pored metal–organic framework (MOF) with oxygen selectivity at exceptionally high temperatures is confirmed by synthesis, sorption, and synchrotron structural analyses. The large-pore MIL-100 framework with access to the metal center (e.g., Sc and Fe) resulted in preferential O2 over N2 gas uptake at temperatures ranging from 77 K to ambient temperatures (258, 298, and 313 K). Most notably, Sc-MIL-100 shows exceptional O2 sorption; pair distribution function analyses indicate that this is due to distortions in the framework owing to the size of Sc atoms, in particular in the trimer metal cluster. Experimental studies also correlate very well withmore » GCMC simulations, confirming more favorable O2-framework interactions at pressures up to 1 bar, due to the close proximity of O2 to the high density of metal centers in the small tetrahedral cages. Both materials maintain their crystallinity upon gas adsorption cycling, are regenerable, and show exceptional promise for use in energy efficient oxygen purification processes, such as Pressure Swing Adsorption.« less

Mechanistic insights of 2,4-D sorption onto biochar: Influence of feedstock materials and biochar properties.

PubMed

Mandal, Sanchita; Sarkar, Binoy; Igalavithana, Avanthi Deshani; Ok, Yong Sik; Yang, Xiao; Lombi, Enzo; Bolan, Nanthi

2017-12-01

Objective of this study was to investigate the mechanisms of 2,4-Dichlorophynoxy acetic acid (2,4-D) sorption on biochar in aqueous solutions. Sorption isotherm, kinetics, and desorption experiments were performed to identify the role of biochars' feedstock and production conditions on 2,4-D sorption. Biochars were prepared from various green wastes (tea, burcucumber, and hardwood) at two pyrolytic temperatures (400 and 700°C). The tea waste biochar produced at 700°C was further activated with steam under a controlled flow. The sorption of 2,4-D was strongly dependent on the biochar properties such as specific surface area, surface functional groups, and microporosity. The steam activated biochar produced from tea waste showed the highest (58.8mgg -1 ) 2,4-D sorption capacity, which was attributed to the high specific surface area (576m 2 g -1 ). The mechanism of 2,4-D removal from aqueous solution by biochar is mainly attributed to the formation of heterogeneous sorption sites due to the steam activation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Infrared Study of CO2 Sorption over ?Molecular Basket? Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve

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

Overbury, Steven; Wang, Xiaoxing; Clark, Jason

2009-01-01

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75 C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75 C. Comparative IR examination of the CO{sub 2} sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO{sub 2}-amine interaction patterns.« less

Mixed-Penetrant Sorption in Ultrathin Films of Polymer of Intrinsic Microporosity PIM-1.

PubMed

Ogieglo, Wojciech; Furchner, Andreas; Ghanem, Bader; Ma, Xiaohua; Pinnau, Ingo; Wessling, Matthias

2017-11-02

Mixed-penetrant sorption into ultrathin films of a superglassy polymer of intrinsic microporosity (PIM-1) was studied for the first time by using interference-enhanced in situ spectroscopic ellipsometry. PIM-1 swelling and the concurrent changes in its refractive index were determined in ultrathin (12-14 nm) films exposed to pure and mixed penetrants. The penetrants included water, n-hexane, and ethanol and were chosen on the basis of their significantly different penetrant-penetrant and penetrant-polymer affinities. This allowed studying microporous polymer responses at diverse ternary compositions and revealed effects such as competition for the sorption sites (for water/n-hexane or ethanol/n-hexane) or enhancement in sorption of typically weakly sorbing water in the presence of more highly sorbing ethanol. The results reveal details of the mutual sorption effects which often complicate comprehension of glassy polymers' behavior in applications such as high-performance membranes, adsorbents, or catalysts. Mixed-penetrant effects are typically very challenging to study directly, and their understanding is necessary owing to a broadly recognized inadequacy of simple extrapolations from measurements in a pure component environment.

Sorption of Groundwater Dissolved Organic Carbon onto Minerals

NASA Astrophysics Data System (ADS)

Rutlidge, H.; Oudone, P.; McDonough, L.; Meredith, K.; Andersen, M. S.; O'Carrol, D. M.; Baker, A.

2017-12-01

Our understanding of groundwater organic matter (OM) as a carbon source or sink in the environmental carbon cycle is limited. The dynamics of groundwater OM is mainly governed by biological processing and its sorption to minerals. In saturated groundwaters, dissolved OM (DOM) represents one part of the groundwater organic carbon pool. Without consideration of the DOM sorption, it is not possible to quantify governing groundwater OM processes. This research explores the rate and extent of DOM sorption on different minerals. Groundwater DOM samples, and International Humic Substances Society (IHSS) standard solutions, were analysed. Each was mixed with a range of masses of iron coated quartz, clean quartz, and calcium carbonate, and shaken for 2 hours to reach equilibrium before being filtered through 0.2 μm for total dissolved organic carbon (DOC) and composition analysis by size-exclusion chromatography-organic carbon detection (LC-OCD). Sorption isotherms were constructed and groundwater DOM sorption were compared to the sorption of IHSS standards. Initial results suggest that for the IHSS standards, the operationally-defined humic substances fraction had the strongest sorption compared to the other LC-OCD fractions and total DOC. Some samples exhibited a small increase in the low molecular weight neutral (LMW-N) aqueous concentration with increasing humic substances sorption. This gradual increase observed could be the result of humic substances desorbing or their breakdown during the experiment. Further results comparing these IHSS standards with groundwater samples will be presented. In conjunction with complementary studies, these results can help provide more accurate prediction of whether groundwater OM is a carbon source or sink, which will enable the management of the groundwater resources as part of the carbon economy.

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging.

PubMed

Waldner, Georg; Friesl-Hanl, Wolfgang; Haberhauer, Georg; Gerzabek, Martin H

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena. The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18 months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy. The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K f , 1/ n exponents, and K d values, respectively) were given for pH = 3 and the unbuffered pH of ∼7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3 months. Sorption increased at acidic pH values. Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.

Understanding mechanisms to predict and optimize biochar for agrochemical sorption

NASA Astrophysics Data System (ADS)

Hall, Kathleen; Gámiz, Beatriz; Cox, Lucia; Spokas, Kurt; Koskinen, William

2017-04-01

The ability of biochars to bind various organic compounds has been widely studied due to the potential effects on pesticide fate in soil and interest in the adoption of biochar as a "low-cost" filter material. However, the sorptive behaviors of biochars are extremely variable and much of the reported data is limited to specific biochar-chemical interactions. The lack of knowledge regarding biochar sorption mechanisms limits our current ability to predict and optimize biochar's use. This work unveils mechanistic drivers of organic pesticide sorption on biochars through targeted alteration of biochar surface chemistry. Changes in the quantity and type of functional groups on biochars and other black carbon materials were achieved through treatments with H2O2, and CO2, and characterized using Fourier transform infrared spectroscopy and scanning electron microscope (SEM/EDX). The sorption capacities of these treated biochars were subsequently measured to evaluate the effects of different surface moieties on the binding of target herbicides cyhalofop acid ((R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionic acid) and clomazone (2-[(2-chlorophenyl)methyl]-4,4-dimethyl-1,2-oxazolidin-3-one). Sorption of both herbicides on the studied biochars increased following H2O2 activation; however, the influence of the H2O2 activation on sorption was more pronounced for cyhalofop acid (pKa = 3.9) than clomazone, which is non-ionizable. Increased cyhalofop acid sorption on H2O2 treated biochars can be attributed to the increase in oxygen containing functional groups as well as the decrease in biochar pH. In contrast, CO2 activation reduced the sorption of cyhalofop acid compared to untreated biochar. FTIR data suggest the reduced sorption on CO2 -treated biochar was due to the removal of surface carboxyl groups, further supporting the role of specific functionality in the sorption of ionizable herbicides. Results from this work offer insight into the mechanisms of sorption and

Interaction of gases with ablative composites. I - Ar, CO2, and N2

NASA Technical Reports Server (NTRS)

King, C. A.; Wightman, J. P.

1974-01-01

The sorption of argon, carbon dioxide, and nitrogen on two heat shield composites (SLA-561 and SLA-561V) and on the SLA components was measured over the pressure range of 0.001 to 760 torr and in the temperature range of 30 to 50 C. The sorption of the gases by both the composites and the components varied directly with pressure. The sorption of CO2 by the phenolic spheres and the silicone elastomer and of Ar by the silicone elastomer varied inversely with temperature. The mechanism involved in the gas sorption was primarily absorption.

Sorption behavior of uranium(VI) on a biotite mineral

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

Idemitsu, K.; Obata, K.; Furuya, H.

1995-12-31

Biotite has the most important role for the sorption of radionuclides in granitic rocks. Experiments on the sorption of uranium(VI) on biotite were conducted to understand the fundamental controls on uranium sorption on biotite mineral, including the effects of pH and uranium concentration in solution. Biotite powder (mesh 32--60) were washed with 1N HCl for a week and were rinsed twice with deionized water for a week. This HCl treatment was necessary to avoid the effects by other minerals. The agreement between surface adsorption coefficient, Ka, of both biotites with and without HCl treatment was within one order of magnitude.more » The peak Ka value was in the range of 0.1 to 0.01 cm{sup 3}/cm{sup 2} around pH 6. A comparison of aqueous uranium speciations and sorption results indicates that neutral uranyl hydroxide could be an important species sorbed on the biotite. Sequential desorption experiments with KCl and HCl solutions were also carried out after sorption experiments to investigate sorption forms of uranium. Approximately 20% of uranium in solution were sorbed on the biotite as an exchangeable ion. The fraction of exchangeable uranium had a little dependence on pH. The other uranium could not be extracted even by 6N HCl solution. It is possible that most of the uranium could be precipitated as U(IV) via Fe(II) reduction on the biotite surface.« less

Sorption of sodium hydroxide by type I collagen and bovine corneas.

PubMed

Whikehart, D R; Edwards, W C; Pfister, R R

1991-01-01

There are no quantitative studies on the uptake of alkali into corneal tissues. To study this phenomenon, both type I collagen and bovine corneas were incubated in sodium hydroxide (NaOH) under varying conditions for periods up to 27.5 h. The sorption (absorption or adsorption) of the alkali to protein and tissue was measured as the quantity of NaOH no longer available for titration to neutrality with hydrochloric acid. Sorption was found to be dependent on the concentration of NaOH (0.01-1 N) but independent of the incubation temperature (4-35 degrees C). In whole cornea, sorption of 1 N NaOH began immediately and increased with time up to 6 h. After 6 h, sorption decreased, together with the observed degradation and solubilization of the tissue. Stripping of the corneal endothelium alone or of the endothelium and epithelium increased sorption in a similar manner when compared to whole corneas for periods up to 4 h. These observations are compatible with ionic and nonionic bonding of hydroxide ions to collagen (including that of the cornea) and the subsequent release of hydroxide ions during hydrolysis of the protein itself. Indirect evidence also suggests the inclusion of quantities of unbound hydroxide ions in hydrated gels of glycosaminoglycans. It is proposed that in a chemical burn of the cornea, alkali is both stored in the tissue (by sorption) and reacted with it (by hydrolysis), without any net consumption of alkali taking place.

[Properties of maize stalk biochar produced under different pyrolysis temperatures and its sorption capability to naphthalene].

PubMed

Huang, Hua; Wang, Ya-Xiong; Tang, Jing-Chun; Tang, Jing-Chun; Zhu, Wen-Ying

2014-05-01

Biochar was made from maize stalk under three different temperatures of 300, 500 and 700 degreeC. The elemental composition of biochar was measured by elemental analyzer. Scanning electron microscope (SEM) was used to measure the surface morphology. Sorption of naphthalene to biochar was researched by batch sorption experiments. Results showed that, with the increase of temperature, C content increased from 66. 79% to 76. 30% , H and O contents decreased from 4.92% and 19. 25% to 3. 18% and 9.53%, respectively; H/C, O/C, (O + N)/C, aromaticity and hydrophobicity increased, and polarity decreased. SEM results showed that maize stalk biochar was platy particles, and its roughness of surface increased with increasing temperature. The sorption of naphthalene on biochar followed the Lagergren pseudo-second order dynamic sorption model. Initial sorption rate and equilibrium sorption capacity increased as preparation temperatures increased at the same initial concentration of naphthalene. The isotherm sorption behavior can be described by the Freundlich model, which indicated that, as pyrolysis temperature increased, the sorption capacity of biochar increased, and nonlinearity increased first and then decreased. Biochar derived from maize stalk had distinct features when compared with other feedstocks, and its elemental composition, surface features and sorption behaviors were significantly influenced by pyrolysis temperature.

Sorption characteristics and separation of tellurium ions from aqueous solutions using nano-TiO2.

PubMed

Zhang, Lei; Zhang, Min; Guo, Xingjia; Liu, Xueyan; Kang, Pingli; Chen, Xia

2010-12-15

Titanium dioxide nanoparticles (nano-TiO(2)) were employed for the sorption of Te(IV) ions from aqueous solution. A detailed study of the process was performed by varying the sorption time, pH, and temperature. The sorption was found to be fast, equilibrium was reached within 8 min. When the concentration of Te(IV) was below 40 mg L(-1), at least 97% of tellurium was adsorbed by nano-TiO(2) in the pH range of 1-2 and 8-9. The sorbed Te(IV) ions were desorbed with 2.0 mL of 0.5 mol L(-1) NaOH. The sorption data could be well interpreted by the Langmuir model with the maximum adsorption capacity of 32.75 mg g(-1) (20 ± 0.1 °C) of Te(IV) on nano-TiO(2). The kinetics and thermodynamics of the sorption of Te(IV) onto nano-TiO(2) were also studied. The kinetic experimental data properly correlated with the second-order kinetic model (k(2)=0.0368 g mg(-1)min(-1), 293 K). The overall rate process appeared to be influenced by both boundary layer diffusion and intra-particle diffusion. The mean energy of adsorption was calculated to be 17.41 kJ mol(-1) from the Dubinin-Radushkevich (D-R) adsorption isotherm at room temperature. Moreover, the thermodynamic parameters for the sorption were estimated, and the ΔH(0) and ΔG(0) values indicated the exothermic and spontaneous nature of the sorption process, respectively. Finally, Nano-TiO(2) as sorbent was successfully applied to the separation of Te(IV) from the environmental samples with satisfactory results (recoveries >95%, relative standard deviations was 2.0%). Copyright © 2010 Elsevier B.V. All rights reserved.

Infrared study of CO{sub 2} sorption over 'molecular basket' sorbent consisting of polyethylenimine-modified mesoporous molecular sieve

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

Wang, X.X.; Schwartz, V.; Clark, J.C.

2009-04-15

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75{sup o}C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75{sup o}C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75{sup o}C.« less

A general computer model for predicting the performance of gas sorption refrigerators

NASA Technical Reports Server (NTRS)

Sigurdson, K. B.

1983-01-01

Projected performance requirements for cryogenic spacecraft sensor cooling systems which demand higher reliability and longer lifetimes are outlined. The gas/solid sorption refrigerator is viewed as a potential solution to cryogenic cooling needs. A software model of an entire gas sorption refrigerator system was developed. The numerical model, evaluates almost any combination and order of refrigerator components and any sorbent-sorbate pair or which the sorption isotherm data are available. Parametric curves for predicting system performance were generated for two types of refrigerators, a LaNi5-H2 absorption cooler and a Charcoal-N2 adsorption cooler. It is found that precooling temperature and heat exchanger effectiveness affect the refrigerator performance. It is indicated that gas sorption refrigerators are feasible for a number of space applications.

Selective O 2 sorption at ambient temperatures via node distortions in Sc-MIL-100

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

Sava Gallis, Dorina F.; Chapman, Karena W.; Rodriguez, Mark A.

2016-04-14

In this study, oxygen selectivity in metal-organic frameworks (MOFs) at exceptionally high temperatures originally predicted by Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) modeling is now confirmed by synthesis, sorption metal center access, in particular Sc and Fe. Based on DFT M-O 2 binding energies, we chose the large pored MIL-100 framework for metal center access, in particular Sc and Fe. Both resulted in preferential O 2 and N 2 gas uptake at temperatures ranging from 77 K to ambient temperatures (258 K, 298 K and 313 K).

Roles of functional groups of naproxen in its sorption to kaolinite.

PubMed

Yu, Chenglong; Bi, Erping

2015-11-01

The sorption of acidic anti-inflammatory drugs to soils is important for evaluating their fate and transformations in the water-soil environment. However, roles of functional groups of ionisable drugs onto mineral surfaces have not been sufficiently studied. In this study, batch experiments of naproxen (NPX, anti-inflammatory drug) and two kinds of competitors to kaolinite were studied. The Kd of naproxen to kaolinite is 1.30-1.62 L kg(-1). The n-π electron donor-acceptor (n-π EDA) interaction between diaromatic ring of naproxen (π-electron acceptors) and the siloxane oxygens (n-donors) of kaolinite is the dominant sorption mechanism. The carboxyl group of naproxen can contribute to the overall sorption. A conception model was put forward to elucidate to sorption mechanisms, in which the contribution of n-π EDA and hydrogen bond to overall sorption was quantified. These sorption mechanisms can be helpful for estimating the fate and mobility of acid pharmaceuticals in soil-water environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorption testing and generalized composite surface complexation models for determining uranium sorption parameters at a proposed in-situ recovery site

DOE PAGES

Johnson, Raymond H.; Truax, Ryan A.; Lankford, David A.; ...

2016-02-03

Solid-phase iron concentrations and generalized composite surface complexation models were used to evaluate procedures in determining uranium sorption on oxidized aquifer material at a proposed U in situ recovery (ISR) site. At the proposed Dewey Burdock ISR site in South Dakota, USA, oxidized aquifer material occurs downgradient of the U ore zones. Solid-phase Fe concentrations did not explain our batch sorption test results,though total extracted Fe appeared to be positively correlated with overall measured U sorption. Batch sorption test results were used to develop generalized composite surface complexation models that incorporated the full genericsorption potential of each sample, without detailedmore » mineralogiccharacterization. The resultant models provide U sorption parameters (site densities and equilibrium constants) for reactive transport modeling. The generalized composite surface complexation sorption models were calibrated to batch sorption data from three oxidized core samples using inverse modeling, and gave larger sorption parameters than just U sorption on the measured solidphase Fe. These larger sorption parameters can significantly influence reactive transport modeling, potentially increasing U attenuation. Because of the limited number of calibration points, inverse modeling required the reduction of estimated parameters by fixing two parameters. The best-fit models used fixed values for equilibrium constants, with the sorption site densities being estimated by the inversion process. While these inverse routines did provide best-fit sorption parameters, local minima and correlated parameters might require further evaluation. Despite our limited number of proxy samples, the procedures presented provide a valuable methodology to consider for sites where metal sorption parameters are required. Furthermore, these sorption parameters can be used in reactive transport modeling to assess downgradient metal attenuation, especially when no other

Sorption testing and generalized composite surface complexation models for determining uranium sorption parameters at a proposed in-situ recovery site

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

Johnson, Raymond H.; Truax, Ryan A.; Lankford, David A.

Solid-phase iron concentrations and generalized composite surface complexation models were used to evaluate procedures in determining uranium sorption on oxidized aquifer material at a proposed U in situ recovery (ISR) site. At the proposed Dewey Burdock ISR site in South Dakota, USA, oxidized aquifer material occurs downgradient of the U ore zones. Solid-phase Fe concentrations did not explain our batch sorption test results,though total extracted Fe appeared to be positively correlated with overall measured U sorption. Batch sorption test results were used to develop generalized composite surface complexation models that incorporated the full genericsorption potential of each sample, without detailedmore » mineralogiccharacterization. The resultant models provide U sorption parameters (site densities and equilibrium constants) for reactive transport modeling. The generalized composite surface complexation sorption models were calibrated to batch sorption data from three oxidized core samples using inverse modeling, and gave larger sorption parameters than just U sorption on the measured solidphase Fe. These larger sorption parameters can significantly influence reactive transport modeling, potentially increasing U attenuation. Because of the limited number of calibration points, inverse modeling required the reduction of estimated parameters by fixing two parameters. The best-fit models used fixed values for equilibrium constants, with the sorption site densities being estimated by the inversion process. While these inverse routines did provide best-fit sorption parameters, local minima and correlated parameters might require further evaluation. Despite our limited number of proxy samples, the procedures presented provide a valuable methodology to consider for sites where metal sorption parameters are required. Furthermore, these sorption parameters can be used in reactive transport modeling to assess downgradient metal attenuation, especially when no other

Selenium(IV) and (VI) sorption by soils surrounding fly ash management facilities

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

Hyun, S.; Burns, P.E.; Murarka, I.

2006-11-15

Leachate derived from unlined coal ash disposal facilities is one of the most significant anthropogenic sources of selenium to the environment. To establish a practical framework for predicting transport of selenium in ash leachate, sorption of Se(IV) and Se(VI) from 1 mM CaSO{sub 4} was measured for 18 soils obtained down-gradient from three ash landfill sites and evaluated with respect to several soil properties. Furthermore, soil attenuation from lab-generated ash leachate and the effect of Ca{sup 2+} and SO{sub 4}{sup 2-} concentrations as well as pH on both Se(IV) and Se(VI) was quantified for a subset of soils. For bothmore » Se(IV) and Se(VI), pH combined with either percentage clay or dithionite-citrate-bicarbonate (DCB)-extractable Fe described {gt} 80% of the differences in sorption across all soils, yielding an easy approach for making initial predictions regarding site-specific selenium transport to sensitive water bodies. Se(IV) consistently exhibited an order of magnitude greater sorption than Se(VI). Selenium sorption was highest at lower pH values, with Se(IV) sorption decreasing at pH values above 6, whereas Se(VI) decreased over the entire pH range (2.5-10). Using these pH adsorption envelopes, the likely effect of ash leachate-induced changes in soil pore water pH with time on selenium attenuation by down gradient soils can be predicted. Selenium sorption increased with increasing Ca{sup 2+} concentrations while SO{sub 4}2- suppressed sorption well above enhancements by Ca{sup 2+}. Soil attenuation of selenium from ash leachates agreed well with sorption measured from 1 mM CaSO{sub 4}, indicating that 1 mM CaSO{sub 4} is a reasonable synthetic leachate for assessing selenium behavior at ash landfill sites.« less

Role of Inherent Inorganic Constituents in SO2 Sorption Ability of Biochars Derived from Three Biomass Wastes.

PubMed

Xu, Xiaoyun; Huang, Daxuan; Zhao, Ling; Kan, Yue; Cao, Xinde

2016-12-06

Biochar is rich in both organic carbon and inorganic components. Extensive work has attributed the high sorption ability of biochar to the pore structure and surface chemical property related to its organic carbon fraction. In this study, three biochars derived from dairy manure (DM-biochar), sewage sludge (SS-biochar), and rice husk (RH-biochar), respectively, were evaluated for their SO 2 sorption behavior and the underlying mechanisms, especially the role of inherent inorganic constituents. The sorption capacities of SO 2 by the three biochars were 8.87-15.9 mg g -1 . With the moisture content increasing from 0% to 50%, the sorption capacities increased by up to about 3 times, mainly due to the formation of alkaline water membrane on the biochar surface which could promote the sorption and transformation of acidic SO 2 . DM- and SS-biochar containing larger mineral constituents showed higher sorption capacity for SO 2 than RH-biochar containing less mineral components. CaCO 3 and Ca 3 (PO 4 ) 2 in DM-biochar induced sorbed SO 2 transformation into K 2 Ca(SO 4 ) 2 ·H 2 O and CaSO 4 ·2H 2 O, while the sorbed SO 2 was converted to Fe 2 (SO 4 ) 3 ·H 2 SO 4 ·2H 2 O, CaSO 4 ·2H 2 O, and Ca 3 (SO 3 ) 2 SO 4 ·12H 2 O in SS-biochar. For RH-biochar, K 3 H(SO 4 ) 2 might exist in the exhausted samples. Overall, the chemical transformation of SO 2 induced by biochar inherent mineral components occupied 44.6%-85.5% of the total SO 2 sorption. The results obtained from this study demonstrated that biochar as a unique carbonaceous material could distinctly be a promising sorbent for acidic SO 2 removal in which the inorganic components played an important role in the SO 2 sorption and transformation.

Sorption of water by biochar: Closer look at micropores

NASA Astrophysics Data System (ADS)

Spokas, Kurt; Hall, Kathleen; Joseph, Stephan; Kammann, Claudia; Novak, Jeffrey; Gámiz, Beatriz; Cox, Lucia

2017-04-01

Typically, biochar has been assumed to increase total water content of the soil system and thereby positively influence plant-soil moisture hydraulics. In this work, we focused on water's interaction with micro-pores (<2 nm) and its influence on water availability. In other words, the main question was if the driving force of water's behavior was the physics or chemistry of biochar pores. The temporal scale of liquid water entry into biochar's pore network is very complex, with observed bubbling occurring days, weeks, and even months after a piece of biochar is immersed under water at ambient conditions. Elevated temperature biochar typically has a positive heat of immersion measured calorimetrically, whereas the calculated BET energy of sorption from a water sorption isotherm typically decrease with production temperatures. To further complicate matters, different pieces of biochar interact differently with water even though the entire batch was created in the same reactor at the same time and after liquid water exposure the physical structure of biochar is irreversibly altered, sometimes negligible other times catastrophically. Nevertheless, based on the estimations of diffusion coefficients in biochar from drying curve analyses, pore surface moieties do reduce the effective diffusivity of water vapor in biochar. Contrary to the rule of thumb in soil physics, where higher gas filled porosity correlates with higher soil moisture holding capacities, our results indicate that biochar's water sorption rate and capacity is actually reduced at ambient conditions by an increase in microporous volume. Thereby, biochar's hydrophobic behavior is partly due to the entrapment of gas within the air-filled porosity which prevents liquid water's entry, even though these biochars possess elevated gas phase sorption capacities (e.g., BET N2/CO2 surface areas).

Nutrient release and ammonium sorption by poultry litter and wood biochars in stormwater treatment.

PubMed

Tian, Jing; Miller, Valentina; Chiu, Pei C; Maresca, Julia A; Guo, Mingxin; Imhoff, Paul T

2016-05-15

The feasibility of using biochar as a filter medium in stormwater treatment facilities was evaluated with a focus on ammonium retention. Successive batch extractions and batch ammonium sorption experiments were conducted in both deionized (DI) water and artificial stormwater using poultry litter (PL) and hardwood (HW) biochars pyrolyzed at 400°C and 500°C. No measureable nitrogen leached from HW biochars except 0.07 μmol/g of org-N from 400°C HW biochar. PL biochar pyrolyzed at 400°C leached 120-127 μmol/g of nitrogen but only 7.1-8.6 μmol/g of nitrogen when pyrolyzed at 500°C. Ammonium sorption was significant for all biochars. At a typical ammonium concentration of 2mg/L in stormwater, the maximum sorption was 150 mg/kg for PL biochar pryolyzed at 400°C. In stormwater, ion competition (e.g. Ca(2+)) suppressed ammonium sorption compared to DI water. Surprisingly, ammonium sorption was negatively correlated to the BET surface area of the tested biochars, but increased linearly with cation exchange capacity. Cation exchange capacity was the primary mechanism controlling ammonium sorption and was enhanced by pyrolysis at 400°C, while BET surface area was enhanced by pyrolysis at 500°C. The optimal properties (BET surface area, CEC, etc.) of biochar as a sorbent are not fixed but depend on the target pollutant. Stormwater infiltration column experiments in sand with 10% biochar removed over 90% of ammonium with influent ammonium concentration of 2mg/L, compared to only 1.7% removal in a sand-only column, indicating that kinetic limitations on sorption were minor for the storm conditions studied. Hardwood and poultry litter biochar pyrolyzed at 500°C and presumably higher temperature may be viable filter media for stormwater treatment facilities, as they showed limited release of organic and inorganic nutrients and acceptable ammonium sorption. Copyright © 2016 Elsevier B.V. All rights reserved.

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil.

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Gautier, Mathieu A; Hawari, Jalal

2004-01-01

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.

High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement.

PubMed

Ogieglo, Wojciech; Ghanem, Bader; Ma, Xiaohua; Wessling, Matthias; Pinnau, Ingo

2018-04-04

Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO 2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, n rel , it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in n rel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO 2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO 2 , the effective reduction of the T g was estimated to be ∼200 °C going from 128 to 7 nm films.

Sorption of organic gases in a furnished room

NASA Astrophysics Data System (ADS)

Singer, Brett C.; Revzan, Kenneth L.; Hotchi, Toshifumi; Hodgson, Alfred T.; Brown, Nancy J.

We present experimental data and semi-empirical models describing the sorption of organic gases in a simulated indoor residential environment. Two replicate experiments were conducted with 20 volatile organic compounds (VOCs) in a 50-m 3 room finished with painted wallboard, carpet and cushion, draperies and furnishings. The VOCs span a wide volatility range and include ten hazardous air pollutants. VOCs were introduced to the static chamber as a pulse and their gas-phase concentrations were measured during a net adsorption period and a subsequent net desorption period. Three sorption models were fit to the measured concentrations for each compound to determine the simplest formulation needed to adequately describe the observed behavior. Sorption parameter values were determined by fitting the models to adsorption period data then checked by comparing measured and predicted behavior during desorption. The adequacy of each model was evaluated using a goodness of fit parameter calculated for each period. Results indicate that sorption usually does not greatly affect indoor concentrations of methyl- tert-butyl ether, 2-butanone, isoprene and benzene. In contrast, sorption appears to be a relevant indoor process for many of the VOCs studied, including C 8-C 10 aromatic hydrocarbons (HC), terpenes, and pyridine. These compounds sorbed at rates close to typical residential air change rates and exhibited substantial sorptive partitioning at equilibrium. Polycyclic aromatic HCs, aromatic alcohols, ethenylpyridine and nicotine initially adsorbed to surfaces at rates of 1.5->6 h -1 and partitioned 95->99% in the sorbed phase at equilibrium.

Sorption of DNA by diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels.

PubMed

Tozak, Kabil Özcan; Erzengin, Mahmut; Sargin, Idris; Ünlü, Nuri

2013-01-01

In this study, the DNA sorption performance of diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels were investigated for the purpose of designing a novel adsorbent that can be utilized for DNA purification, separation and immunoadsorption studies such as removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. Poly(2-hydroxyethyl methacrylate) [p(HEMA)]-based monolithic cryogel column embedded with Zn(2+)-diatomite particles was prepared by free radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm). The polymerization reaction was initiated by N,N,N',N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS) pair in an ice bath. After thawing, the monolithic composite cryogels were used for affinity sorption and then subsequent desorption of DNA molecules from aqueous solutions. Diatomite (DA) particles were characterized by XRF and BET method. The characterization of composite cryogel was done through SEM imaging. The effects of pH of the solution, initial DNA concentration, ionic strength, temperature and flow rates on adsorption were investigated to determine the optimum conditions for adsorption/desorption experiments. The particle embedding procedure was shown to yield significantly enhanced adsorption of DNA on the adsorbent. Furthermore, considering its excellent bio-compatibility, p(HEMA) cryogels are promising a candidate for further DNA sorption studies.

The specific sorption of Np(V) on the corundum (α-Al2O3) surface in the presence of trivalent lanthanides Eu(III) and Gd(III): A batch sorption and XAS study.

PubMed

Virtanen, S; Bok, F; Ikeda-Ohno, A; Rossberg, A; Lützenkirchen, J; Rabung, T; Lehto, J; Huittinen, N

2016-12-01

The sorption of pentavalent neptunium, Np(V), on corundum (α-Al2O3) was investigated in the absence and presence of trivalent europium or gadolinium as a competing element under CO2-free conditions. The objective of this study was to investigate how a trivalent metal ion with a higher charge than that of the neptunyl(V) ion would affect the sorption of Np(V) when allowed to adsorb on the mineral surface before the addition of Np(V). Batch sorption experiments conducted as a function of pH (pH-edges) and as a function of Np(V) concentration (isotherms) in the absence and presence of 1×10(-5)M Eu(III) showed no sign of Eu being able to block Np sorption sites. Surface complexation modelling using the diffuse double layer model was applied to the batch data to obtain surface complexation constants for the formed Np(V) complexes on corundum. To account for potential changes occurring in the coordination environment of the neptunium ion in the presence of a trivalent lanthanide, X-ray absorption spectroscopy (XAS) measurements were carried out on the samples containing only Np(V) and Np(V)+Gd(III). The results reveal the presence of a bidentate Np(V) edge-sharing complex on the corundum surface in the absence of Gd(III), while the coordination environment of Np(V) on the corundum surface could be changed when Gd(III) is added to the sample before the sorption of Np(V). Copyright © 2016 Elsevier Inc. All rights reserved.

Sorption of aromatic organic pollutants to grasses from water

USGS Publications Warehouse

Barbour, J.P.; Smith, J.A.; Chiou, C.T.

2005-01-01

The influence of plant lipids on the equilibrium sorption of three aromatic solutes from water was studied. The plant-water sorption isotherms of benzene, 1,2-dichlorobenzene, and phenanthrene were measured over a large range of solute concentrations using sealed vessels containing water, dried plant material, and solute. The plant materials studied include the shoots of annual rye, tall fescue, red fescue, and spinach as well as the roots of annual rye. Seven out of eight sorption isotherms were linear with no evidence of competitive effects between the solutes. For a given plant type, the sorption coefficient increased with decreasing solute water solubility. For a given solute, sorption increased with increasing plant lipid content. The estimated lipid-water partition coefficients of individual solutes were found to be significantly greater than the corresponding octanol-water partition coefficients. This indicates that plant lipids are a more effective partition solvent than octanol for the studied aromatic compounds. As expected, the solute lipid-water partition coefficients were log-linearly related to the respective water solubilities. For the compounds studied, partitioning into the lipids is believed to be the primary sorption mechanism. ?? 2005 American Chemical Society.

SORPTION OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN FROM WATER BY SURFACE SOILS

EPA Science Inventory

The sorption of l4C-labeled 2,3,7,8-tetrachlorodibenzo- p-dioxin (TCDD) from water by two uncontaminated surface soils from the Times Beach, MO, area was evalu- ated by using batch shake testing. Sorption isotherm plots for the soil with the lower fraction organic carbon (f,) wer...

Validation of TOF-SIMS and FE-SEM/EDS Techniques Combined with Sorption and Desorption Experiments to Check Competitive and Individual Pb2+ and Cd2+ Association with Components of B Soil Horizons

PubMed Central

Andrade, María Luisa; Vega, Flora A.

2015-01-01

Sorption and desorption experiments were performed by the batch method on the B horizons of five natural soils: Umbric Cambisol, Endoleptic Luvisol, Mollic Umbrisol, Dystric Umbrisol, and Dystric Fluvisol. Individual and competitive sorption and desorption capacity and hysteresis were determined. The results showed that Pb2+ was sorbed and retained in a greater quantity than Cd2+ and that the hysteresis of the first was greater than that of the second. The most influential characteristics of the sorption and retention of Pb2+ were pH, ECEC, Fe and Mn oxides and clay contents. For Cd2+ they were mainly pH and, to a lesser extent, Mn oxides and clay content. The combined use of TOF-SIMS, FE-SEM/EDS and sorption and desorption analyses was suitable for achieving a better understanding of the interaction between soil components and the two heavy metals. They show the preferential association of Pb2+ with vermiculite, chlorite, Fe and Mn oxides, and of Cd2+ with the same components, although to a much lesser extent and intensity. This was due to the latter’s higher mobility as it competed unfavourably with the Pb2+ sorption sites. TOF-SIMS and FE-SEM/EDS techniques confirmed the results of the sorption experiments, and also provided valuable information on whether the soil components (individually or in association) retain Cd2+ and / or Pb2+; this could help to propose effective measures for the remediation of contaminated soils. PMID:25893518

Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO 2 Sorption

DOE PAGES

Zha, Jie; Zhang, Xueyi

2018-04-17

Here, two-dimensional (2D) metal-organic frameworks (MOFs), as a newly emerged member of 2D materials, have gained extensive attention due to their great potential in gas separation, sensing, and catalysis. However, it is still challenging to synthesize 2D MOFs with controllable size and functionalities using direct and scalable approaches at mild conditions (e.g., room temperature). Herein, we demonstrated onestep, room-temperature synthesis of a series of 2D MOFs based on Cu(II) paddle-wheel units, where the intrinsically anisotropic building blocks led to the anisotropic growth of 2D MOF nanoparticles, and the pillared structure led to high surface areas. The size of 2D MOFsmore » can be adjusted by using a DMF/H 2O mixed solvent. The thinnest particles were around 3 nm, and the highest aspect ratio was up to 200. The functionalization of 2D MOFs was also achieved by selecting ligands with desired functional groups. The gas sorption results revealed that amino and nitro-functionalized 2D MOFs showed higher CO 2 sorption selectivity over CH 4 and N 2, suggesting these materials can be further applied in natural gas sweetening (CO 2/CH 4 separation) and carbon capture from flue gas (CO 2/N 2 separation).« less

Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO 2 Sorption

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

Zha, Jie; Zhang, Xueyi

Here, two-dimensional (2D) metal-organic frameworks (MOFs), as a newly emerged member of 2D materials, have gained extensive attention due to their great potential in gas separation, sensing, and catalysis. However, it is still challenging to synthesize 2D MOFs with controllable size and functionalities using direct and scalable approaches at mild conditions (e.g., room temperature). Herein, we demonstrated onestep, room-temperature synthesis of a series of 2D MOFs based on Cu(II) paddle-wheel units, where the intrinsically anisotropic building blocks led to the anisotropic growth of 2D MOF nanoparticles, and the pillared structure led to high surface areas. The size of 2D MOFsmore » can be adjusted by using a DMF/H 2O mixed solvent. The thinnest particles were around 3 nm, and the highest aspect ratio was up to 200. The functionalization of 2D MOFs was also achieved by selecting ligands with desired functional groups. The gas sorption results revealed that amino and nitro-functionalized 2D MOFs showed higher CO 2 sorption selectivity over CH 4 and N 2, suggesting these materials can be further applied in natural gas sweetening (CO 2/CH 4 separation) and carbon capture from flue gas (CO 2/N 2 separation).« less

Sorption Behavior of Dye Compounds onto Natural Sediment of Qinghe River.

PubMed

Liu, Ruixia; Liu, Xingmin; Tang, Hongxiao; Su, Yongbo

2001-07-15

The objective of this study is to assess the adsorption behavior of C.I. Basic Yellow X-5GL, C.I. Basic Red 13, C.I. Direct Blue 86, C.I. Vat Yellow 2, and C.I. Mordant Black 11 on natural sediment and to identify sediment characteristics that play a predominant role in the adsorption of the dyes. The potentiometric titration experiment is used to investigate acid-base properties of the sediment surface with a constant capacitance surface complexation model. The parameters controlling the sorption such as solution pH and ion strength, as well as the influence of organic carbon and Ca(2+) ion on the adsorption, are evaluated. It is shown that the titration data can be successfully described by the surface protonation and deprotonation model with the least-squares FITEQL program 2.0. The sorption isotherm data are fitted to the Freundlich equation in a nonlinear form (1/n=0.3-0.9) for all tested dyes. With increasing pH value, the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86 on the sediment decreases, while for C.I. Basic Yellow X-5GL and C.I. Basic Red 13, the extent of sorption slightly increases. In addition, ion strength also exhibits a considerably different effect on the sorption behavior of these dye compounds. The addition of Ca(2+) can greatly reduce the sorption of C.I. Basic Red 13 on the sediment surface, while it enhances the sorption of C.I. Direct Blue 6. The removal of organic carbon decreases the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86. In contrast, the sorption of C.I. Basic Red 13 and C.I. Basic Yellow X-5GL is obviously enhanced after the removal of organic carbon. The differences in adsorption behavior are mainly attributed to the physicochemical properties of these dye compounds. Copyright 2001 Academic Press.

Combining experimental techniques with non-linear numerical models to assess the sorption of pesticides on soils

NASA Astrophysics Data System (ADS)

Magga, Zoi; Tzovolou, Dimitra N.; Theodoropoulou, Maria A.; Tsakiroglou, Christos D.

2012-03-01

The risk assessment of groundwater pollution by pesticides may be based on pesticide sorption and biodegradation kinetic parameters estimated with inverse modeling of datasets from either batch or continuous flow soil column experiments. In the present work, a chemical non-equilibrium and non-linear 2-site sorption model is incorporated into solute transport models to invert the datasets of batch and soil column experiments, and estimate the kinetic sorption parameters for two pesticides: N-phosphonomethyl glycine (glyphosate) and 2,4-dichlorophenoxy-acetic acid (2,4-D). When coupling the 2-site sorption model with the 2-region transport model, except of the kinetic sorption parameters, the soil column datasets enable us to estimate the mass-transfer coefficients associated with solute diffusion between mobile and immobile regions. In order to improve the reliability of models and kinetic parameter values, a stepwise strategy that combines batch and continuous flow tests with adequate true-to-the mechanism analytical of numerical models, and decouples the kinetics of purely reactive steps of sorption from physical mass-transfer processes is required.

Measuring and modeling surface sorption dynamics of organophosphate flame retardants in chambers

EPA Science Inventory

Understanding the sorption mechanisms for organophosphate flame retardants (OPFRs) on impervious surfaces is important to improve our understanding of the fate and transport of OPFRs in indoor environments. Langmuir and Freundlich models are widely adopted to describe sorption be...

Moisture sorption characteristics of freeze-dried human platelets*

PubMed Central

Xu, Meng-jie; Chen, Guang-ming; Fan, Ju-li; Liu, Jin-hui; Xu, Xian-guo; Zhang, Shao-zhi

2011-01-01

Freeze-drying is a promising method for a long-term storage of human platelets. The moisture sorption characteristics of freeze-dried human platelets (FDHPs) were studied in this paper. The moisture sorption isotherms of FDHPs and freeze-dried lyophilization buffer (FDLB) were measured at 4, 25, and 37 °C. The experimental data were fitted to Brunauer-Emmett-Teller (BET) and Guggenheim-Anderson-de Boer (GAB) equations. There were no significant statistical differences (P>0.05) between the sorption characteristics of FDHPs and FDLB at 4 and 25 °C, while FDHPs absorbed more water at 37 °C. The net isosteric heat of sorption was derived. The heat for FDHPs showed an abnormal negative value at low moisture contents when 25 and 37 °C data were used. Dynamic sorption experiments were carried out at 25 °C with environmental water activity controlled at 0.75, 0.85, and 0.90. The moisture diffusion coefficient was fitted to be 8.24×10−12 m2/s when experimental data at initial time were used. These results would be helpful in choosing prehydration and storage condition for FDHPs. PMID:21370506

Model coupling intraparticle diffusion/sorption, nonlinear sorption, and biodegradation processes

USGS Publications Warehouse

Karapanagioti, Hrissi K.; Gossard, Chris M.; Strevett, Keith A.; Kolar, Randall L.; Sabatini, David A.

2001-01-01

Diffusion, sorption and biodegradation are key processes impacting the efficiency of natural attenuation. While each process has been studied individually, limited information exists on the kinetic coupling of these processes. In this paper, a model is presented that couples nonlinear and nonequilibrium sorption (intraparticle diffusion) with biodegradation kinetics. Initially, these processes are studied independently (i.e., intraparticle diffusion, nonlinear sorption and biodegradation), with appropriate parameters determined from these independent studies. Then, the coupled processes are studied, with an initial data set used to determine biodegradation constants that were subsequently used to successfully predict the behavior of a second data set. The validated model is then used to conduct a sensitivity analysis, which reveals conditions where biodegradation becomes desorption rate-limited. If the chemical is not pre-equilibrated with the soil prior to the onset of biodegradation, then fast sorption will reduce aqueous concentrations and thus biodegradation rates. Another sensitivity analysis demonstrates the importance of including nonlinear sorption in a coupled diffusion/sorption and biodegradation model. While predictions based on linear sorption isotherms agree well with solution concentrations, for the conditions evaluated this approach overestimates the percentage of contaminant biodegraded by as much as 50%. This research demonstrates that nonlinear sorption should be coupled with diffusion/sorption and biodegradation models in order to accurately predict bioremediation and natural attenuation processes. To our knowledge this study is unique in studying nonlinear sorption coupled with intraparticle diffusion and biodegradation kinetics with natural media.

Water vapor sorption properties of cellulose nanocrystals and nanofibers using dynamic vapor sorption apparatus.

PubMed

Guo, Xin; Wu, Yiqiang; Xie, Xinfeng

2017-10-27

Hygroscopic behavior is an inherent characteristic of nanocellulose which strongly affects its applications. In this study, the water vapor sorption behavior of four nanocellulose samples, such as cellulose nanocrystals and nanofibers with cellulose I and II structures (cellulose nanocrystals (CNC) I, CNC II, cellulose nanofibers (CNF) I, and CNF II) were studied by dynamic vapor sorption. The highly reproducible data including the running time, real-time sample mass, target relative humidity (RH), actual RH, and isotherm temperature were recorded during the sorption process. In analyzing these data, significant differences in the total running time, equilibrium moisture content, sorption hysteresis and sorption kinetics between these four nanocellulose samples were confirmed. It was important to note that CNC I, CNC II, CNF I, and CNF II had equilibrium moisture contents of 21.4, 28.6, 33.2, and 38.9%, respectively, at a RH of 95%. Then, the sorption kinetics behavior was accurately described by using the parallel exponential kinetics (PEK) model. Furthermore, the Kelvin-Voigt model was introduced to interpret the PEK behavior and calculate the modulus of these four nanocellulose samples.

Sericitization of illite decreases sorption capabilities for cesium

NASA Astrophysics Data System (ADS)

Choung, S.; Hwang, J.; Han, W.; Shin, W.

2017-12-01

Release of radioactive cesium (137Cs) to environment occurs through nuclear accidents such as Chernobyl and Fukushima. The concern is that 137Cs has long half-life (t1/2 = 30.2 years) with chemical toxicity and γ-radiation. Sorption techniques are mainly applied to remove 137Cs from aquatic environment. In particular, it has been known well that clay minerals (e.g, illite) are effective and economical sorbents for 137Cs. Illite that was formed by hydrothermal alteration exist with sericite through "sericitization" processes. Although sericite has analogous composition and lattice structure with illite, the sorptive characteristics of illite and sericite for radiocesium could be different. This study evaluated the effects of hydrothermal alteration and weathering process on illite cesium sorption properties. Natural illite samples were collected at Yeongdong area in Korea as the world-largest hydrothermal deposits for illite. The samples were analyzed by XRF, XRD and SEM-EDX to determine mineralogy, chemical compositions and morphological characteristics, and used for batch sorption experiments. The Yeongdong illites predominantly consist of illite, sericite, quartz, and albite. The measured cesium sorption distribution coefficients (Kd,Cs) of reference illite and sericite were approximately 6000 and 400 L kg-1 at low aqueous concentration (Cw 10-7 M), respectively. In contrast, Kd,Cs values for the Yeongdong illite samples ranged from 500 to 4000 L kg-1 at identical concentration. The observed narrow and sharp XRD peak of sericite indicated that the sericite has better crystallinity compared to illite. These experimental results suggested that sericitization processes of illite can decline the sorption capabilities of illite for cesium under various hydrothermal conditions. In particular, weathering experiments raised the cesium sorption to illite, which seems to be related to the increase of preferential sorption sites for cesium through crystallinity destruction

Sorption of DNA by diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels

PubMed Central

Tozak, Kabil Özcan; Erzengin, Mahmut; Sargin, Idris; Ünlü, Nuri

2013-01-01

In this study, the DNA sorption performance of diatomite-Zn(II) embedded supermacroporous monolithic p(HEMA) cryogels were investigated for the purpose of designing a novel adsorbent that can be utilized for DNA purification, separation and immunoadsorption studies such as removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. Poly(2-hydroxyethyl methacrylate) [p(HEMA)]-based monolithic cryogel column embedded with Zn2+-diatomite particles was prepared by free radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm). The polymerization reaction was initiated by N,N,N',N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS) pair in an ice bath. After thawing, the monolithic composite cryogels were used for affinity sorption and then subsequent desorption of DNA molecules from aqueous solutions. Diatomite (DA) particles were characterized by XRF and BET method. The characterization of composite cryogel was done through SEM imaging. The effects of pH of the solution, initial DNA concentration, ionic strength, temperature and flow rates on adsorption were investigated to determine the optimum conditions for adsorption/desorption experiments. The particle embedding procedure was shown to yield significantly enhanced adsorption of DNA on the adsorbent. Furthermore, considering its excellent bio-compatibility, p(HEMA) cryogels are promising a candidate for further DNA sorption studies. PMID:26600734

Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

PubMed

Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

2015-12-09

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and

Influence of the isomerism on the sorption of imazamethabenz-methyl by soil.

PubMed

Pinna, Maria Vittoria; Pusino, Alba

2013-04-01

The sorption of meta and para isomers of the herbicide imazamethabenz-methyl, methyl 6-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-m- or p-toluate, by three soils and soil organic matter, was studied. Sorption isotherms conformed to the Freundlich equation. It was found that pH was the main factor influencing the adsorption in all of the systems. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, at low pH value, the soil rich in smectite clays, favoured the sorption of meta rather than para isomer. The higher affinity of clay surfaces for the meta isomer of the herbicide is due to the stabilization of the meta protonated form by resonance. At all pH values, the sorption on soil organic matter did not differ between two isomers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Properties of biochar-amended soils and their sorption of imidacloprid, isoproturon, and atrazine.

PubMed

Jin, Jie; Kang, Mingjie; Sun, Ke; Pan, Zezhen; Wu, Fengchang; Xing, Baoshan

2016-04-15

Biochars produced from rice straw, wheat straw and swine manure at 300, 450 and 600°C were added to soil at 1, 5, 10, or 20% levels to determine whether they would predictably reduce the pore water concentration of imidacloprid, isoproturon, and atrazine. The sorption capacity of the mixtures increased with increasing biochar amounts. The enhanced sorption capacity could be attributed to the increased organic carbon (OC) content and surface area (SA) as well as the decreased hydrophobicity. Biochar dominated the overall sorption when its content was above 5%. The OC contents of the mixtures with 10% and 20% biochar were generally lower than the predicted values. This implies possible interaction between soil components and biochar and/or the effect of biochar oxidation. For soils amended with biochars produced at 300°C, the N2 SA (N2-SA) values were underestimated. The predicted CO2 SA (CO2-SA) values of the mixtures at the biochar content of 10% and 20% were generally higher than the experimental values. Sorption of imidacloprid to the soils amended with biochar at 10% and 20% levels, excluding the soils amended with rice (SR300) and wheat (SW300) straw-derived biochar produced at 300°C, was lower than the predicted value. For SR300 and SW300, the intrinsic sorption capacity of biochar was enhanced by 1.3-5.6 times, depending on the biochar, solute concentration, and biochar dose. This study indicates that biochars would be helpful to stabilize the soil contaminated with imidacloprid, isoproturon, and atrazine, but the sorption capacity of the mixtures could exceed or fall short of predicted values without assuming a cross-effect between soil and biochar. Copyright © 2016 Elsevier B.V. All rights reserved.

Inhibitory effect on the uptake and diffusion of Cd(2+) onto soybean hull sorbent in Cd-Pb binary sorption systems.

PubMed

Módenes, Aparecido N; Espinoza-Quiñones, Fernando R; Colombo, Andréia; Geraldi, Claudinéia L; Trigueros, Daniela E G

2015-05-01

The uptake of Cd(2+) and Pb(2+) ions by a soybean hull (SH) biosorbent in single and binary systems has been investigated. Sorption tests regarding SH in natura and chemically treated were carried out testing a suitable value range of solution pH, sorption temperature and shaking velocity. Sorption capacity is improved at pH 4, 30 °C temperature and 100 rpm. When a strong base is applied, a related-to-untreated SH increasing of 20% in the sorption capacity of Pb(2+) ions was observed, but with poor results for Cd(2+) uptake. Additionally, a relatively strong decreasing in both sorption capacities of Pb(2+) and Cd(2+) ions was evidenced for all acidic treatments. Regarding untreated SH, kinetic sorption data of both metals were well-interpreted by a pseudo second-order model and a rate-limiting step on the basis of an intra-particle diffusion model was suggested to occur. An inhibitory effect of Pb(2+) diffusion over Cd(2+) one was observed, limiting to reach the obtained maximum sorption capacity in single system. Maximum adsorption capacities of 0.49 and 0.67mequivg(-1) for Cd(2+) and Pb(2+), respectively, were predicted by the Langmuir isotherm model that reproduced well the equilibrium sorption data for single systems. The inhibitory effect of one metal over the other one was verified in equilibrium sorption data for binary systems interpreted on the basis of a modified extended Langmuir isotherm model, predicting changes in metal affinity onto the SH surface. Finally, SH is an alternative biosorbent with a great potential for the wastewater treatment containing cadmium and lead ions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of Curing Mode on the Surface Energy and Sorption/Solubility of Dental Self-Adhesive Resin Cements

PubMed Central

Kim, Hyun-Jin; Bagheri, Rafat; Kim, Young Kyung; Son, Jun Sik; Kwon, Tae-Yub

2017-01-01

This study investigated the influence of curing mode (dual- or self-cure) on the surface energy and sorption/solubility of four self-adhesive resin cements (SARCs) and one conventional resin cement. The degree of conversion (DC) and surface energy parameters including degree of hydrophilicity (DH) were determined using Fourier transform infrared spectroscopy and contact angle measurements, respectively (n = 5). Sorption and solubility were assessed by mass gain or loss after storage in distilled water or lactic acid for 60 days (n = 5). A linear regression model was used to correlate between the results (%DC vs. DH and %DC/DH vs. sorption/solubility). For all materials, the dual-curing consistently produced significantly higher %DC values than the self-curing (p < 0.05). Significant negative linear regressions were established between the %DC and DH in both curing modes (p < 0.05). Overall, the SARCs showed higher sorption/solubility values, in particular when immersed in lactic acid, than the conventional resin cement. Linear regression revealed that %DC and DH were negatively and positively correlated with the sorption/solubility values, respectively. Dual-curing of SARCs seems to lower the sorption and/or solubility in comparison with self-curing by increased %DC and occasionally decreased hydrophilicity. PMID:28772489

Atomic-deficient nanostructurization in water-sorption alumomagnesium spinel ceramics MgAl2O4

NASA Astrophysics Data System (ADS)

Ingram, A.

2018-02-01

Atomic-deficient nanostructurization in alumomagnesium MgAl2O4 ceramics sintered at 1100-1400 °C caused by water sorption are studied employing positron annihilation lifetime spectroscopy. Detected PAL spectra are reconstructed from unconstrained x4-term decomposition, and further transformed to x3-term form to be applicable for analysis with x3-x2-CDA (coupling decomposition algorithm). It is proved that water-immersion processes reduce positronium (Ps) decaying in large-size holes of ceramics (1.70-1.84 nm in radius) at the expense of enhanced trapping in tiny ( 0.2 nm in radius) Ps-traps. The water sorption is shown to be more pronounced in structurally imperfect ceramics sintered at T s = 1100-1200 °C due to irreversible transformations between constituting phases, while reversible physical-sorption processes are dominated in structurally uniform ceramics composed of main spinel phase.

Effects of hydrodynamic conditions on the sorption behaviors of aniline on sediment with coexistence of nitrobenzene.

PubMed

Wang, Peng; Hua, Zulin; Cai, Yunjie; Shen, Xia; Li, Qiongqiong; Liu, Xiaoyuan

2015-08-01

The sorption behaviors of pollutants affected by hydrodynamic conditions were confirmed in natural water environment. The effects of hydrodynamic conditions on the sorption behaviors of aniline on sediment with coexistence of nitrobenzene were investigated. The particle entrainment simulator (PES) was used to simulate varied bottom shear stresses. The batch equilibrium method was applied to the experiments with the stress levels and the action time controlled at 0.2-0.5 N/m(2) and 24 h, respectively. The findings indicated that apparent partition coefficient of aniline on sediment increased with the shear stress significantly, while decreased with nitrobenzene concentration. On the contrary, both the sorption amount of aniline on suspended particulate matter (Q s) and the effect of nitrobenzene concentration on Q s declined as the shear stress increased. The sorption kinetic results showed that the sorption process followed the pseudo-second-order kinetics equation, and the process included two stages: fast sorption stage and slow sorption stage, among which the average sorption rate of fast stage was 7.5-9.5 times that of slow one. The effect of shear stress on the average sorption rate of aniline was enhanced with the increase of nitrobenzene concentration. And shear stress weakened the disturbance of cosolute on main solute sorption process. In addition, experiment results of sorption kinetic show that only the initial sorption rate was affected by shear stress and cosolute concentration. In the first 5 min, shear stress had positive effects on the sorption rate. After that, the sorption rate barely changed with shear stress and cosolute concentration.

Competitive sorption of organic contaminants in chalk.

PubMed

Graber, E R; Borisover, M

2003-12-01

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed

Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

USDA-ARS?s Scientific Manuscript database

Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and...

Water Sorption and Vapor-Phase Deuterium Exchange Studies on Methemoglobin CC, SC, SS, AS, and AA

PubMed Central

Killion, Philip J.; Cameron, Bruce F.

1972-01-01

Five hemoglobins whose genetic relationship to one another involves one set of alleles, hemoglobins CC, SC, SS, AS, and AA, were studied in the Met form. Two different investigations were conducted at 28°C on these methemoglobins within a McBain gravimetric sorption system: sorption of H2O vapor and vapor-phase deuterium-hydrogen exchange. For each of the five samples there was close agreement between the per cent hydration of polar sites as determined from sorption studies and the maximum per cent of labile hydrogens that were exchanged during the vapor-phase deuterium exchange study. Both studies measured a slight increase in the number of polar sites accessible to H2O or D2O vapor for those samples in which the substituent in the sixth position from the N-terminus of the two β-chains had a positively charged side chain and a slight decrease for those in which the substituent had a negatively charged side chain. The in-exchange of deuterium for hydrogen occurred at a faster observed rate than the out-exchange of hydrogen for deuterium. PMID:5030563

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 ...

Predicting sorption of organic acids to a wide range of carbonized sorbents

NASA Astrophysics Data System (ADS)

Sigmund, Gabriel; Kah, Melanie; Sun, Huichao; Hofmann, Thilo

2016-04-01

Many contaminants and infochemicals are organic acids that undergo dissociation under environmental conditions. The sorption of dissociated anions to biochar and other carbonized sorbents is typically lower than that of neutral species. It is driven by complex processes that are not yet fully understood. It is known that predictive approaches developed for neutral compounds are unlikely to be suitable for organic acids, due to the effects of dissociation on sorption. Previous studies on the sorption of organic acids to soils have demonstrated that log Dow, which describes the decrease in hydrophobicity of acids upon dissociation, is a useful alternative to log Kow. The aim of the present study was to adapt a log Dow based approach to describe the sorption of organic acids to carbonized sorbents. Batch experiments were performed with a series of 9 sorbents (i.e., carbonized wood shavings, pig manure, and sewage sludge, carbon nanotubes and activated carbon), and four acids commonly used for pesticidal and biocidal purposes (i.e., 2,4-D, MCPA, 2,4-DB, and triclosan). Sorbents were comprehensively characterized, including by N2 and CO2 physisorption, Fourier transform infrared spectroscopy, and elemental analysis. The wide range of sorbents considered allows (i) discussing the mechanisms driving the sorption of neutral and anionic species to biochar, and (ii) their dependency on sorbate and sorbent properties. Results showed that the sorption of the four acids was influenced by factors that are usually not considered for neutral compounds (i.e., pH, ionic strength). Dissociation affected the sorption of the four compounds, and sorption of the anions ranged over five orders of magnitude, thus substantially contributing to sorption in some cases. For prediction purposes, most of the variation in sorption to carbonized sorbents (89%) could be well described with a two-parameter regression equation including log Dow and sorbent specific surface area. The proposed model

Experimental and theoretical study of Co sorption in clay montmorillonites

NASA Astrophysics Data System (ADS)

Gil Rebaza, A. V.; Montes, M. L.; Taylor, M. A.; Errico, L. A.; Alonso, R. E.

2018-03-01

Montmorillonite (MMT) clays are 2:1 layered structures which in natural state may allocate different hydrated cations such as M-nH2O (M = Na, Ca, Fe, etc) in its interlayer space. Depending on the capability for ion sorption, these materials are interesting for environmental remediation. In this work we experimentally study the Co sorption in a natural Na-MMT using UV-visible spectrometry and XRD on semi-oriented samples, and then analyze the sorption ability of this clay by means of ab initio calculation performed on pristine MMT. The structural properties of Na-MMT and Co-adsorbed MMT, and the hyperfine parameters at different atomic sites were analyzed and compared with the experimental ones for the first, and for the case of the hyperfine parameters, presented for the first time for the last. The theoretical predictions based on total energy considerations confirm that Co incorporation replacing Na is energetically favorable. Also, the basal spacing d001 experimentally obtained is well reproduced.

Effects of prolonged light exposure times on water sorption, solubility and cross-linking density of simplified etch-and-rinse adhesives.

PubMed

Wambier, Letícia; Malaquias, Tamirez; Wambier, Denise Stadler; Patzlaff, Rafael T; Bauer, José; Loguercio, Alessandro D; Reis, Alessandra

2014-06-01

This study evaluated the effects of light exposure times on water sorption, solubility, and polymer cross-linking density of simplified etch-and-rinse adhesives. Four commercial adhesives (XP Bond, Adper Single Bond 2, Tetric N-Bond, and Ambar) were selected, and resin disks 5 mm in diameter and 1.0 mm thick were prepared and light cured for 20, 40, or 80 s using an LED light-curing unit at 1200 mW/cm2. Water sorption and solubility were evaluated over a 28-day period. For polymer cross-linking density, additional specimens were prepared and their Knoop hardness measured before and after immersion in 100% ethanol. The data from each test were evaluated using a two-way ANOVA and Tukey's test (α = 0.05). The XP Bond adhesive showed higher water sorption (similar to Adper Single Bond 2) and solubility (p < 0.05) than did the other materials. Prolonged exposure times did not reduce the water sorption but did reduce the solubility of all tested materials (p < 0.05). For Ambar, the increase in the exposure time resulted in a significantly lower percent reduction in hardness. Water sorption, solubility, and cross-linking density of the materials selected in this study seem to be mainly influenced by the adhesive composition. Prolonged light exposure times reduced the solubility of the materials.

Enhanced sorption of PAHs in natural-fire-impacted sediments from Oriole Lake, California.

PubMed

Sullivan, Julia; Bollinger, Kevyn; Caprio, Anthony; Cantwell, Mark; Appleby, Peter; King, John; Ligouis, Bertrand; Lohmann, Rainer

2011-04-01

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ(13)C isotope ratios. Sediments displayed high OC (20-25%) and increasing BC concentrations from ∼0.40% (in 1800 C.E.) to ∼0.60% dry weight (in 2000 C.E.). Petrographic analysis confirmed the presence of fire-derived carbonaceous particles/BC at ∼2% of total OC. Natural fires were the most likely cause of both elevated polycyclic aromatic hydrocarbon (PAH) concentrations and enhanced sorption in Oriole Lake sediments prior to 1850, consistent with their tree-ring-based fire history. In contrast to other PAHs, retene and perylene displayed decreasing concentrations during periods with natural fires, questioning their use as fire tracers. The occurrence of natural fires, however, did not result in elevated concentrations of black carbon or chars in the sediments. Only the 1912-2007 sediment layer contained anthropogenic particles, such as soot BC. In this layer, combining OC absorption with adsorption to soot BC (using a Freundlich coefficient n = 0.7) explained the observed sorption well. In the older layers, n needed to be 0.3 and 0.5 to explain the enhanced sorption to the sediments, indicating the importance of natural chars/inertinites in sorbing PAHs. For phenanthrene, values of n differed significantly between sorption to natural chars (0.1-0.4) and sorption to anthropogenic black carbon (>0.5), suggesting it could serve as an in situ probe of sorbents.

Dependence of pesticide degradation on sorption: nonequilibrium model and application to soil reactors

NASA Astrophysics Data System (ADS)

Guo, Lei; Jury, William A.; Wagenet, Robert J.; Flury, Markus

2000-04-01

The effect of sorption on degradation of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in a soil amended with various amounts of activated carbon (AC). The relationship between sorption and decay of 2,4-D was analyzed using analytical solutions for equilibrium sorption and to a two-site nonequilibrium adsorption model coupled with two first-order degradation terms for the dissolved and sorbed pesticide, respectively. The sorption parameters in the latter model were determined based on data obtained from batch sorption experiments, while those for degradation were obtained from incubation experiments. The adsorption coefficients, ranging from 0.811 to >315 ml g -1, increased at higher AC, and were negatively related to degradation as measured by the first-order rate constant, implying that degradation is faster from the liquid phase than from the sorbed phase. A nonlinear fit of the decay curves to the nonequilibrium model revealed that degradation rate constants were 0.157 and 0.00243 day -1 for the liquid and sorbed phases, respectively, differing by a factor of 65. Similar results were also obtained using the equilibrium model. A parameter sensitivity analysis of the nonequilibrium model indicates that nonequilibrium sorption will initially favor degradation; however, over the long term, will decrease degradation when desorption kinetics becomes the limiting factor in the degradation process. In the presence of a lag phase that allows appreciable amounts of chemical to diffuse into kinetic sorption sites, nonequilibrium sorption will only impede degradation.

Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material.

PubMed

Bai, Jing; Liu, Chongxuan; Ball, William P

2009-10-15

A diffusion cell method was applied to measure the effective pore diffusion coefficient (Dp) for U(VI) under strictly controlled chemical conditions in a silt/clay sediment from the U.S. Department of Energy Hanford site, WA. "Inward-flux" diffusion studies were conducted in which [U(VI)] in both aqueous and solid phases was measured as a function of distance in the diffusion cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed contaminant U(VI) in the solid phase containing extractable background U(VI). The effect of sorption kinetics on U(VI) interparticle diffusion was evaluated by comparing sorption-retarded diffusion models with sorption described either as equilibrium or intraparticle diffusion-limited processes. Both experimental and modeling results indicated that (1) a single pore diffusion coefficient can simulate the diffusion of total aqueous U(VI), and (2) the local equilibrium assumption (LEA) is appropriate for modeling sorption-retarded diffusion under the given experimental conditions. Dp of 1.6-1.7 x 10(-6) cm2/s was estimated in aqueous solution at pH 8.0 and saturated with respect to calcite, as relevant to some subsurface regions of the Hanford site.

Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

PubMed Central

Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

1993-01-01

The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

Sorption of selected pesticides on soils, sediment and straw from a constructed agricultural drainage ditch or pond.

PubMed

Vallée, Romain; Dousset, Sylvie; Billet, David; Benoit, Marc

2014-04-01

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K fads) values was obtained, from 0.74 to 442.63 mg(1 - n) L (n) kg(-1), and the corresponding K foc values ranged from 56 to 3,725 mg(1 - n) L (n) kg(-1). Based on potential retention, the substrates may be classified as straw > sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz > tebuconazole-boscalid > napropamide > MCPA-isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil-sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: I. Laboratory development

USGS Publications Warehouse

Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.

2008-01-01

A gel probe equilibrium sampler has been developed to study arsenic (As) geochemistry and sorption behavior in sediment porewater. The gels consist of a hydrated polyacrylamide polymer, which has a 92% water content. Two types of gels were used in this study. Undoped (clear) gels were used to measure concentrations of As and other elements in sediment porewater. The polyacrylamide gel was also doped with hydrous ferric oxide (HFO), an amorphous iron (Fe) oxyhydroxide. When deployed in the field, HFO-doped gels introduce a fresh sorbent into the subsurface thus allowing assessment of in situ sorption. In this study, clear and HFO-doped gels were tested under laboratory conditions to constrain the gel behavior prior to field deployment. Both types of gels were allowed to equilibrate with solutions of varying composition and re-equilibrated in acid for analysis. Clear gels accurately measured solution concentrations (??1%), and As was completely recovered from HFO-doped gels (??4%). Arsenic speciation was determined in clear gels through chromatographic separation of the re-equilibrated solution. For comparison to speciation in solution, mixtures of As(III) and As(V) adsorbed on HFO embedded in gel were measured in situ using X-ray absorption spectroscopy (XAS). Sorption densities for As(III) and As(V) on HFO embedded in gel were obtained from sorption isotherms at pH 7.1. When As and phosphate were simultaneously equilibrated (in up to 50-fold excess of As) with HFO-doped gels, phosphate inhibited As sorption by up to 85% and had a stronger inhibitory effect on As(V) than As(III). Natural organic matter (>200 ppm) decreased As adsorption by up to 50%, and had similar effects on As(V) and As(III). The laboratory results provide a basis for interpreting results obtained by deploying the gel probe in the field and elucidating the mechanisms controlling As partitioning between solid and dissolved phases in the environment. ?? 2008 American Chemical Society.

Strong sorption of PCBs to nanoplastics, microplastics, carbon nanotubes, and fullerenes.

PubMed

Velzeboer, I; Kwadijk, C J A F; Koelmans, A A

2014-05-06

The presence of microplastic and carbon-based nanoparticles in the environment may have implications for the fate and effects of traditional hydrophobic chemicals. Here we present parameters for the sorption of 17 CB congeners to 10-180 μm sized polyethylene (micro-PE), 70 nm polystyrene (nano-PS), multiwalled carbon nanotubes (MWCNT), fullerene (C60), and a natural sediment in the environmentally relevant 10(-5)-10(-1) μg L(-1) concentration range. Effects of salinity and sediment organic matter fouling were assessed by measuring the isotherms in fresh- and seawater, with and without sediment present. Sorption to the "bulk" sorbents sediment organic matter (OM) and micro-PE occurred through linear hydrophobic partitioning with OM and micro-PE having similar sorption affinity. Sorption to MWCNT and nano-PS was nonlinear. PCB sorption to MWCNT and C60 was 3-4 orders of magnitude stronger than to OM and micro-PE. Sorption to nano-PS was 1-2 orders of magnitude stronger than to micro-PE, which was attributed to the higher aromaticity and surface-volume ratio of nano-PS. Organic matter effects varied among sorbents, with the largest OM fouling effect observed for the high surface sorbents MWCNT and nano-PS. Salinity decreased sorption for sediment and MWCNT but increased sorption for the polymers nano-PS and micro-PE. The exceptionally strong sorption of (planar) PCBs to C60, MWCNT, and nano-PS may imply increased hazards upon membrane transfer of these particles.

Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

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

Powell, Brian; Kaplan, Daniel I; Arai, Yuji

2016-12-29

This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influencedmore » by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.« less

Effect of ten quaternary ammonium cations on tetrachloromethane sorption to clay from water

USGS Publications Warehouse

Smith, J.A.

1990-01-01

The mineral surface of Wyoming bentonite (clay) was modified by replacing inorganic ions by each of 10 quaternary ammonium compounds, and tetrachloromethane sorption to the modified sorbents from water was studied. Tetrachloromethane sorption from solution to clay modified with tetramethyl-, tetraethyl-, benzyltrimethyl-, or benzyltriethylammonium cations generally is characterized by relatively high solute uptake, isotherm nonlinearity, and competitive sorption (with trichloroethene as the competing sorbate). For these sorbents, the ethyl functional groups yield reduced sorptive capacity relative to methyl groups, whereas the benzyl group appears to have a similar effect on sorbent capacity as the methyl group. Sorption of tetrachloromethane to clay modified with dodecyldimethyl(2-phenoxyethyl)-, dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, or benzyldimethylhexadecylammonium bromide is characterized by relatively low solute uptake, isotherm linearity, and noncompetitive sorption. For these sorbents, an increase in the size of the nonpolar functional group(s) causes an increase in the organic carbon normalized sorption coefficient (Koc). No measurable uptake of tetrachloromethane sorption by the unmodified clay or clay modified by ammonium bromide was observed. ?? 1990 American Chemical Society.

Sorption-desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions.

PubMed

Kandil, Mahrous M; El-Aswad, Ahmed F; Koskinen, William C

2015-01-01

Sorption-desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption-desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd(ads), varied according to its initial concentration and was ranged 40-84 for HA, 14-58 for clay and 1.85-4.15 for bulk soil. Freundlich sorption coefficient, Kf(ads), values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ∼800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n(ads) values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.

Sorption characteristics of cadmium in a clay soil of Mae Ku creek, Tak Province, Thailand

NASA Astrophysics Data System (ADS)

Thunyawatcharakul, P.; Chotpantarat, S.

2018-05-01

Mae Sot is a district in Tak province, the northern part of Thailand where has encountered with cadmium (Cd) contaminated in soils. Exposure of Cd can lead to severe health effect, for examples, bone softening, osteoporosis, renal dysfunction, and Itai-Itai disease. This study aims at elucidating sorption behavior of Cd in the contaminated soil collected from Mae Ku creek, Mae Sot district, Thailand. Batch sorption experiment was conducted in order to investigate sorption characteristics of Cd onto the contaminated soil. The soil sample taken from the study area consists of 26% sand, 16% silt 58% clay, which categorized as a clay soil, based on USDA classification. Soil pH is slightly alkaline (pH∼7.7) and organic matter in the soil is 2.93%. The initial concentration in the batch sorption experiment was in the range from 0- 200 ppm. The result from the batch sorption experiment showed that soil sample can adsorb Cd up to 173.5 ppm and the sorption behavior of the soil sample can be well described by Freundlich isotherm, indicating the multilayer sorption (R2 = 0.9964), with Freundlich constants of 0.312 and 1.760 L g-1 for 1/n and Kf, respectively.

Water Sorption in Electron-Beam Evaporated SiO2 on QCM Crystals and Its Influence on Polymer Thin Film Hydration Measurements.

PubMed

Kushner, Douglas I; Hickner, Michael A

2017-05-30

Spectroscopic ellipsometry (SE) and quartz crystal microbalance (QCM) measurements are two critical characterization techniques routinely employed for hydration studies of polymer thin films. Water uptake by thin polymer films is an important area of study to investigate antifouling surfaces, to probe the swelling of thin water-containing ionomer films, and to conduct fundamental studies of polymer brush hydration and swelling. SiO 2 -coated QCM crystals, employed as substrates in many of these hydration studies, show porosity in the thin electron-beam (e-beam) evaporated SiO 2 layer. The water sorption into this porous SiO 2 layer requires correction of the optical and mass characterization of the hydrated polymer due to changes in the SiO 2 layer as it sorbs water. This correction is especially important when experiments on SiO 2 -coated QCM crystals are compared to measurements on Si wafers with dense native SiO 2 layers. Water adsorption filling void space during hydration in ∼200-260 nm thick SiO 2 layers deposited on a QCM crystal resulted in increased refractive index of the layer during water uptake experiments. The increased refractive index led to artificially higher polymer swelling in the optical modeling of the hydration experiments. The SiO 2 -coated QCM crystals showed between 6 and 8% void as measured by QCM and SE, accounting for 60%-85% of the measured polymer swelling in the low humidity regime (<20% RH) and 25%-40% of the polymer swelling in the high humidity regime (>70% RH) from optical modeling for 105 and 47 nm thick sulfonated polymer films. Correcting the refractive index of the SiO 2 layer for its water content resulted in polymer swelling that successfully resembled swelling measured on a silicon wafer with nonporous native oxide.

The implications of water extractable organic matter (WEOM) on the sorption of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics.

PubMed

Li, Ruilong; Tan, Huadong; Zhang, Linlin; Wang, Shaopeng; Wang, Yinghui; Yu, Kefu

2018-07-30

Microplastics sorption of persistent organic pollutants (POPs) was the core processes that cause negative effects to biota, and their influencing factors and related mechanisms are poorly understood. In this study, we explored the impacts of water extractable organic matter (WEOM), an important source of endogenous dissolved organic matter in mangrove sediment, on the sorption coefficients of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics. The presence of L-WEOM (D) impeded the PAHs sorption as the coefficients (K f ) decreased to 10.17 (μg/kg)/(μg/L) n and to 8.39 (μg/kg)/(μg/L) n for fluorene (Flu) and 1-methyl-fluorene (1-M-Flu), respectively. The K f exhibited good linear relationships with the aliphaticity of L-WEOM (p < 0.05) rather than the aromatic carbon/alkyl carbon content (p > 0.05). Under the presences of L-WEOM (D), (S) and (K), the lone pair electrons of N/O/S-containing PAHs was the dominant factor contributing to the obvious difference of the K f values from the other groups. Moreover, the largest impact of L-WEOM (D) on the Flu sorption was in the case of PVC microplastics, while almost no effect was in the case of PS microplastics. The findings of our work may be helpful in improving our understanding of the role of WEOM on the sorption of PAHs to microplastics in the field mangrove sediment. Copyright © 2018 Elsevier Inc. All rights reserved.

Controlling parameters of fluorescent tracer sorption on soils and sediments

NASA Astrophysics Data System (ADS)

Bork, Marcus; Graf-Rosenfellner, Markus; Lange, Jens; Lang, Friederike

2017-04-01

Fluorescent dyes like uranine (UR) and sulforhodamine B (SRB) have been widely used, especially for tracing hydrological processes. In the recent past, efforts have intensified to use fluorescent tracers also in soils, for example as proxies for organic pollutants. However, the sorption properties of both organic pollutants and fluorescent tracers have to be exactly known to succeed. Yet existing knowledge for soils is still incomplete and poorly standardized. For this reason, we carried out laboratory batch experiments to determine sorption isotherms of UR and SRB with varying pH, soil texture and organic carbon content (OC). As sorbents we used a sandy sediment with low OC, a silty loamy topsoil with 2.8 %-OC and a similar textured subsoil containing 0.6 %-OC. For both tracers six concentration steps each were prepared and shaken with the suspended sorbent for 42 h using a sorbent:solution ratio of 1:5. During the equilibration, the pH was repeatedly adjusted to 5.5, 6.5, and 7.5 by adding hydrochloric acid (HCl) or sodium hydroxide (NaOH). Subsequently, the tracer-sorbent-suspension was centrifuged and the fluorescence of the tracer in the supernatant was measured. In order to examine the influence of OC and the clay fraction on the tracer sorption, batch-experiments at pH 7.5 were also conducted with manipulated sorbents: top- and subsoil samples were treated with H2O2 to remove organic matter and the clay mineral montmorillonite was added to the sandy sediment to achieve final clay contents of 0.1 %, 0.5 %, 1 %, 2 %, 2.5 %, 5 % and 10 % clay. We observed a negative relationship between the linear sorption coefficient Kd and pH, which was stronger for UR than for SRB. Increasing numbers of negative sorption sites and functional groups of both tracers and sorbents with increasing pH might be the reason for this observation. Besides the pH-value, quantity and quality of clay and OC had a crucial influence on the sorption of UR and SRB in soils and sediment. As

Cr(VI) Sorption by Nanosized FeS-Coated Sand

NASA Astrophysics Data System (ADS)

Park, M.; Jeong, H. Y.; Lee, S.; Kang, N.; Kim, K. H.; Choi, H. J.

2015-12-01

Cr(VI) sorption experiments were conducted as a function of pH (4.7, 7.0 and 9.7) using nanosized FeS-coated sand under anoxic environments. Under the experimental conditions, the sand used, with the FeS content of 0.068 mmol per 1 g sand, completely reduced the initially added Cr(VI) to Cr(III) over the pH range examined. The sorption of the once-reduced Cr(III) varied greatly with the solution pH. By the solution-phase analysis, significant amounts of Cr(III) remained as dissolved species at pH 4.7. On the other hands, dissolved Cr was below the detection limit (0.2 μM) at pH 7.0 and 9.7, indicating the greater sorption of Cr(III) at neutral to basic pH than acidic pH. From Cr-K edge X-ray absorption spectroscopy (XAS) analysis of the solid products, the sorbed Cr was shown to be present predominantly as trivalent state in all samples. Regardless of pH, the second coordination shell around Cr (i.e., the Cr-Cr(Fe) shell) was shown to be located at ~2.6 Å, which was far shorter than those in Cr(III)-bearing model compounds such as Cr(OH)3(s) and [Cr, Fe](OH)3(s). Furthermore, the coordination numbers of the second and third shells in the sorption samples (N = 0.7-1.8) were much lower than those in Cr(OH)3(s) and [Cr, Fe](OH)3(s). Taken together, the sorption of the once-reduced Cr(III) was likely to occur via surface-mediated processes (e.g., surface complexation and/or surface precipitation) rather than the bulk-phase precipitation. Financial support was provided by the "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

Simulation of gas diffusion and sorption in nanoceramic semiconductors

NASA Astrophysics Data System (ADS)

Skouras, E. D.; Burganos, V. N.; Payatakes, A. C.

1999-05-01

Gas diffusion and sorption in nanoceramic semiconductors are studied using atomistic simulation techniques and numerical results are presented for a variety of sorbate-sorbent systems. SnO2, BaTiO3, CuO, and MgO substrates are built on the computer using lattice constants and atomic parameters that have been either measured or computed by ab initio methods. The Universal force field is employed here for the description of both intramolecular and nonbonded interactions for various gas sorbates, including CH4, CO, CO2, and O2, pure and in binary mixtures. Mean residence times are determined by molecular dynamics computations, whereas the Henry constant and the isosteric heat of adsorption are estimated by a Monte Carlo technique. The effects of surface hydroxylation on the diffusion and sorption characteristics are quantified and discussed in view of their significance in practical gas sensing applications. The importance of fast diffusion on the response time of the sensitive layer and of the sorption efficiency on the overall sensitivity as well as the potential synergy of the two phenomena are discussed.

Application of green seaweed biomass for MoVI sorption from contaminated waters. Kinetic, thermodynamic and continuous sorption studies.

PubMed

Bertoni, Fernando A; Medeot, Anabela C; González, Juan C; Sala, Luis F; Bellú, Sebastián E

2015-05-15

Spongomorpha pacifica biomass was evaluated as a new sorbent for Mo(VI) removal from aqueous solution. The maximum sorption capacity was found to be 1.28×10(6)±1×10(4) mg kg(-1) at 20°C and pH 2.0. Sorption kinetics and equilibrium studies followed pseudo-first order and Langmuir adsorption isotherm models, respectively. FTIR analysis revealed that carboxyl and hydroxyl groups were mainly responsible for the sorption of Mo(VI). SEM images show that morphological changes occur at the biomass surface after Mo(VI) sorption. Activation parameters and mean free energies obtained with Dubinin-Radushkevich isotherm model demonstrate that the mechanism of sorption process was chemical sorption. Thermodynamic parameters demonstrate that the sorption process was spontaneous, endothermic and the driven force was entropic. The isosteric heat of sorption decreases with surface loading, indicating that S. pacifica has an energetically non-homogeneous surface. Experimental breakthrough curves were simulated by Thomas and modified dose-response models. The bed depth service time (BDST) model was employed to scale-up the continuous sorption experiments. The critical bed depth, Z0 was determined to be 1.7 cm. S.pacifica biomass showed to be a good sorbent for Mo(VI) and it can be used in continuous treatment of effluent polluted with molybdate ions. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of soil humic and fulvic acids, pH and ionic strength on Th(IV) sorption to TiO2 nanoparticles.

PubMed

Tan, Xiaoli; Wang, Xiangke; Chen, Changlun; Sun, Aihua

2007-04-01

Thorium is considered as a chemical analog of other tetravalent actinides. Herein, the sorption of Th(IV) on TiO(2) in the presence or absence of soil fulvic acid (FA)/humic acid (HA) as a function of pH, ionic strength and FA/HA concentration has been studied by a batch method. The morphology was characterized by scanning electron microscopy (SEM). The results indicate that sorption of Th(IV) on TiO(2) increases from 0% to approximately 94% at pH 1 approximately 4, and then maintains level with increasing pH values. Both FA and HA have a positive effect on Th(IV) sorption at low pH values and the contribution of FA on Th(IV) sorption is rather higher than that of HA at pH<4. The sorption is weakly dependent on the concentration of KNO(3) in solution, but the cations K(+), Na(+) and Li(+) influence Th(IV) sorption more obviously. The batch results indicate that the inner sphere complex formation is formed at bare surfaces or FA/HA-bound TiO(2) particle surfaces. Results of SEM analysis show that the particle sizes of TiO(2), Th-TiO(2) and Th-HA-TiO(2) colloids are quite different. Surface complexation may be considered as the main sorption mechanism.

Sorption of selected veterinary antibiotics onto dairy farming soils of contrasting nature.

PubMed

Srinivasan, Prakash; Sarmah, Ajit K; Manley-Harris, Merilyn

2014-02-15

The sorption potential for three sulfonamides (SAs), sulfamethoxazole (SMO), sulfachloropyridazine (SCP) and sulfamethazine (SM) and a macrolide, tylosin tartrate (TT) was assessed on six New Zealand dairy farming soils of contrasting physico-chemical properties. Kinetics studies showed that the sorption was rapid in the first few hours of the contact time (0-2h for SA and 0-4h for TT) and thereafter apparent equilibrium was achieved. Batch sorption isotherm data revealed that the degree of isotherm linearity (N) for SCP and SM varied between 0.50 and 1.08 in the six soils. Isotherms of both TT and SMO were mostly non-linear with the degree of non-linearity for TT (N=0.38-0.71) being greater than for SMO (0.42-0.75) in all soils except Manawatu (TT) and Te Kowhai (SMO) where a linear pattern was observed. Concentration-dependent effective distribution coefficient (Kd(eff)) values for the SMO, SCP and SM antibiotics in the soils ranged from 0.85 to 16.35 L kg(-1), while that for TT was 1.6 to 1,042 L kg(-1). The sorption affinity for all soils followed an order: TT>SCP>SM>SMO. Remarkable high sorption for tylosin in Matawhero soil as compared to other soils was attributed to the presence of oxygen containing acidic polar functional groups as evident in the FT-IR spectra of the soil. Furthermore, it was hypothesised that sorption of TT onto soils was mostly driven by metal oxide-surface mediated transformations whereas for sulfonamides it was primarily due to hydrophobic interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Mg2+ Doped into Electro-synthesized HKUST-1 and Their Initial Hydrogen Sorption Properties

NASA Astrophysics Data System (ADS)

Lestari, W. W.; Ni'maturrohmah, D.; Arrozi, U. S. F.; Suwarno, H.

2018-01-01

The hydrogen storage materials are essentially play important roles in supporting the utilization of hydrogen as a promising alternative energy. Several innovative materials have been proposed and intensively investigated in this regard, including Metal-Organic Framework (MOFs). MOFs type HKUST-1 [Cu3(BTC)2] (BTC = benzene-tri-carboxylate) is the most explored materials in hydrogen storage. In this research, HKUST-1 was electro-synthesized under 15 volt for 1.5 h. This material was ex-situ modified with magnesium(II) ion with variation: 3, 5 and 10 wt% to add attractive sites for hydrogen to form Mg2+@HKUST-1. The final materials were characterized by XRD, FTIR, SEM-EDX, and SAA. Hydrogen sorption measurement was conducted using Sievert system at 30 and 80 °C with pressure from 0.2 to 1.5 bar in 10 minutes for each condition. According to XRD analysis, the basic structure of Mg2+@HKUST-1 was remaining stable. In contrary, SEM analysis showed that HKUST-1 morphology was changed after modification with Mg2+. In addition, the surface area of materials significantly increased from 372.112 to 757.617m2/g, based on SAA analysis. The presence of Mg2+ in the HKUST-1 increased the hydrogen sorption capacity up to 0.475 wt% at 1.4 bar at 30 °C and 0.256 wt% at 80 °C (1.4 bar).

Analysis of (n,2n) cross-section measurements for nuclei up to mass 238

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

Davey, W.G.; Goin, R.W.; Ross, J.R.

All suitable measurements of the energy dependence of (n,2n) cross sections of all isotopes up to mass 238 have been analyzed. The objectives were to display the quality of the measured data for each isotope and to examine the systematic dependence of the (n,2n) cross section upon N, Z, and A. Graphs and tables are presented of the ratio of the asymptotic (n,2n) and nonelastic cross section to the neutron-asymmetry parameter (N--Z)/A. Similar data are presented for the derived nuclear temperature, T, and level-density parameter, $alpha$, as a function of N, Z, and A. This analysis of the results ofmore » over 145 experiments on 61 isotopes is essentially a complete review of the current status of (n,2n) cross-section measurements. (auth)« less

Surfactant-assisted hydrothermal crystallization of nanostructured lithium metasilicate (Li{sub 2}SiO{sub 3}) hollow spheres: II-Textural analysis and CO{sub 2}-H{sub 2}O sorption evaluation

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

Ortiz-Landeros, Jose; Gomez-Yanez, Carlos; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

In a previous work, the synthesis and structural-microstructural characterization of different nanocrystalline lithium metasilicate (Li{sub 2}SiO{sub 3}) samples were performed. Then, in this work, initially, a textural analysis was performed over the same samples. Li{sub 2}SiO{sub 3} samples prepared with a non-ionic surfactant (TRITON X-114) presented the best textural properties. Therefore, this sample was selected to evaluate its water vapor (H{sub 2}O) and carbon dioxide (CO{sub 2}) sorption properties. Sorption experiments were performed at low temperatures (30-80 deg. C) in presence of water vapor using N{sub 2} or CO{sub 2} as carrier gases. Results clearly evidenced that CO{sub 2} sorptionmore » on these materials is highly improved by H{sub 2}O vapor, and of course, textural properties enhanced the H{sub 2}O-CO{sub 2} sorption efficiency, in comparison with the solid-state reference sample. - Graphical abstract: Li{sub 2}SiO{sub 3} varied significantly its capacity of CO{sub 2} absorption as a function of the microstructural properties and by the water presence. Highlights: > We studied the CO{sub 2} absorption on different Li{sub 2}SiO{sub 3} samples in presence of H{sub 2}O vapor. > It was proved that CO{sub 2} absorption on Li{sub 2}SiO{sub 3} is controlled by different factors. > Li{sub 2}SiO{sub 3} with a porous microstructure produces a higher CO{sub 2} absorption. > H{sub 2}O vapor favors the CO{sub 2} absorption on Li{sub 2}SiO{sub 3} due to a surface hydroxylation.« less

Tandem Gravimetric and Volumetric Apparatus for Methane Sorption Measurements

NASA Astrophysics Data System (ADS)

Burress, Jacob; Bethea, Donald

Concerns about global climate change have driven the search for alternative fuels. Natural gas (NG, methane) is a cleaner fuel than gasoline and abundantly available due to hydraulic fracturing. One hurdle to the adoption of NG vehicles is the bulky cylindrical storage vessels needed to store the NG at high pressures (3600 psi, 250 bar). The adsorption of methane in microporous materials can store large amounts of methane at low enough pressures for the allowance of conformable, ``flat'' pressure vessels. The measurement of the amount of gas stored in sorbent materials is typically done by measuring pressure differences (volumetric, manometric) or masses (gravimetric). Volumetric instruments of the Sievert type have uncertainties that compound with each additional measurement. Therefore, the highest-pressure measurement has the largest uncertainty. Gravimetric instruments don't have that drawback, but can have issues with buoyancy corrections. An instrument will be presented with which methane adsorption measurements can be performed using both volumetric and gravimetric methods in tandem. The gravimetric method presented has no buoyancy corrections and low uncertainty. Therefore, the gravimetric measurements can be performed throughout an entire isotherm or just at the extrema to verify the results from the volumetric measurements. Results from methane sorption measurements on an activated carbon (MSC-30) and a metal-organic framework (Cu-BTC, HKUST-1, MOF-199) will be shown. New recommendations for calculations of gas uptake and uncertainty measurements will be discussed.

Water sorption and solubility of polyamide denture base materials

PubMed Central

Nguyen, Long G.; Kopperud, Hilde M.; Øilo, Marit

2017-01-01

Abstract Purpose: Some patients experience adverse reactions to poly(methyl methacrylate)-based (PMMA) dentures. Polyamide (PA) as an alternative to PMMA has, however, not been well documented with regard to water sorption and water solubility. The aim of this in vitro study was to measure water sorption and water solubility of two PA materials compared with PMMA, and to evaluate the major components released from the PA materials and the effect on hardness of the materials. Methods: Ten discs (40.0 mm diameter, 2.0 mm thick) of each material (PA: Valplast and Breflex; PMMA: SR Ivocap HIP) were prepared according to manufacturers’ recommendations. The specimens were tested for water sorption and water solubility, according to a modification of ISO 20795-1:2008. Released substances were analysed by gas chromatography/mass spectrometry (GC/MS). Results: There were statistically significant differences among the materials regarding water sorption, water solubility and time to water saturation. Breflex had the highest water sorption (30.4 μg/mm3), followed by PMMA-material (25.8 μg/mm3) and Valplast (13.6 μg/mm3). Both PA materials had statistically significant lower water solubility than the PMMA. Both PA had a net increase in weight. Analysis by GC/MS identified release of the compound 12-aminododecanolactam from the material Valplast. No release was found from the Breflex material. Conclusions: The PA denture materials show differences in water sorption and solubility, but within the limits of the standard requirements. The PA showed a net increase in weight after long-term water sorption. The clinical implications of the findings are not elucidated. PMID:28642931

Water sorption and solubility of polyamide denture base materials.

PubMed

Nguyen, Long G; Kopperud, Hilde M; Øilo, Marit

2017-01-01

Purpose: Some patients experience adverse reactions to poly(methyl methacrylate)-based (PMMA) dentures. Polyamide (PA) as an alternative to PMMA has, however, not been well documented with regard to water sorption and water solubility. The aim of this in vitro study was to measure water sorption and water solubility of two PA materials compared with PMMA, and to evaluate the major components released from the PA materials and the effect on hardness of the materials. Methods: Ten discs (40.0 mm diameter, 2.0 mm thick) of each material (PA: Valplast and Breflex; PMMA: SR Ivocap HIP) were prepared according to manufacturers' recommendations. The specimens were tested for water sorption and water solubility, according to a modification of ISO 20795-1:2008. Released substances were analysed by gas chromatography/mass spectrometry (GC/MS). Results: There were statistically significant differences among the materials regarding water sorption, water solubility and time to water saturation. Breflex had the highest water sorption (30.4 μg/mm 3 ), followed by PMMA-material (25.8 μg/mm 3 ) and Valplast (13.6 μg/mm 3 ). Both PA materials had statistically significant lower water solubility than the PMMA. Both PA had a net increase in weight. Analysis by GC/MS identified release of the compound 12-aminododecanolactam from the material Valplast. No release was found from the Breflex material. Conclusions: The PA denture materials show differences in water sorption and solubility, but within the limits of the standard requirements. The PA showed a net increase in weight after long-term water sorption. The clinical implications of the findings are not elucidated.

Study on the sorption behaviour of estrone on marine sediments.

PubMed

Zhang, Jing; Yang, Gui-Peng; Li, Quan; Cao, Xiaoyan; Liu, Guangxing

2013-11-15

The sorption behaviour of estrone (E1) on marine sediments treated by different methods was systematically investigated. About 22 h was required for sorption equilibrium of E1. Sorption isotherms of E1 were well fitted with Freundlich model. The sorption behaviour of E1 on HCl-treatment and H2O-treatment sediments related significantly with the sediment organic carbon contents. Additionally, clay minerals and surface areas of sediments played dominant roles in the sorption of E1 on H2O2-treatment sediments. Some external factors which could affect sorption behaviour of E1 were also investigated. Our results showed that the sorption capacity of E1 on the sediments increased with the increasing concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB), nonionic surfactant polyoxyethylene (80) sorbitan esters (Tween 80) and salinity of seawater. In contrast, the sorption capacity of E1 decreased with the increasing concentration of anionic surfactant sodium dodecylbenzene sulfonate (SDBS), pH value and temperature of seawater. Copyright © 2013 Elsevier Ltd. All rights reserved.

Magnetometory Measurement of AlGaN/GaN 2DEG

NASA Astrophysics Data System (ADS)

Tsubaki, K.; Maeda, N.; Saitoh, T.; Kobayashi, N.

2004-03-01

AlGaN/GaN heterostructure devices have been attracting much attention because of their potential for high-performance microwave applications. Therefore, the electronic properties of a 2DEG in AlGaN/GaN heterostructures have recently been discussed. In this paper, we performed the magnetometory measurement of AlGaN/GaN 2DEG at low temperature. The AlGaN/GaN heterostructures were grown by low-pressure metal-organic chemical vapour phase epitaxy on (0001) SiC substrate using AlN buffers. The electron mobility and electron concentration at 4.2 K are 9,540 cm^2/Vs and 6.6 × 10^12 cm-2, respectively. When the temperature is lower than 4.5 K the hysteresis of magnetometric data is observed near zero magnetic field. At the temperature larger than 4.5 K, the hysteresis of magnetometric data disappears and the slope of magnetometric data with respect to magnetic field becomes lower as obeying Currie-Weiss law. In general the hysteresis and Currie-Weiss law behavior in magnetometric data imply the possibility of the ferromagnetism, but the conformation of the ferromagnetism of AlGaN/GaN heterostructure is still difficult and the detailed physical mechanism is still unclear.

Determination of Sorption Coefficient of Phosphorus Applied for Sugarcane Production in Southwestern Florida.

PubMed

Muwamba, A; Nkedi-Kizza, P; Morgan, K T

2016-09-01

Phosphorus is among the essential nutrients applied to sugarcane ( L.) fields in the form of a fertilizer mixture (N, P, and K) in southwestern Florida. Sorption coefficient is used for modeling P movement, and in this study, we hypothesized that the sorption coefficient determined using fertilizer mixture (N, P, and K) will be significantly different from values determined using KCl and CaCl, the electrolytes most commonly used for conducting sorption experiments. Supporting electrolytes, 0.01 mol L KCl, 0.005 mol L CaCl, deionized (DI) water, simulated Florida rain, and fertilizer mixture prepared in Florida rain were used to characterize P sorption. Immokalee (Sandy, siliceous, hyperthermic Arenic Alaquods) and Margate (Sandy, siliceous hyperthermic Mollic Psammaquents) are the dominant mineral soils used for sugarcane production in southwestern Florida; we used the A and B horizons of Margate soil and the A and B horizons of the Immokalee soil for sorption experiments in this study. Freundlich sorption isotherms described P sorption data. The Freundlich sorption isotherm coefficients followed the trend 0.005 mol L CaCl > 0.01 mol L KCl ≈ fertilizer mixture > simulated Florida rain ≈ DI water. Sorption coefficients were used for modeling P movement with HYDRUS 1D; similar P results were obtained with the 0.01 mol L KCl and fertilizer mixture electrolyte treatments. The sorption coefficient for DI water and simulated Florida rain overpredicted P movement. The P sorption data showed the importance of choosing the appropriate electrolyte for conducting experiments based on the composition of fertilizer. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Sorption of phenol and alkylphenols from aqueous solution onto organically modified montmorillonite and applications of dual-mode sorption model

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

Huh, J.K.; Song, D.I.; Jeon, Y.W.

2000-01-01

Single- and multisolute competitive sorptions were carried out in a batch reactor to investigate the uptake of phenol, 4-methylphenol (MeP), 2,4-dimethylphenol (DMeP), and 4-ethylphenol (EtP) dissolved in water at 25 C onto organically modified montmorillonite. Hexadecyltrimethylammonium (HDTMA) cation was exchanged for metal cations on the montmorillonite to the extent of the cation-exchange capacity (CEC) of the montmorillonite to prepare HDTMA-montmorillonite, changing its surface property from hydrophilic to organophilic. It was observed from the experimental results that the adsorption affinity on HDTMA-montmorillonite was in the order 4-EtP {approx} 2,4-DMeP > 4-MeP > phenol. The Langmuir, dual-mode sorption (DS), and Redlich-Peterson (RP)more » models were used to analyze the single-solute sorption equilibria. The competitive Langmuir model (CLM), competitive dual-mode sorption model (CDSM), and ideal adsorbed solution theory (IAST), coupled with the single-solute models (i.e., Langmuir, DS, and RP models), were used to predict the multisolute competitive sorption equilibria. All the models considered in this work yielded favorable representations of both single- and multisolute sorption behaviors. DSM, CDSM, and IAST coupled with the DSM were found to be other satisfactory models to describe the single- and multisolute sorption of the phenolic compounds onto HDTMA-montmorillonite.« less

Detailed sorption characteristics of the anti-diabetic drug metformin and its transformation product guanylurea in agricultural soils.

PubMed

Briones, Rowena M; Sarmah, Ajit K

2018-07-15

Detection of metformin, an antidiabetic drug and its transformation product guanylurea in various environmental matrices such as surface water and groundwater, coupled with their effects on aquatic organisms warrant an understanding of the compounds fate and behaviour in the environment. Batch studies were conducted with the aim of evaluating the sorption of these two emerging contaminants in six New Zealand agricultural soils of contrasting physico-chemical properties. Kinetic studies revealed that metformin and guanylurea sorption in Te Kowhai soil was very rapid initially achieving 90% sorption within the first 4 and 13h, respectively. Fit of several isotherm models to the measured batch sorption data showed that the hybrid models Langmuir-Freundlich and Redlich-Peterson best described the isotherms. Freundlich isotherm showed higher linearity for guanylurea (n F =0.58-0.93) in all soils compared to metformin (n F =0.25-0.71). A linear isotherm was fitted at environmentally relevant low concentrations (< 3mg/L) of target compounds and calculated values of sorption distribution coefficient (K d ) were in the range of 8.97 to 53.49L/kg for metformin and between 10.6 and 37.51L/kg for guanylurea. Sorption of both metformin and guanylurea was dependent on the soil characteristics, however, no generalisation could be made as to which had higher affinity to soils studied. Pearson's correlation and multiple regression analyses indicate that Si/Al (p=0.042) and clay (p=0.015) significantly influenced metformin K d values, whereas the soil's cation exchange capacity (p=0.024) is the single most significant factor determining guanylurea sorption in soils. It is likely that the type of minerals present in soils and its ion-exchange capacity could play an important role in metformin and guanylurea sorption, respectively. Copyright © 2018. Published by Elsevier B.V.

Micropollutant and sludge characterization for modeling sorption equilibria.

PubMed

Barret, Maialen; Carrère, Hélène; Latrille, Eric; Wisniewski, Christelle; Patureau, Dominique

2010-02-01

The sorption of hydrophobic micropollutants in sludge is one of the major mechanisms which drive their fate within wastewater treatment systems. The objective of this study was to investigate the influence of both sludge and micropollutant characteristics on the equilibria of sorption to particles and to dissolved and colloidal matter (DCM). For this purpose, the equilibrium constants were measured for 13 polycyclic aromatic hydrocarbons, 5 polychlorobiphenyls and the nonylphenol, and five different sludge types encountered in treatment systems: a primary sludge, a secondary sludge, the same secondary sludge after thermal treatment, after anaerobic digestion, and after both treatments. After thermal treatment, no more sorption to DCM was observed. Anaerobic biological treatment was shown to enhance micropollutants sorption to particles and to DCM of one logarithmic unit, due to matter transformation. Partial least-squares linear regressions of sorption data as a function of micropollutant and sludge properties revealed that sludge physical and chemical characteristics were more influential than micropollutant characteristics. Two models were provided to predict the sorption of such micropollutants in any sludge. To our knowledge, this is the first time that a three-compartment approach is used to accurately model micropollutant sorption in sludge and to understand the driving mechanisms.

Micropollutant sorption to membrane polymers: a review of mechanisms for estrogens.

PubMed

Schäfer, Andrea I; Akanyeti, Ime; Semião, Andrea J C

2011-05-11

Organic micropollutants such as estrogens occur in water in increasing quantities from predominantly anthropogenic sources. In water such micropollutants partition not only to surfaces such as membrane polymers but also to any other natural or treatment related surfaces. Such interactions are often observed as sorption in treatment processes and this phenomenon is exploited in activated carbon filtration, for example. Sorption is important for polymeric materials and this is used for the concentration of such micropollutants for analytical purposes in solid phase extraction. In membrane filtration the mechanism of micropollutant sorption is a relatively new discovery that was facilitated through new analytical techniques. This sorption plays an important role in micropollutant retention by membranes although mechanisms of interaction are to date not understood. This review is focused on sorption of estrogens on polymeric surfaces, specifically membrane polymers. Such sorption has been observed to a large extent with values of up to 1.2 ng/cm(2) measured. Sorption is dependent on the type of polymer, micropollutant characteristics, solution chemistry, membrane operating conditions as well as membrane morphology. Likely contributors to sorption are the surface roughness as well as the microporosity of such polymers. While retention-and/or reflection coefficient as well as solute to effective pore size ratio-controls the access of such micropollutants to the inner surface, pore size, porosity and thickness as well as morphology or shape of inner voids determines the available area for sorption. The interaction mechanisms are governed, most likely, by hydrophobic as well as solvation effects and interplay of molecular and supramolecular interactions such as hydrogen bonding, π-cation/anion interactions, π-π stacking, ion-dipole and dipole-dipole interactions, the extent of which is naturally dependent on micropollutant and polymer characteristics. Systematic

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I. Effects of pH

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) as a function of pH has been combined with Hg L III-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density ??=0.39-0.42 ??mol/m2) and bayerite (??=0.39-0.44 ??mol/m2), while sorbing more weakly to ??-alumina (??=0.04-0.13 ??mol/m 2). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the ??-Al2O3 sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments. ?? 2003 Elsevier Inc. All rights reserved.

Sorption and Transport of Pharmaceutical chemicals in Organic- and Mineral-rich Soils

NASA Astrophysics Data System (ADS)

Vulava, V. M.; Schwindaman, J.; Murphey, V.; Kuzma, S.; Cory, W.

2011-12-01

Pharmaceutical, active ingredients in personal care products (PhACs), and their derivative compounds are increasingly ubiquitous in surface waters across the world. Sorption and transport of four relatively common PhACs (naproxen, ibuprofen, cetirizine, and triclosan) in different natural soils was measured. All of these compounds are relatively hydrophobic (log KOW>2) and have acid/base functional groups, including one compound that is zwitterionic (cetirizine.) The main goal of this study was to correlate organic matter (OM) and clay content in natural soils and sediment with sorption and degradation of PhACs and ultimately their potential for transport within the subsurface environment. A- and B-horizon soils were collected from four sub-regions within a pristine managed forested watershed near Charleston, SC, with no apparent sources of anthropogenic contamination. These four soil series had varying OM content (fOC) between 0.4-9%, clay mineral content between 6-20%, and soil pH between 4.5-6. The A-horizon soils had higher fOC and lower clay content than the B-horizon soils. Sorption isotherms measured from batch sorption experimental data indicated a non-linear sorption relationship in all A- and B-horizon soils - stronger sorption was observed at lower PhAC concentrations and lower sorption at higher concentrations. Three PhACs (naproxen, ibuprofen, and triclosan) sorbed more strongly with higher fOC A-horizon soils compared with the B-horizon soils. These results show that soil OM had a significant role in strongly binding these three PhACs, which had the highest KOW values. In contrast, cetirizine, which is predominantly positively charged at pH below 8, strongly sorbed to soils with higher clay mineral content and least strongly to higher fOC soils. All sorption isotherms fitted well to the Freundlich model. For naproxen, ibuprofen, and triclosan, there was a strong and positive linear correlation between the Freundlich adsorption constant, Kf, and f

Sorption-desorption of carbamazepine by palygorskite-montmorillonite (PM) filter medium.

PubMed

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

2015-01-23

Palygorskite-montmorillonite (PM) was studied as a potential sewage treatment effluent filter material for carbamazepine. Batch sorption experiments were conducted as a function of granule size (0.3-0.6, 1.7-2.0 and 2.8mm) and different sewage effluent conditions (pH, ionic strength and temperature). Results showed PM had a mix of fibrous and plate-like morphologies. Sorption and desorption isotherms were fitted to the Freundlich model. Sorption is granule size-dependent and the medium granule size would be an appropriate size for optimizing both flow and carbamazepine retention. Highest and lowest sorption capacities corresponded to the smallest and the largest granule sizes, respectively. The lowest and the highest equilibrium aqueous (Ce) and sorbed (qe) carbamazepine concentrations were 0.4 mg L(-1) and 4.5 mg L(-1), and 0.6 mg kg(-1) and 411.8 mg kg(-1), respectively. Observed higher relative sorption at elevated concentrations with a Freundlich exponent greater than one, indicated cooperative sorption. The sorption-desorption hysteresis (isotherm non-singularity) indicated irreversible sorption. Higher sorption observed at higher rather than at lower ionic strength conditions is likely due to a salting-out effect. Negative free energy and the inverse sorption capacity-temperature relationship indicated the carbamazepine sorption process was favorable or spontaneous. Solution pH had little effect on sorption. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption of Pseudomonas putida onto differently structured kaolinite minerals

NASA Astrophysics Data System (ADS)

Vasiliadou, I. A.; Papoulis, D.; Chrysikopoulos, C.; Panagiotaras, D.; Karakosta, E.; Fardis, M.; Papavassiliou, G.

2010-12-01

The presence of bio-colloids (e.g. bacteria and viruses) in the subsurface could be attributed to the release of particles from septic tanks, broken sewer lines or from artificial recharge with treated municipal wastewater. Bio-colloid transport in the subsurface is significantly affected by sorption onto the solid matrix. Bio-colloid attachment onto mobile or suspended in the aqueous phase soil particles (e.g. clay or other minerals) also may influence their fate and transport in the subsurface. The present study focuses on the investigation of Pseudomonas (Ps.) putida sorption onto well (KGa-1) and poorly (KGa-2) crystallized kaolinite minerals. Batch experiments were carried out to determine the sorption isotherms of Ps. putida onto both types of kaolinite particles. The sorption process of Ps. putida onto KGa-1 and KGa-2 is adequately described by a Langmuir isotherm. Attenuated Total Reflection Fourier Transform Infrared Spectroscopy as well as Nuclear Magnetic Resonance were employed to study the sorption mechanisms of Ps. putida. Experimental results indicated that KGa-2 presented higher affinity and sorption capacity than KGa-1. It was shown that electrostatic interactions and structural disorders can influence the sorption capacity of clay particles.

Structural characteristics and sorption properties of lithium-selective composite materials based on TiO2 and MnO2

NASA Astrophysics Data System (ADS)

Chaban, M. O.; Rozhdestvenska, L. M.; Palchyk, O. V.; Dzyazko, Y. S.; Dzyazko, O. G.

2018-04-01

A number of nanomaterials containing titanium dioxide and manganese dioxide were synthesized. The effect of synthesis conditions on structural and sorption characteristics for the selective extraction of lithium ions from solutions was studied. The ion-exchange materials were investigated with the methods of electron microscopy, thermogravimetric and X-ray analyses. During thermal synthesis phases of lithium manganese titanium spinel and TiO2 are being formed. Replacing a part of manganese with titanium ions leads to a decrease in the dissolution of Mn and to an increase in chemical stability. Composites with optimal values of selectivity and sorption rates were used to remove lithium ions from solutions with high salt background. The recovery degree of lithium ions under dynamic conditions reached 99%, the highest sorption capacity was found at pH 10.

Sorption of Organophosphorus Flame Retardants (OPFRs) on ...

EPA Pesticide Factsheets

Organophosphorus flame retardants (OPFRs) are widely used as additives in industrial and consumer products such as electrical and electronic products, furniture, plastics, textiles, and building/construction materials. Due to human exposure and potential health effects, OPFRs including tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP) are EPA Action Plan chemicals for chemical assessments under the Toxic Substances Control Act (TSCA). This work investigated the sorption of these three compounds from the air to settled Arizona Test Dust (ATD) and house dust (HD) in a dual small chamber system. The OPFR exposed dust was analyzed to determine the sorption concentration and sorption rate of OPFRs on the dust. The effect of the composition of the dust on OPFR sorption was evaluated. The results showed that ATD and HD have varied sorption capacity for OPFRs from air. This work explores the relationship between OPFR concentrations in settled dust and air. The data can be used to determine partitioning of OPFRs between the gas phase and settled dust indoors and to inform strategies to reduce exposure and risk.

Theoretical Investigations of CO2 and CH4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material

PubMed Central

2015-01-01

Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal–organic material (MOM) consisting of a 7-fold interpenetrated net of Co2+ ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels—this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM’s high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity. PMID:24835550

Enhancement of the bentonite sorption properties.

PubMed

Mockovciaková, Annamária; Orolínová, Zuzana; Skvarla, Jirí

2010-08-15

The almost monomineral fraction of bentonite rock-montmorillonite was modified by magnetic particles to enhance its sorption properties. The method of clay modification consists in the precipitation of magnetic nanoparticles, often used in preparing of ferrofluids, on the surface of clay. The influence of the synthesis temperature (20 and 85 degrees C) and the weight ratio of bentonite/iron oxides (1:1 and 5:1) on the composite materials properties were investigated. The obtained materials were characterized by the X-ray diffraction method and Mössbauer spectroscopy. Changes in the surface and pore properties of the magnetic composites were studied by the low nitrogen adsorption method and the electrokinetic measurements. The natural bentonite and magnetic composites were used in sorption experiments. The sorption of toxic metals (zinc, cadmium and nickel) from the model solutions was well described by the linearized Langmuir and Freundlich sorption model. The results show that the magnetic bentonite is better sorbent than the unmodified bentonite if the initial concentration of studied metals is very low. Copyright 2010 Elsevier B.V. All rights reserved.

Sorption of silver, gold and palladium with a polythioether foam.

PubMed

Khan, A S; Chow, A

1986-02-01

Silver, gold and palladium can be sorbed by a thiopolymer of the type [HO(CH(2)CH(2)CH(2)SS)(n)CH(2)CH(2)OH]. The distribution coefficient for palladium increases with halide concentration, with iodide having the largest effect. Silver can be extracted from chloride, nitrate or picrate media. The different distribution coefficients for gold in hydrochloric acid and in sodium chloride suggest that different sorption mechanisms predominate.

Effect of temperature and salinity on phosphate sorption on marine sediments.

PubMed

Zhang, Jia-Zhong; Huang, Xiao-Lan

2011-08-15

Our previous studies on the phosphate sorption on sediments in Florida Bay at 25 °C in salinity 36 seawater revealed that the sorption capacity varies considerably within the bay but can be attributed to the content of sedimentary P and Fe. It is known that both temperature and salinity influence the sorption process and their natural variations are the greatest in estuaries. To provide useful sorption parameters for modeling phosphate cycle in Florida Bay, a systematic study was carried out to quantify the effects of salinity and temperature on phosphate sorption on sediments. For a given sample, the zero equilibrium phosphate concentration and the distribution coefficient were measured over a range of salinity (2-72) and temperature (15-35 °C) conditions. Such a suite of experiments with combinations of different temperature and salinity were performed for 14 selected stations that cover a range of sediment characteristics and geographic locations of the bay. Phosphate sorption was found to increase with increasing temperature or decreasing salinity and their effects depended upon sediment's exchangeable P content. This study provided the first estimate of the phosphate sorption parameters as a function of salinity and temperature in marine sediments. Incorporation of these parameters in water quality models will enable them to predict the effect of increasing freshwater input, as proposed by the Comprehensive Everglades Restoration Plan, on the seasonal cycle of phosphate in Florida Bay.

Ultraselective Carbon Molecular Sieve Membranes with Tailored Synergistic Sorption Selective Properties.

PubMed

Zhang, Chen; Koros, William J

2017-09-01

Membrane-based separations can reduce the energy consumption and the CO 2 footprint of large-scale fluid separations, which are traditionally practiced by energy-intensive thermally driven processes. Here, a new type of membrane structure based on nanoporous carbon is reported, which, according to this study, is best referred to as carbon/carbon mixed-matrix (CCMM) membranes. The CCMM membranes are formed by high-temperature (up to 900 °C) pyrolysis of polyimide precursor hollow-fiber membranes. Unprecedentedly high permselectivities are seen in CCMM membranes for CO 2 /CH 4 , N 2 /CH 4 , He/CH 4 , and H 2 /CH 4 separations. Analysis of permeation data suggests that the ultrahigh selectivities result from substantially increased sorption selectivities, which is hypothetically owing to the formation of ultraselective micropores that selectively exclude the bulkier CH 4 molecules. With tunable sorption selectivities, the CCMM membranes outperform flexible polymer membranes and traditional rigid molecular-sieve membranes. The capability to increase sorption selectivities is a powerful tool to leverage diffusion selectivities, and has opened the door to many challenging and economically important fluid separations that require ultrafine differentiation of closely sized molecules. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative structure-property relationships for predicting sorption of pharmaceuticals to sewage sludge during waste water treatment processes.

PubMed

Berthod, L; Whitley, D C; Roberts, G; Sharpe, A; Greenwood, R; Mills, G A

2017-02-01

Understanding the sorption of pharmaceuticals to sewage sludge during waste water treatment processes is important for understanding their environmental fate and in risk assessments. The degree of sorption is defined by the sludge/water partition coefficient (K d ). Experimental K d values (n=297) for active pharmaceutical ingredients (n=148) in primary and activated sludge were collected from literature. The compounds were classified by their charge at pH7.4 (44 uncharged, 60 positively and 28 negatively charged, and 16 zwitterions). Univariate models relating log K d to log K ow for each charge class showed weak correlations (maximum R 2 =0.51 for positively charged) with no overall correlation for the combined dataset (R 2 =0.04). Weaker correlations were found when relating log K d to log D ow . Three sets of molecular descriptors (Molecular Operating Environment, VolSurf and ParaSurf) encoding a range of physico-chemical properties were used to derive multivariate models using stepwise regression, partial least squares and Bayesian artificial neural networks (ANN). The best predictive performance was obtained with ANN, with R 2 =0.62-0.69 for these descriptors using the complete dataset. Use of more complex Vsurf and ParaSurf descriptors showed little improvement over Molecular Operating Environment descriptors. The most influential descriptors in the ANN models, identified by automatic relevance determination, highlighted the importance of hydrophobicity, charge and molecular shape effects in these sorbate-sorbent interactions. The heterogeneous nature of the different sewage sludges used to measure K d limited the predictability of sorption from physico-chemical properties of the pharmaceuticals alone. Standardization of test materials for the measurement of K d would improve comparability of data from different studies, in the long-term leading to better quality environmental risk assessments. Copyright © 2016 British Geological Survey, NERC. Published by

Comparative phosphorus sorption by marine sediments and agricultural soils in a tropical environment.

PubMed

Fox, Robert L; Fares, Ali; Wan, Y; Evensen, Carl I

2006-01-01

The influence of soil phosphorus (P) sources on P sorption characteristics of marine sediments was investigated for Pearl Harbor and off shore Molokai in Hawaii. Estuary sediments were sampled in seven locations; these represented different soils and on-shore activities. The soil samples included nine major soils that contributed sediment to the Harbor and coastal sediments near the island of Molokai. Sediment and soil samples were equilibrated for 6 days in 0.01 M CaCl(2) solution and synthetic seawater containing differing amounts of P. Phosphorus sorption curves were constructed. The equilibrated solution P, with no P added, ranged from 0.01 to 0.2 mg L(-1); P sorption by sediments at standard solution concentration 0.2 mg L(-1), ranged from 0 to 230 mg kg(-1). Sediment P sorption corresponded closely with soil sorption characteristics. Soils contributing sediments to the west reach of Pearl Harbor are highly weathered Oxisols with high standard P sorption values while those in the southeast of the Harbor were Vertisols and Mollisols which sorb little P. The influence of source materials on sediment P sorption was also observed for off-shore sediments near Molokai. Sediments serve as both source and sink for P in Pearl Harbor and in this role can be a stabilizing influence on P concentration in the water column. Phosphorus sorption curves in conjunction with water quality data can help to understand P dynamics between sediments and the water column and help evaluate concerns about P loading to a water body. For Pearl Harbor, solution P in equilibrium with sediments from the Lochs was 0.021 mg L(-1); a value unlikely to produce an algal bloom. (Measured total P in the water columns (mean) was 0.060.).

Sorption and Transport of Diphenhydramine in Natural Soils

NASA Astrophysics Data System (ADS)

Rutherford, C. J.; Vulava, V. M.

2013-12-01

reaction rates for A-horizon soils were -0.20/day, and for B-horizon soils were -0.60/day. The sorption isotherms measured from batch reactor experiments were nonlinear and were fit using the Freundlich model (q=KfCn, where q is sorbed concentration and C is concentration in solution, Kf and n are fitting parameters). Chromatography glass columns were uniformly packed with soils, saturated with 5 mM CaCl2, then spiked with tracer solution containing 50 mg/L diphenhydramine. The concentrations in the effluent solutions were plotted as a function of time to create breakthrough curves. Shape of the breakthrough curves and the retardation factors reflected nonlinear sorption processes observed during batch sorption experiments. Data show that diphenhydramine sorbs more strongly into clay-rich soils than organic-rich soils that have less clay. This could be partly attributed to ionic bonding between the amine functional groups present in the compound with the negatively charged clay surfaces. The benzene rings in the compound can also partition into the soil organic matter. The results have implications for how diphenhydramine sorbs into different soil environments, and eventually affect a much larger ecosystem.

2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils.

PubMed

Boivin, Arnaud; Amellal, Samira; Schiavon, Michel; van Genuchten, Martinus Th

2005-11-01

The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.

Measurements of d 2 n and A 1 n : Probing the neutron spin structure

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

Flay, D.; Posik, M.; Parno, D. S.

We report on the results of the E06-014 experiment performed at Jefferson Lab in Hall A, where a precision measurement of the twist-3 matrix element d(2) of the neutron (d(2)(n)) was conducted. The quantity d(2)(n) represents the average color Lorentz force a struck quark experiences in a deep inelastic electron scattering event off a neutron due to its interaction with the hadronizing remnants. This color force was determined from a linear combination of the third moments of the He-3 spin structure functions, g(1) and g(2), after nuclear corrections had been applied to these moments. The structure functions were obtained frommore » a measurement of the unpolarized cross section and of double-spin asymmetries in the scattering of a longitudinally polarized electron beam from a transversely and a longitudinally polarized He-3 target. The measurement kinematics included two average Q(2) bins of 3.2 GeV2 and 4.3 GeV2, and Bjorken-x 0.25 <= x <= 0.90 covering the deep inelastic and resonance regions. We have found that d(2)(n) is small and negative for < Q(2)> = 3.2 GeV2, and even smaller for < Q(2)> = 4.3 GeV2, consistent with the results of a lattice QCD calculation. The twist-4 matrix element f(2)(n) was extracted by combining our measured d(2)(n) with the world data on the first moment in x of g(1)(n), Gamma(n)(1). We found f(2)(n) to be roughly an order of magnitude larger than d(2)(n). Utilizing the extracted d(2)(n) and f(2)(n) data, we separated the Lorentz color force into its electric and magnetic components, F-E(y,n) and F-B(y,n), and found them to be equal and opposite in magnitude, in agreement with the predictions from an instanton model but not with those from QCD sum rules. Furthermore, using the measured double-spin asymmetries, we have extracted the virtual photon-nucleon asymmetry on the neutron A(1)(n), the structure function ratio g(1)(n)/F-1(n), and the quark ratios (Delta u + Delta(u) over bar)/(u + (u) over bar) and (Delta d + Delta(d) over

Formation and Release of Cobalt(II) Sorption and Precipitation Products in Aging Kaolinite-Water Slurries.

PubMed

Thompson; Parks; Brown

2000-02-15

The uptake and release behavior of cobalt(II) was studied over thousands of hours in CO(2)-free aqueous suspensions of kaolinite under three pairs of total cobalt concentration (Co(T)) and near-neutral pH (7.5-7.8) conditions. Dissolved cobalt, aluminum, and silicon concentrations were monitored by ICPMS, and cobalt-containing products were identified by EXAFS spectroscopy. In each uptake experiment, cobalt sorbed to kaolinite as a mixture of surface-adsorbed monomers or polymers and hydrotalcite-like precipitates of the approximate composition Co(x)Al(OH)(2x+2)(A(n-))(1/n), where 2n-) is nitrate or silicate anion. Precipitate stoichiometry varied with experimental conditions, with the highest Co:Al ratio in the high Co(T)/high pH experiment. Cobalt surface adsorption occurred within seconds, whereas precipitation was slower and continued for the duration of the experiments. Consequently, the proportion of precipitate in the sorbed mixture increased with time in all experiments. The most rapid precipitation occurred in the high Co(T)/high pH experiment, where solutions were most supersaturated with respect to cobalt hydrotalcite. Precipitates incorporated some previously adsorbed cobalt, as well as cobalt from solution. Cobalt release from the solid phase was effected by lowering solution pH to 7.0. Release experiments initiated after shorter sorption times returned a larger fraction of cobalt to solution than those initiated after longer sorption times, for a fixed duration of release. In other words, sorption product stability increased with sorption time. Specifically, under the conditions of the release experiments, the hydrotalcite-like precipitates are more stable than smaller adsorbates, and precipitates that formed over longer time periods are more stable than those that formed rapidly. The latter result suggests that precipitates ripened or modified their structure or composition to become more stable over the course of the several

Sorption capacity of plastic debris for hydrophobic organic chemicals.

PubMed

Lee, Hwang; Shim, Won Joon; Kwon, Jung-Hwan

2014-02-01

The occurrence of microplastics (MPs) in the ocean is an emerging world-wide concern. Due to high sorption capacity of plastics for hydrophobic organic chemicals (HOCs), sorption may play an important role in the transport processes of HOCs. However, sorption capacity of various plastic materials is rarely documented except in the case of those used for environmental sampling purposes. In this study, we measured partition coefficients between MPs and seawater (KMPsw) for 8 polycyclic aromatic hydrocarbons (PAHs), 4 hexachlorocyclohexanes (HCHs) and 2 chlorinated benzenes (CBs). Three surrogate polymers - polyethylene, polypropylene, and polystyrene - were used as model plastic debris because they are the major components of microplastic debris found. Due to the limited solubility of HOCs in seawater and their long equilibration time, a third-phase partitioning method was used for the determination of KMPsw. First, partition coefficients between polydimethylsiloxane (PDMS) and seawater (KPDMSsw) were measured. For the determination of KMPsw, the distribution of HOCs between PDMS or plastics and solvent mixture (methanol:water=8:2 (v/v)) was determined after apparent equilibrium up to 12 weeks. Plastic debris was prepared in a laboratory by physical crushing; the median longest dimension was 320-440 μm. Partition coefficients between polyethylene and seawater obtained using the third-phase equilibrium method agreed well with experimental partition coefficients between low-density polyethylene and water in the literature. The values of KMPsw were generally in the order of polystyrene, polyethylene, and polypropylene for most of the chemicals tested. The ranges of log KMPsw were 2.04-7.87, 2.18-7.00, and 2.63-7.52 for polyethylene, polypropylene, and polystyrene, respectively. The partition coefficients of plastic debris can be as high as other frequently used partition coefficients, such as 1-octanol-water partition coefficients (Kow) and log KMPsw showed good linear

High resolution measurements of the {sup 241}Am(n,2n) reaction cross section

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

Sage, C.; European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, Retieseweg 111, B-2440 Geel; Commissariat a L'Energie Atomique Cadarache, DEN/CAD/DER/SPRC/LEPh, F-13108 St Paul-lez-Durance

Measurements of the {sup 241}Am(n,2n) reaction cross section have been performed at the Joint Research Centre (JRC) Geel in the frame of a collaboration between the European Commission (EC) JRC and French laboratories from CNRS and the Commissariat a L'Energie Atomique (CEA) Cadarache. Raw material coming from the Atalante facility of CEA Marcoule has been transformed by JRC Karlsruhe into suitable {sup 241}AmO{sub 2} samples embedded in Al{sub 2}O{sub 3} matrices specifically designed for these measurements. The irradiations were carried out at the 7-MV Van de Graaff accelerator. The {sup 241}Am(n,2n) reaction cross section was determined relative to the {supmore » 27}Al(n,alpha){sup 24}Na standard cross section. The measurements were performed in four sessions, using quasi-mono-energetic neutrons with energies ranging from 8 to 21 MeV produced via the {sup 2}H(d,n){sup 3}He and the {sup 3}H(d,n){sup 4}He reactions. The induced activity was measured by standard gamma-ray spectrometry using a high-purity germanium detector. Below 15 MeV, the present results are in agreement with data obtained earlier. Above 15 MeV, these measurements allowed the experimental investigation of the {sup 241}Am(n,2n) reaction cross section for the first time. The present data are in good agreement with predictions obtained with the talys code that uses an optical and fission model developed at CEA.« less

Competitive sorption and desorption behavior for three fluoroquinolone antibiotics in a wastewater treatment wetland soil.

PubMed

Conkle, Jeremy L; Lattao, Charisma; White, John R; Cook, Robert L

2010-09-01

Significant amounts of pharmaceuticals are discharged into the environment through wastewater effluent. Sorption has been shown to be a significant aqueous removal pathway for many of these compounds. Competition between ciprofloxacin (CIP), ofloxacin (OFL) and norfloxacin (NOR) and their sorption to, and desorption from, a surrogate Louisiana wastewater treatment wetland soil were investigated to gain insight into the fate and transport of the pollutants within wastewater treatment wetlands. This study was undertaken in the context of a treatment wetland that continuously receives pharmaceuticals. Therefore it is important to understand the total capacity of this soil to sorb these compounds. Sorption to this treatment wetland soil was found to provide a major and potentially long-term removal pathway for these antibiotics from wastewater. LogK(F) values for all three compounds were between 4.09 and 3.90 for sorption and 4.24 and 4.05 microg(1-1/)(n)(cm(3))(1/)(n)g(-1) for desorption. The compounds were sorbed in amounts ranging from 60% to 90% for high and low loading, respectively. The majority of the compounds were sorbed to the soil within the first 20h, indicating that treatment wetland may not need long retention times (weeks to months) in order to remove these compounds. Sorption K(D) values for competition (20 ppm of each compound for 60 ppm of total fluoroquinolones) ranged from 2300 to 3800 cm(3)g(-1) which is between both the 20 (4300-5800 cm(3)g(-1)) and 60 (1300-3000 cm(3)g(-1)) ppm single compound K(D) values, indicating that there is competition between these three compound for sorption sites. Sorption and desorption data (single component and mixture) collectively provide the following evidence: (1) NOR and, to a lesser extent, CIP outcompete OFL for sorption sites, (2) OFL sorbes to its share of "quality" sorption sites, and (3) competition only occurs for lesser "quality" binding sites. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Combination volumetric and gravimetric sorption instrument for high accuracy measurements of methane adsorption

NASA Astrophysics Data System (ADS)

Burress, Jacob; Bethea, Donald; Troub, Brandon

2017-05-01

The accurate measurement of adsorbed gas up to high pressures (˜100 bars) is critical for the development of new materials for adsorbed gas storage. The typical Sievert-type volumetric method introduces accumulating errors that can become large at maximum pressures. Alternatively, gravimetric methods employing microbalances require careful buoyancy corrections. In this paper, we present a combination gravimetric and volumetric system for methane sorption measurements on samples between ˜0.5 and 1 g. The gravimetric method described requires no buoyancy corrections. The tandem use of the gravimetric method allows for a check on the highest uncertainty volumetric measurements. The sources and proper calculation of uncertainties are discussed. Results from methane measurements on activated carbon MSC-30 and metal-organic framework HKUST-1 are compared across methods and within the literature.

Combination volumetric and gravimetric sorption instrument for high accuracy measurements of methane adsorption.

PubMed

Burress, Jacob; Bethea, Donald; Troub, Brandon

2017-05-01

The accurate measurement of adsorbed gas up to high pressures (∼100 bars) is critical for the development of new materials for adsorbed gas storage. The typical Sievert-type volumetric method introduces accumulating errors that can become large at maximum pressures. Alternatively, gravimetric methods employing microbalances require careful buoyancy corrections. In this paper, we present a combination gravimetric and volumetric system for methane sorption measurements on samples between ∼0.5 and 1 g. The gravimetric method described requires no buoyancy corrections. The tandem use of the gravimetric method allows for a check on the highest uncertainty volumetric measurements. The sources and proper calculation of uncertainties are discussed. Results from methane measurements on activated carbon MSC-30 and metal-organic framework HKUST-1 are compared across methods and within the literature.

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

PubMed

Banihashemi, Bahman; Droste, Ronald L

2014-07-15

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

Structural and Kinetic Hydrogen Sorption Properties of Zr0.8Ti0.2Co Alloy Prepared by Ball Milling

PubMed Central

He, Hui; Tang, Tao; Huang, Zhiyong; Sang, Ge; Zhang, Guanghui; Ba, Jingwen; Liu, Meng

2018-01-01

The effects of ball milling on the hydrogen sorption kinetics and microstructure of Zr0.8Ti0.2Co have been systematically studied. Kinetic measurements show that the hydrogenation rate and amount of Zr0.8Ti0.2Co decrease with increasing the ball milling time. However, the dehydrogenation rate accelerates as the ball milling time increases. Meanwhile, the disproportionation of Zr0.8Ti0.2Co speeds up after ball milling and the disproportionation kinetics is clearly inclined to be linear with time at 500°C. It is found from X-ray powder diffraction (XRD) results that the lattice parameter of Zr0.8Ti0.2Co gradually decreases from 3.164 Å to 3.153 Å when the ball milling time extends from 0 h to 8 h, which is mainly responsible for the hydrogen absorption/desorption behaviors. In addition, scanning electron microscope (SEM) images demonstrate that the morphology of Zr0.8Ti0.2Co has obviously changed after ball milling, which is closely related to the hydrogen absorption kinetics. Besides, high-resolution transmission electron microscopy (HRTEM) images show that a large number of disordered microstructures including amorphous regions and defects exist after ball milling, which also play an important role in hydrogen sorption performances. This work will provide some insights into the principles of how to further improve the hydrogen sorption kinetics and disproportionation property of Zr0.8Ti0.2Co. PMID:29721128

Effects of sorption competition on caesium diffusion through compacted argillaceous rock

NASA Astrophysics Data System (ADS)

Jakob, Andreas; Pfingsten, Wilfried; Van Loon, Luc

2009-05-01

We carried out a small-scale laboratory diffusion experiment on a disk-like sample of Opalinus clay from the Mont Terri underground laboratory (Switzerland) using 134Cs as tracer. A through-diffusion phase was followed by an out-diffusion phase where the tracer taken up by the sample was released again. Since the tracer concentration at both boundaries was monitored, careful mass-balance considerations were feasible. A first analysis of the experimental data was done in the frame of a single-species model accounting only for transport and non-linear sorption of caesium. The model could match the data of the through-diffusion phase, however only, when strongly reducing the sorption data based on batch sorption experiments. Yet, such a procedure was in strong contradiction with sorption measurements performed on dispersed and compacted systems. In addition, predictions concerning tracer out-diffusion and mass-balance considerations clearly revealed the shortcomings of this type of model. In a second attempt we applied a multi-species transport model where now the whole water chemistry and a sorption model for caesium were considered. First, the value for the diffusion coefficient was fixed to the best-fit value of the single-species model. But again, the sorption site densities had to be reduced strongly albeit the reduction factor was smaller. Only when fixing the sorption site densities to those values of the sorption model and letting the effective diffusion coefficient D e free for the adjustment, could through-diffusion data be reasonably well fitted and out-diffusion as well as mass-balances be predicted in a satisfying manner. The main results are: (1) The best-fit could be achieved with a value for D e of 1.8 × 10 -10 m 2 s -1 which is rather high but corroborated by results of a molecular modelling study. (2) If caesium arrives in the Opalinus clay sample potassium and sodium (calcium etc.) ions are released and caesium ions are sorbed. The released cations

Rates and equilibria of perfluorooctanoate (PFOA) sorption on soils from different regions of China.

PubMed

Miao, Yu; Guo, Xuetao; Dan Peng; Fan, Tingyu; Yang, Chen

2017-05-01

Understanding sorption of PFOA on soil particles is crucial to evaluate its environmental risk. Here, sorption of PFOA onto ten agricultural soils was examined. The influence of soil physico-chemical properties on PFOA sorption was investigated. The sorption rate of PFOA followed a pseudo-second-order kinetics. Isotherm data of PFOA sorption was fitted with both Freundlich and linear models and the latter fitted better. The sorption-desorption of PFOA onto ten soil samples depended on soil organic carbon content and composition of soil minerals. The sorption and desorption isotherms of PFOA on ten soils were linear, except for the sorption of PFOA onto a few soils, which was described by the Freundlich equation with the parameter N >1. The main sorption mechanism of PFOA was hydrophobic interaction between the perfluorinated carbon chain and the organic matter of soil, as evidenced by the correlation between the solid-liquid distribution coefficient and the fraction of soil organic carbon. The sorption of PFOA in soils was highly irreversible. Copyright © 2017 Elsevier Inc. All rights reserved.

Competitive sorption of atenolol, trimetoprim, carbamazepine and sulfamethoxazole in three soil types

NASA Astrophysics Data System (ADS)

Kočárek, Martin; Kodešová, Radka; Klement, Aleš; Golovko, Oksana; Fér, Miroslav; Nikodem, Antonín; Vondráčková, Lenka; Jakšík, Ondřej; Grabic, Roman

2016-04-01

Transport of human and veterinary pharmaceuticals in soils and consequent ground-water contamination are influenced by many factors, including compound sorption on soil particles and dissipation. Batch sorption experiment for 9 soils (3 soil types with 3 (Greyic Phaeozem on loess), 4 (Haplic Luvisol on loess) and 2 (Haplic Cambisol on gneiss) horizons) and mixture of 4 pharmaceuticals (atenolol, trimetoprim, carbamazepine and sulfamethoxazole) was performed to study competitive sorption of compounds in each soil sample. Sorption affinities and dissipation half-lives of all compounds in topsoils were previously studied by Kodešová et al. (2015 and 2016). Ten grams of dry soil was placed directly into the plastic centrifuge tubes and 20 ml of solution of a known pharmaceutical concentration was added. The same concentrations (0.5, 1, 2.5, 5 and 10 mg/l) were used for all compounds. Three replicates of each concentration were applied for each soil. Tube was shaken for 24 h using the shaking apparatus at 20 C. After shaking, the analyzed soil suspension was centrifuged for 10 min at 6,000 rotations per minute. The actual initial and final equilibrium pharmaceutical concentrations were measured using two-dimensional liquid chromatography-tandem mass spectrometry LC/LC-MS/MS using isotope dilution and internal standard methods. The pharmaceutical concentration adsorbed on soil particles was calculated using the initial and final (i.e. after incubation) pharmaceutical concentrations. The Freundlich equations were used to fit data points of the measured adsorption isotherms. In the case of carbamazepine (neutral form) and sulfamethoxazole (partly negatively charged) sorption affinity of compounds decrease with soil depth. On the other hand in the case of atenolol and trimethoprim (both positively charged) compound sorption affinity was not depth dependent. Data obtained for top soils were compared with sorption affinities for single compounds published by (Kodešová et

Indoor sorption of surrogates for sarin and related nerve agents.

PubMed

Singer, Brett C; Hodgson, Alfred T; Destaillats, Hugo; Hotchi, Toshifumi; Revzan, Kenneth L; Sextro, Richard G

2005-05-01

Sorption rate parameters were determined for three organophosphorus (OP) compounds [dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP)] as surrogates for the G-type nerve agents sarin (GB), soman (GD), and tabun (GA). OP surrogates were injected and vaporized with additional volatile organic compounds into a 50 m3 chamber finished with painted wallboard. Experiments were conducted at two furnishing levels: (i) chamber containing only hard surfaces including a desk, a bookcase, tables, and chairs and (ii) with the addition of plush materials including carpet with cushion, draperies, and upholstered furniture. Each furnishing level was studied with aged and new painted wallboard. Gas-phase concentrations were measured during sealed chamber adsorb and desorb phases and then fit to three mathematical variations of a previously proposed sorption model having a surface sink and allowing for an embedded sink. A four-parameter model allowing unequal transport rates between surface and embedded sinks provided excellent fits for all conditions. To evaluate the potential effect of sorption, this model was incorporated into an indoor air quality simulation model to predict indoor concentrations of a G-type agent and a nonsorbing agent for hypothetical outdoor releases with shelter-in-place (SIP) response. Sorption was simulated using a range of parameters obtained experimentally. Simulations considered outdoor Gaussian plumes of 1- and 5-h duration and infiltration rates of 0.1, 0.3, and 0.9 h(-1). Indoor toxic loads (TL) for a 10-h SIP were calculated as integral C2 dt for a G-type agent. For the 5-h plume, sheltering reduced TLs for the nonsorbing agent to approximately 10-65% of outdoor levels. Analogous TLs for a G-type agent were 2-31% or 0.3-12% of outdoor levels assuming slow or moderate sorption. The relative effect of sorption was more pronounced for the longer plume and higher infiltration rates.

Use of thermodynamic sorption models to derive radionuclide Kd values for performance assessment: Selected results and recommendations of the NEA sorption project

USGS Publications Warehouse

Ochs, M.; Davis, J.A.; Olin, M.; Payne, T.E.; Tweed, C.J.; Askarieh, M.M.; Altmann, S.

2006-01-01

For the safe final disposal and/or long-term storage of radioactive wastes, deep or near-surface underground repositories are being considered world-wide. A central safety feature is the prevention, or sufficient retardation, of radionuclide (RN) migration to the biosphere. To this end, radionuclide sorption is one of the most important processes. Decreasing the uncertainty in radionuclide sorption may contribute significantly to reducing the overall uncertainty of a performance assessment (PA). For PA, sorption is typically characterised by distribution coefficients (Kd values). The conditional nature of Kd requires different estimates of this parameter for each set of geochemical conditions of potential relevance in a RN's migration pathway. As it is not feasible to measure sorption for every set of conditions, the derivation of Kd for PA must rely on data derived from representative model systems. As a result, uncertainty in Kd is largely caused by the need to derive values for conditions not explicitly addressed in experiments. The recently concluded NEA Sorption Project [1] showed that thermodynamic sorption models (TSMs) are uniquely suited to derive K d as a function of conditions, because they allow a direct coupling of sorption with variable solution chemistry and mineralogy in a thermodynamic framework. The results of the project enable assessment of the suitability of various TSM approaches for PA-relevant applications as well as of the potential and limitations of TSMs to model RN sorption in complex systems. ?? by Oldenbourg Wissenschaftsverlag.

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

PubMed

Trigo, Carmen; Koskinen, William C; Kookana, Rai S

2014-01-01

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. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 5.9, 1/nf = 0.7, Kfoc = 447; sandy loam: Kf = 3.9, 1/nf = 0.9, Kfoc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 2.1, 1/nf = 0.8, Kfoc = 177; sandy loam: Kf = 1.7, 1/nf = 0.9, Kfoc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 28; sandy loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22; sandy loam: Kf = 0.5, 1/nf = 0.8, Kfoc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow Kd's were lower than batch Kd's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch Kd's would overpredict potential offsite transport if desorption hysteresis is not taken into account.

Spectroscopic study of carbaryl sorption on smectite from aqueous suspension.

PubMed

de Oliveira, Maurilio Fernandes; Johnston, Cliff T; Premachandra, G S; Teppen, Brian J; Li, Hui; Laird, David A; Zhu, Dongqiang; Boyd, Stephen A

2005-12-01

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the

Competitive sorption of heavy metals by water hyacinth roots.

PubMed

Zheng, Jia-Chuan; Liu, Hou-Qi; Feng, Hui-Min; Li, Wen-Wei; Lam, Michael Hon-Wah; Lam, Paul Kwan-Sing; Yu, Han-Qing

2016-12-01

Heavy metal pollution is a global issue severely constraining aquaculture practices, not only deteriorating the aquatic environment but also threatening the aquaculture production. One promising solution is adopting aquaponics systems where a synergy can be established between aquaculture and aquatic plants for metal sorption, but the interactions of multiple metals in such aquatic plants are poorly understood. In this study, we investigated the absorption behaviors of Cu(II) and Cd(II) in water by water hyacinth roots in both single- and binary-metal systems. Cu(II) and Cd(II) were individually removed by water hyacinth roots at high efficiency, accompanied with release of protons and cations such as Ca 2+ and Mg 2+ . However, in a binary-metal arrangement, the Cd(II) sorption was significantly inhibited by Cu(II), and the higher sorption affinity of Cu(II) accounted for its competitive sorption advantage. Ionic exchange was identified as a predominant mechanism of the metal sorption by water hyacinth roots, and the amine and oxygen-containing groups are the main binding sites accounting for metal sorption via chelation or coordination. This study highlights the interactive impacts of different metals during their sorption by water hyacinth roots and elucidates the underlying mechanism of metal competitive sorption, which may provide useful implications for optimization of phytoremediation system and development of more sustainable aquaculture industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Lithium sorption properties of HMnO in seawater and wastewater.

PubMed

Park, HyunJu; Singhal, Naresh; Jho, Eun Hea

2015-12-15

The lithium concentration in seawater is 0.17 mg/L, which is very low, but the overall quantity is approximately 2.5 × 10(14) kg. Therefore, seawater, which contains a vast amount of lithium, could be a major alternative source that might supply the rising demand for lithium. This research was undertaken to evaluate the feasibility of a manganese oxide (HMnO) adsorbent, which was produced after leaching lithium from lithium manganese oxide, for lithium collection from seawater. The HMnO was synthesized and deformed to a plastic after wet blending of manganese oxide and lithium hydroxide, and subsequently, the influence of pH, sorption isotherms, sorption rates, sorption energies, and effects of the co-ions were measured. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° indicated that the nature of the lithium sorption was both spontaneous and endothermic. The used HMnO could be regenerated by washing it with an HCl solution. The results demonstrated that HMnO could be effectively used for the collection of lithium from seawater with good selectivity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Time-dependent sorption of two novel fungicides in soils within a regulatory framework.

PubMed

Gulkowska, Anna; Buerge, Ignaz J; Poiger, Thomas; Kasteel, Roy

2016-12-01

Convincing experimental evidence suggests increased sorption of pesticides on soil over time, which, so far, has not been considered in the regulatory assessment of leaching to groundwater. Recently, Beulke and van Beinum (2012) proposed a guidance on how to conduct, analyse and use time-dependent sorption studies in pesticide registration. The applicability of the recommended experimental set-up and fitting procedure was examined for two fungicides, penflufen and fluxapyroxad, in four soils during a 170 day incubation experiment. The apparent distribution coefficient increased by a factor of 2.5-4.5 for penflufen and by a factor of 2.5-2.8 for fluxapyroxad. The recommended two-site, one-rate sorption model adequately described measurements of total mass and liquid phase concentration in the calcium chloride suspension and the calculated apparent distribution coefficient, passing all prescribed quality criteria for model fit and parameter reliability. The guidance is technically mature regarding the experimental set-up and parameterisation of the sorption model for the two moderately mobile and relatively persistent fungicides under investigation. These parameters can be used for transport modelling in soil, thereby recognising the existence of the experimentally observed, but in the regulatory leaching assessment of pesticides not yet routinely considered phenomenon of time-dependent sorption. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Using Weighted Least Squares Regression for Obtaining Langmuir Sorption Constants

USDA-ARS?s Scientific Manuscript database

One of the most commonly used models for describing phosphorus (P) sorption to soils is the Langmuir model. To obtain model parameters, the Langmuir model is fit to measured sorption data using least squares regression. Least squares regression is based on several assumptions including normally dist...

Sorption and transport of five sulfonamide antibiotics in agricultural soil and soil-manure systems.

PubMed

Wang, Na; Guo, Xinyan; Xu, Jing; Hao, Lijun; Kong, Deyang; Gao, Shixiang

2015-01-01

Animal manure application is a main spreading route of veterinary antibiotics in soil and groundwater. The sorption and leaching behavior of five commonly used sulfonamides in five typical soil and soil/manure mixtures from China were investigated in this study. Results showed that the empirical Freundlich equation fits well the sorption behavior of selected sulfonamides (r(2) was between 0.803 and 0.999, 1/n was between 0.68 and 1.44), and pH and soil organic carbon (OC) were the key impact factors to sorption and leaching. Addition of manure was found to increase the Kd values of sulfonamides in five different soils, following the rules that the more polar substances, the more increased extent of sorption after manure amendment (5.87 times for sulfadiazine with Log Kow = -0.09, and 2.49 times for sulfamethoxazole with Log Kow = 0.89). When the simulated rainfall amount reached 300 mL (180 mm), sulfonamides have high migration potential to the groundwater, especially in the soil with low OC and high pH. However, manure amendment increased the sorption capacity of sulfonamides in the top layer, thus it might play a role in decreasing the mobility of sulfonamides in soils. The systematic study would be more significant to assess the ecological risks and suggest considering the influence of manure amendment for the environmental fate of antibiotics.

A concentration-dependent multi-term linear free energy relationship for sorption of organic compounds to soils based on the hexadecane dilute-solution reference state.

PubMed

Zhu, Dongqiang; Pignatello, Joseph J

2005-11-15

A LFER of the type in the title is applied to sorption of numerous compounds to polyethylene and three soils for which sorption to natural organic matter (NOM) is presumed dominant. It provides fractional contributions to the Gibbs free energy of sorption corresponding to hydrophobic effects, dipolar/polarizability (D/P) effects in excess of the reference state, and the sum of possible specific forces such as H-bonding and pi-pi electron donor-acceptor (pi-pi EDA) interactions in excess of the reference state. Minimal inputs are the isotherm, the n-hexadecane-water partition coefficient and the Abraham pi parameter representing D/P effects. Sorption of all compounds to polyethylene can be described by considering only hydrophobic effects. Sorption of a calibration set of apolar compounds (aromatic and aliphatic hydrocarbons and chlorinated hydrocarbons) to the natural sorbents is well-described by a combination of hydrophobic and D/P effects. For the apolar set, D/P contributes approximately 15-40% (2-8% for cyclohexane) of sorption free energy. D/P effects increase with the degree of chlorination for aliphatic compounds. For aromatic compounds D/P effects increase with fused ring size but do not vary with degree of chlorination and chlorine substitution pattern. H-bonding contributes substantially to sorption of alcohols, and similarly for 2-nonanol and 2,4-dichlorophenol (33-44%). pi-pi EDA forces contribute to phenanthrene sorption in one case. The effects of concentration, sorbent aromaticity (literature NMR), and sorbent polarity [(O + N)/C] on hydrophobic and D/P contributions for all compounds indicate that (a) molecules fill sites of progressively greater hydrophilic character; (b) the energy penalty for cavity formation in the solid decreases with concentration due to plasticization and greater intermolecular contact; (c) sorbent aromatic content more than sorbent polarity controls D/P interactions. Basing free energy on an inert electrostatic chemical

Sorption and Transport of Ranitidine in Natural Soils

NASA Astrophysics Data System (ADS)

Gaynor, A. J.; Vulava, V. M.

2013-12-01

Increasing levels of pharmaceuticals and their degradants are being discovered in natural water systems all over the world. These chemicals are reported to be discharged from wastewater treatment plants, sewage overflow, and leaking septic tanks. Ranitidine is an example of one such pharmaceutical chemical found in municipal drinking water, streams, and streambed sediments. It is a histamine H2-receptor antagonist, which inhibits the production of stomach acid and is commonly used to treat peptic ulcers and gastro esophageal reflux disease. Ranitidine is a complex organic compound; it is acidic, highly polar, and has two pKa values of approximately 8.2 and 2.7 because of the amine functional groups. When administered orally 25 - 30% of unchanged ranitidine has been shown to expel through urine. The objective of this research is to establish sorption and transport patterns of ranitidine in natural soils and to determine which soil properties influence these patterns the most. Laboratory experiments were preformed on A-horizon and B-horizon soil samples collected from the relatively undisturbed Francis Marion National Forest, a managed forest near Charleston, SC. The soils were characterized for chemical and physical properties: ranges of clay content = 6-20%, total organic content = 1-8%, and pH = 3.6-4.9. Kinetic reaction rates and equilibrium sorption isotherms were measured using batch experiments, whereas column experiments were used to quantify transport behavior. The reaction rates were -0.22/day and -0.33/day for organic-rich and clay-rich soils, respectively. The kinetic reaction rates were used to determine equilibration times for further equilibrium batch reactor experiments, which have soil solutions spiked with concentrations of ranitidine ranging from 0.1 mg/L to 100 mg/L. The concentration remaining in solution (C, mg/L) was plotted against the concentration in the soil (q, mg/kg) to create sorption isotherms. Ranitidine was more strongly sorbed to B

Valorisation of post-sorption materials: Opportunities, strategies, and challenges.

PubMed

Harikishore Kumar Reddy, D; Vijayaraghavan, K; Kim, Jeong Ae; Yun, Yeoung-Sang

2017-04-01

Adsorption is a facile, economic, eco-friendly and low-energy requiring technology that aims to separate diverse compounds (ions and molecules) from one phase to another using a wide variety of adsorbent materials. To date, this technology has been used most often for removal/recovery of pollutants from aqueous solutions; however, emerging post-sorption technologies are now enabling the manufacture of value-added key adsorption products that can subsequently be used for (i) fertilizers, (ii) catalysis, (iii) carbonaceous metal nanoparticle synthesis, (iv) feed additives, and (v) biologically active compounds. These new strategies ensure the sustainable valorisation of post-sorption materials as an economically viable alternative to the engineering of other green chemical products because of the ecological affability, biocompatibility, and widespread accessibility of post-sorption materials. Fertilizers and feed additives manufactured using sorption technology contain elements such as N, P, Cu, Mn, and Zn, which improve soil fertility and provide essential nutrients to animals and humans. This green and effective approach to managing post-sorption materials is an important step in reaching the global goals of sustainability and healthy human nutrition. Post-sorbents have also been utilized for the harvesting of metal nanoparticles via modern catalytic pyrolysis techniques. The resulting materials exhibited a high surface area (>1000m 2 /g) and are further used as catalysts and adsorbents. Together with the above possibilities, energy production from post-sorbents is under exploration. Many of the vital 3E (energy, environment, and economy) problems can be addressed using post-sorption materials. In this review, we summarize a new generation of applications of post-adsorbents as value-added green chemical products. At the end of each section, scientific challenges, further opportunities, and issues related to toxicity are discussed. We believe this critical

Describing sorption of pharmaceuticals to lake and river sediments, and sewage sludge from UNESCO Biosphere Reserve Kristianstads Vattenrike by chromatographic asymmetry factors and recovery measurements.

PubMed

Svahn, Ola; Björklund, Erland

2015-10-09

Over the past 30 years a vast number of studies have demonstrated the presence of pharmaceutical residues in the environment. But still knowledge is scarce regarding the interaction of these emerging pollutants with various matrices in nature. A chromatographic system with on-line detection was developed to perform a sorption study of six selected pharmaceuticals to four natural sediments and dewatered digested sewage treatment plant sludge with differing physicochemical characteristics. Sorption effects, measured as asymmetry factors and recoveries, differed pronouncedly among the pharmaceuticals and between the matrices, which could be explained by basic physicochemical properties of the investigated compounds in relation to matrix characteristics. Protonated and deprotonated molecular properties had the greatest importance for sorbate-sorbent interactions. Atenolol, with cationic properties, showed the highest degree of sorption regardless of the matrix studied. Diclofenac and furosemide, both acids, showed the least tendency towards interactions to natural matrices. Among the neutral compounds bendroflumethiazide, carbamazepine and oxazepam, weaker forces, such as van der Waals, aromatic electron donor-acceptor interactions, and hydrogen forces, seemed more important to determine sorption differences. Results revealed that sorption of pharmaceuticals on natural sediments decreased in the order: atenolol (+)>bendroflumethiazide>oxazepam>carbamazepine>diclofenac (-)>furosemide (-). The matrix content of organic matter measured as total organic carbon (TOC) clearly dictated drug sorption. Beside from studying matrix interaction, these results and the developed technique and methodology might find use in the development of new removal processes of pharmaceuticals from wastewater based on improved knowledge concerning chemical interactions to filter materials. Copyright © 2015 Elsevier B.V. All rights reserved.

Sorption of chromium with struvite during phosphorus recovery.

PubMed

Rouff, Ashaki A

2012-11-20

Struvite (MgNH(4)PO(4)·6H(2)O; MAP) precipitation is a viable means of phosphorus (P) recovery from animal and human wastes. The behavior of metal contaminants such as chromium (Cr) during struvite precipitation, however, requires consideration. Here the influence of both Cr concentration and oxidation state on sorption is assessed. The Cr content of struvite precipitated in the presence of 1-100 μM Cr as Cr(III) (22.3-3030.1 mg/kg) was higher than that of solids from Cr(VI) (4.5-5.1 mg/kg) solutions. For 1-20 μM Cr(III) solids, scanning electron microscopy (SEM) revealed etch pit formation on struvite crystal surfaces, indicative of a surface interaction. The formation of an adsorbate was confirmed by X-ray absorption fine structure spectroscopy (XAFS). At initial concentrations ≥20 μM Cr(III), XAFS confirmed the formation of a Cr(OH)(3)·nH(2)O(am) precipitate. Fourier transform infrared (FT-IR) spectroscopy revealed that both Cr(III) and Cr(VI) sorption resulted in distortion of the PO(4)(3-) tetrahedra in the mineral structure. This, combined with SEM results revealed that even at low sorbed concentrations, the Cr impurity can affect the mineral surface and structure. Thus, the initial Cr concentration and oxidation state in wastes targeted for P recovery will dictate the final Cr content, the mechanism of sorption, and impact on the struvite structure.

Sorption J-T refrigeration utilizing manganese nitride chemisorption

NASA Technical Reports Server (NTRS)

Jones, Jack; Lund, Alan

1990-01-01

The equilibrium pressures and compositions have been measured for a system of finely powdered manganese nitride and nitrogen gas at 650, 700, 800, and 850 C for various nitrogen loadings. Pressures ranged from less than 0.02 MPa at 650 C to 6.38 MPa at 850 C. Analysis of the test results has shown that under certain conditions Mn(x)N(y) could potentially be used in a triple regenerative sorption compressor refrigeration system, but the potential power savings are small compared to the increased complexity and reliability problems associated with very high temperature (above 950 C) pressurized systems.

Sorption of a nonionic surfactant Tween 80 by minerals and soils.

PubMed

Kang, Soyoung; Jeong, Hoon Young

2015-03-02

Batch experiments were conducted to evaluate Tween 80 sorption by oxides, aluminosilicates, and soils. For oxides, the sorption by silica and alumina follow linear isotherms, and that by hematite follows a Langmuir isotherm. Considering isotherm type and surface coverage, Tween 80 may partition into the silica/alumina-water interface, whereas it may bind to hematite surface sites. Among aluminosilicates, montmorillonite shows the greatest sorption due to the absorption of Tween 80 into interlayers. For other aluminosilicates, it sorbs to surfaces, with the sorption increasing as plagioclasesorption. The greater sorption by untreated soils than H2O2-treated soils indicates that soil organic matter is a vital sorbent. The sorption hysteresis, contributed to by clay minerals and soil organic matter, is characterized by the greater sorption during the desorption than the sorption stages. This suggests the potential difficulty in removing surfactants from soils. Also, sorption of surfactants can adversely affect surfactant-enhanced remediation by decreasing the aquifer permeability and the availability of surfactants for micellar solubilization. Copyright © 2014 Elsevier B.V. All rights reserved.

Dispersion, sorption and photodegradation of petroleum hydrocarbons in dispersant-seawater-sediment systems.

PubMed

Zhao, Xiao; Liu, Wen; Fu, Jie; Cai, Zhengqing; O'Reilly, S E; Zhao, Dongye

2016-08-15

This work examined effects of model oil dispersants on dispersion, sorption and photodegradation of petroleum hydrocarbons in simulated marine systems. Three dispersants (Corexit 9500A, Corexit 9527A and SPC 1000) were used to prepare dispersed water accommodated oil (DWAO). While higher doses of dispersants dispersed more n-alkanes and PAHs, Corexit 9500A preferentially dispersed C11-C20 n-alkanes, whereas Corexit 9527A was more favorable for smaller alkanes (C10-C16), and SPC 1000 for C12-C28 n-alkanes. Sorption of petroleum hydrocarbons on sediment was proportional to TPH types/fractions in the DWAOs. Addition of 18mg/L of Corexit 9500A increased sediment uptake of 2-3 ring PAHs, while higher dispersant doses reduced the uptake, due to micelle-enhanced solubilization effects. Both dispersed n-alkanes and PAHs were susceptible to photodegradation under simulated sunlight. For PAHs, both photodegradation and photo-facilitated alkylation were concurrently taking place. The information can facilitate sounder assessment of fate and distribution of dispersed oil hydrocarbons in marine systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

SORPTION OF VOLATILE ORGANIC SOLVENTS FROM AQUEOUS SOLUTION ONTO SUBSURFACE SOLIDS

EPA Science Inventory

Sorption isotherms for tetrachloroethene on low-carbon subsurface core samples were linear to equilibrium solution concentrations of 2 mg L−1. Concentrations above this value produced pronounced curvature in the sorption isotherms. Sorption of tetrachloroethene, benzene, trichlor...

Sorption of perfluoroalkyl substances to two types of minerals.

PubMed

Hellsing, Maja S; Josefsson, Sarah; Hughes, Arwel V; Ahrens, Lutz

2016-09-01

The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Equilibrium sorption and diffusion rate studies with halogenated organic chemical and sandy aquifer material

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

Ball, W.P.

1990-01-01

Concepts for rate limitation of sorptive uptake of hydrophobic organic solutes by aquifer solids are reviewed, emphasizing physical diffusion models and in the context of effects on contaminant transport. Data for the sorption of tetrachloroethene (PCE) and 1,2,4,5-tetrachlorobenzene (TeCB) on Borden sand are presented, showing that equilibrium is attained very slowly, requiring equilibration times on the order of tens of days for PCE and hundreds of days for TeCB. The rate of approach to equilibrium decreased with increasing particle size and sorption distribution coefficient, in accordance with retarded intragranular diffusion models. Pulverization of the samples significantly decreased the required timemore » to equilibrium without changing the sorption capacity of the solids. Batch sorption methodology was refined to allow accurate measurement of long-term distribution coefficients, using purified {sup 14}C-labelled solute spikes and sealed glass ampules. Sorption isotherms for PCE and TeCB were conducted with size fractions of Borden sand over four to five orders of magnitude in aqueous concentration, and were found to be slightly nonlinear (Freundlich exponent = 0.8). A concentrated set of data in the low concentration range (<50 ug/L) revealed that sorption in this range could be equally well described by a linear isotherm. Distribution coefficients of the two solutes with seven size fractions of Borden sand, measured at low concentration and at full equilibrium, were between seven and sixty times the value predicted on the basis of recent correlations with organic carbon content. Rate results for coarse size fractions support a simple pore diffusion model, with pore diffusion coefficients estimated to be approximately 3 {times} 10{sup {minus}8} cm{sup 2}/sec, more than 200{times} lower than the aqueous diffusivities.« less

The thermodynamic parameters of sorption and enantioselectivity of the chiral smectic liquid crystal 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid

NASA Astrophysics Data System (ADS)

Onuchak, L. A.; Stepanova, R. F.; Akopova, O. B.; Glebova, O. V.; Chernova, O. M.

2008-06-01

The thermodynamic characteristics of sorption of n-alkanes, arenes, aldehydes, monoatomic alcohols, and optical isomers of camphene and butanediol-2,3 by a chiral smectic liquid crystal, 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid, from the gas phase were studied over the temperature range including the S*C and S*A mesophases and isotropic phase. The standard and excess thermodynamic functions of sorption were determined for 26 sorbates of the classes of substances specified. The S*C and S*A mesophases exhibited selectivity with respect to the separation of para and meta xylenes (α p/m = 1.06 1.07, 90 108°C) and pronounced enantioselectivity (αR/S = 1.05 1.09, 87 108°C). The helically twisted structure of the smectic liquid crystal was shown to play an important role in the mechanism of the chiral recognition of optical isomers of polar and low-polarity compounds under gas-liquid chromatography conditions.

The influence of storage time and pH variation on water sorption by different composite resins.

PubMed

Gusmão, George Mário de Araújo Silva; De Queiroz, Thiago Vinicius Veras; Pompeu, Guilherme Ferrer; Menezes Filho, Paulo Fonseca; da Silva, Cláudio Heliomar Vicente

2013-01-01

The objective of this work was to assess the influence of storage time and pH cycling on water sorption by different composite resins. Nine resin brands were selected and divided into groups: G1-ROK (SDI), G2-ICE (SDI), G3-GLACIER (SDI), G4-Z350 (3M/ESPE), G5-Z250 (3M/ESPE), G6-TPH 3 (DENTSPLY), G7-ESTHET X (DENTSPLY), G8-SUPRAFILL (SSWHITE), and G9-MASTERFILL (BIODINΒMICS). Ninety specimens, ten per group, were obtained using an aluminum matrix. Specimens measured 10 mm diameter × 2 mm width. The groups were divided into subgroups according to the immersion solution: A - control (n = 05) stored in artificial saliva pH = 7.0 and B-test (n = 05) submitted to seven consecutive days of pH cycling (cariogenic challenger) that consisted of immersion in a pH° = 4.3 solution for 6 h followed by immersion in a pH¹ =7.0 solution for 18 h and stored in artificial saliva pH = 7.0 until the end of the experiment. The specimens were weighed on six occasions: T 0 (after fabrication), T 1 (24 h), T 2 (7 days), T 3 (15 days), T 4 (30 days), T 5 (60 days), and then analyzed. The water sorption was determined by the weight difference between the specimens at the time intervals. The mean weight gain was exactly the same for both the subgroups within group G4. The highest means for the control subgroup were found in groups: G1, G5, G7, G8, and G9. For the pH cycling subgroup, the highest means were found in G2, G3, and G6; however, significant differences between the subgroups compared to the mean-weight gain were found for G1, G5, and G7. The water sorption of composite resins is dependent upon their storage time. The pH cycling created a significant impact on resins G1, G5, and G7. The sorption and solubility of composite resins vary according to their chemical composition.

Agro-waste biosorbents: Effect of physico-chemical properties on atrazine and imidacloprid sorption.

PubMed

Mandal, Abhishek; Singh, Neera; Nain, Lata

2017-09-02

Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with K F values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values <1. The Freundlich constant Correlating atrazine/imidacloprid sorption parameter [K F .(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.

[Sorption mechanism of ofloxacin by carbon nanotubes].

PubMed

Zhao, Xing-Xing; Yu, Shui-Li; Wang, Zhe

2014-02-01

Sorption of ofloxacin (OFL) by carbon nanotubes is an effective method to control its fate in aquatic environment. The sorption process of OFL by mixed acid-treated and non-treated multi-walled carbon nanotubes was discussed. Sorption kinetics, sorption isotherm, desorption, sorption thermodynamics and effect of pH were investigated. The results indicated that the sorption kinetics followed the pseudo-second order kinetics model. The equilibrium sorption capacity of OFL on MWCNTs-O was higher. The sorption isotherm could be fitted by both the Langmuir and Freundlich models. The equilibrium sorption capacity dropped when the pH of aqueous solution was in the range of 6.0 to 10.0. Obvious desorption hysteresis was observed during the desorption experiments, especially on MWCNTs-O. Sorption thermodynamics analysis showed that the interactions between the OFL and sorbents were mainly between molecules. More oxygen-containing functional groups introduced on MWCNTs provided OFL molecules with more sorptive sites, which facilitated the generation of hydrogen bonds, a relatively strong interaction. The hydrogen bonds dominated the sorption process of OFL by MWCNTs/MWCNTs-O, explaining the experimental phenomena.

High-Precision Measurements of 15N15N, 14N15N, and 14N2 in N2 and Potential Applications to Oceanic Nitrogen Cycle Research

NASA Astrophysics Data System (ADS)

Li, S.; Yeung, L.; Young, E. D.; Ostrom, N. E.; Haslun, J. A.

2016-02-01

The balance of nitrogen fixation and nitrogen loss in the oceans is uncertain. For example, anaerobic ammonia oxidation could account for 50% or more of marine N2 production, although its global importance is still poorly known. Isotopic ratios in fixed nitrogen species (e.g., δ15N and δ18O values of NO2- and NO3-) are widely used to trace preservation and removal of N-bearing compounds and/or isotopic variations of their different sources. However, these approaches in general probe only one side of the nitrogen mass balance—the "fixed" nitrogen reservoir—so they offer few constraints on the ultimate loss of nitrogen from that pool as N2. The rare isotopologue ratio 15N15N/14N2 in N2may provide information about those nitrogen-loss processes directly. We will report the first measurements of Δ30 (the abundance of 15N15N relative to that predicted by chance alone), made on a unique high-resolution mass spectrometer (the Nu Instruments Panorama), and we will discuss the potential utility of Δ30 as an independent tracer of the nitrogen cycle. The parameter Δ30 is insensitive to the bulk 15N/14N isotopic ratio of the reservoir; instead, it reflects isotopic ordering in N2, which is altered when N-N bonds are made or broken. Our preliminary measurements of N2 from denitrifying soils and pure cultures of denitrifiers indicate large kinetic isotopic effects during N-N bond formation that favor 15N15N production during denitrification. We also observed a nonstochastic excess of 15N15N in tropospheric N2 [Δ30 = +19.05 ± 0.12‰ (1σ)]. This excess likely comes from fixed-nitrogen loss processes in the biosphere. Variations in Δ30 of N2 from pure culture experiments (+16.96 to +18.95‰) probably reflect the different isotopic signatures of the enzymes that catalyze denitrification. So, enzyme-specific Δ30 values of dissolved N2 should provide information about the importance of different biochemical pathways of fixed-nitrogen loss (e.g., denitrification vs

The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA 2- to goethite and a subsurface sediment

NASA Astrophysics Data System (ADS)

Zachara, John M.; Smith, Steven C.; Fredrickson, James K.

2000-04-01

Laboratory experiments were conducted with suspensions of goethite (α-FeOOH) and a subsurface sediment to assess the influence of bacterial iron reduction on the fate of Co(II)EDTA 2-, a representative metal-ligand complex of intermediate stability (log K Co(II)EDTA = 17.97). The goethite was synthetic (ca. 55 m 2/g) and the sediment was a Pleistocene age, Fe(III) oxide-containing material from the Atlantic coastal plain (Milford). Shewanella alga strain BrY, a dissimilatory iron reducing bacterium (DIRB), was used to promote Fe(III) oxide reduction. Sorption isotherms and pH adsorption edges were measured for Co 2+, Fe 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- on the two sorbents in 0.001 mol/L Ca(ClO 4) 2 to aid in experiment interpretation. Anoxic suspensions of the sorbents in PIPES buffer at pH 6.5-7.0 were spiked with Co(II)EDTA 2- (10 -5 mol/L, 60Co and 14EDTA labeled), inoculated with BrY (1-6 × 10 8 organisms/mL), and the headspace filled with a N 2/H 2 gas mix. The experiments were conducted under non-growth conditions. The medium did not contain PO 43- (with one exception), trace elements, or vitamins. The tubes were incubated under anoxic conditions at 25°C for time periods in excess of 100 d. Replicate tubes were sacrificed and analyzed at desired time periods for pH, Fe(II) TOT, Fe (aq)2+, 60Co, and 14EDTA. Abiotic analogue experiments were conducted where Fe (aq)2+ was added in increasing concentration to Co(II)EDTA 2-/mineral suspensions to simulate the influence of bacterial Fe(II) evolution. The DIRB generated Fe(II) from both goethite and the Milford sediment that was strongly sorbed by mineral surfaces. Aqueous Fe 2+ increased during the experiment as surfaces became saturated; Fe (aq)2+ induced the dissociation of Co(II)EDTA 2- into a mixture of Co 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- (log K Fe(II)EDTA = 15.98). The extent of dissociation of Co(II)EDTA 2- was greater in the subsurface sediment because it sorbed Fe(II) less strongly than did

Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

PubMed

Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

2014-07-01

Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

USGS Publications Warehouse

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

1987-01-01

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

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

PubMed

Hung, Nguyen Viet; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori; Tsunoi, Shinji; Tanaka, Minoru

2004-01-01

Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

Sorption of diclofenac and naproxen onto MWCNT in model wastewater treated by H2O2 and/or UV.

PubMed

Czech, Bożena; Oleszczuk, Patryk

2016-04-01

The application of oxidation processes such as UV and/or H2O2 will change the physicochemical properties of carbon nanotubes (CNT). It may affect the sorption affinity of CNT to different contaminants and then affect their fate in the environment. In the present study the adsorption of two very common used pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or UV/H2O2 was investigated. Four different adsorption models (Freundlich, Langmuir, Temkin, Dubinin-Radushkevich) were tested. The best fitting of experimental data was observed for Freundlich or Langmuir model. The significant relationships between Q calculated from Langmuir model with O% and dispersity were observed. Kinetics of diclofenac and naproxen followed mainly pseudo-second order indicating for chemisorption limiting step of adsorption. The data showed that the mechanism of sorption was physical or chemical depending on the type of CNT modification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Measuring N2 Pressure Using Cyanobacteria Discipline: Geomicrobiology

NASA Technical Reports Server (NTRS)

Silverman, Shaelyn N.; Kopf, Sebastian; Gordon, Richard; Bebout, Brad M.; Som, Sanjoy

2017-01-01

The evolution of Earth's atmosphere has been governed by biological evolution. Dinitrogen (N2) has been a major constituent of Earth's atmosphere throughout the planet's history, yet only a few constraints exist for the partial pressure of N2 (pN2). In this study we evaluate two new potential proxies for pN2: the physical spacing between heterocysts and the isotopic signature of nitrogen fixation in filamentous cyanobacteria. Heterocyst-forming filamentous cyanobacteria are some of the oldest photosynthetic microorganisms on Earth, and debated fossilized specimens have been found in sedimentary rocks as old as 2 Ga. These organisms overcome nitrogen limitation in their aqueous environment through cellular differentiation along their filaments. The specialized cells that develop, known as heterocysts, fix the nitrogen and laterally distribute it to neighboring cells along the filaments. Because the concentration of the dissolved N2 available to the filaments correlates directly with pN2, any preservable physiological response of the organism to the changed N2 availability constitutes a potential proxy for pN2. In the laboratory, we have examined how pN2 is reflected in the heterocyst spacing pattern and in the isotopic signature of nitrogen fixation by subjecting the representative species Anabaena cylindrica and Anabaena variabilis to different N2 partial pressures during growth at constant temperature and lighting (in media free of combined nitrogen). We show experimentally that the distance between heterocysts and the nitrogen isotope fractionation measured in bulk biomass reflect the pN2 experienced by Anabaena cylindrica. Current work is investigating these responses in Anabaena variabilis. When heterocystous cyanobacteria fossilize, these morphological and isotopic signatures should preserve information about pN2 at that time. Application of this relationship to the rock record may provide a paleoproxy to complement the two existing geobarometers.

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

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

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

Measurement of 235U(n,n'γ) and 235U(n,2nγ) reaction cross sections

NASA Astrophysics Data System (ADS)

Kerveno, M.; Thiry, J. C.; Bacquias, A.; Borcea, C.; Dessagne, P.; Drohé, J. C.; Goriely, S.; Hilaire, S.; Jericha, E.; Karam, H.; Negret, A.; Pavlik, A.; Plompen, A. J. M.; Romain, P.; Rouki, C.; Rudolf, G.; Stanoiu, M.

2013-02-01

The design of generation IV nuclear reactors and the studies of new fuel cycles require knowledge of the cross sections of various nuclear reactions. Our research is focused on (n,xnγ) reactions occurring in these new reactors. The aim is to measure unknown cross sections and to reduce the uncertainty on present data for reactions and isotopes of interest for transmutation or advanced reactors. The present work studies the 235U(n,n'γ) and 235U(n,2nγ) reactions in the fast neutron energy domain (up to 20 MeV). The experiments were performed with the Geel electron linear accelerator GELINA, which delivers a pulsed white neutron beam. The time characteristics enable measuring neutron energies with the time-of-flight (TOF) technique. The neutron induced reactions [in this case inelastic scattering and (n,2n) reactions] are identified by on-line prompt γ spectroscopy with an experimental setup including four high-purity germanium (HPGe) detectors. A fission ionization chamber is used to monitor the incident neutron flux. The experimental setup and analysis methods are presented and the model calculations performed with the TALYS-1.2 code are discussed.

Meta-analysis of pesticide sorption in subsoils

NASA Astrophysics Data System (ADS)

Jarvis, Nicholas

2017-04-01

It has been known for several decades that sorption koc values tend to be larger in soils that are low in organic carbon (i.e. subsoils). Nevertheless, in a regulatory context, the models used to assess leaching of pesticides to groundwater still rely on a constant koc value, which is usually measured on topsoil samples. This is mainly because the general applicability of any improved model approach that is also simple enough to use for regulatory purposes has not been demonstrated. The objective of this study was therefore first to summarize and generalize available literature data in order to assess the magnitude of any systematic increase of koc values in subsoil and to test an alternative model of subsoil sorption that could be useful in pesticide risk assessment and management. To this end, a database containing the results of batch sorption experiments for pesticides was compiled from published studies in the literature, which placed at least as much emphasis on measurements in subsoil horizons as in topsoil. The database includes 967 data entries from 46 studies and for 34 different active substances (15 non-ionic compounds, 13 weak acids, 6 weak bases). In order to minimize pH effects on sorption, data for weak acids and bases were only included if the soil pH was more than two units larger than the compound pKa. A simple empirical model, whereby the sorption constant is given as a power law function of the soil organic carbon content, gave good fits to most data sets. Overall, the apparent koc value, koc(app), for non-ionic compounds and weak bases roughly doubled as the soil organic carbon content decreased by a factor of ten. The typical increase in koc(app) was even larger for weak acids: on average koc(app) increased by a factor of six as soil organic carbon content decreased by a factor of ten. These results suggest the koc concept currently used in leaching models should be replaced by an alternative approach that gives a more realistic

Biotransformation and sorption of trace organic compounds in biological nutrient removal treatment systems.

PubMed

Lakshminarasimman, Narasimman; Quiñones, Oscar; Vanderford, Brett J; Campo-Moreno, Pablo; Dickenson, Eric V; McAvoy, Drew C

2018-05-28

This study determined biotransformation rates (k bio ) and sorption-distribution coefficients (K d ) for a select group of trace organic compounds (TOrCs) in anaerobic, anoxic, and aerobic activated sludge collected from two different biological nutrient removal (BNR) treatment systems located in Nevada (NV) and Ohio (OH) in the United States (US). The NV and OH facilities operated at solids retention times (SRTs) of 8 and 23 days, respectively. Using microwave-assisted extraction, the biotransformation rates of the chosen TOrCs were measured in the total mixed liquor. Sulfamethoxazole, trimethoprim, and atenolol biotransformed in all three redox regimes irrespective of the activated sludge source. The biotransformation of N, N-diethyl-3-methylbenzamide (DEET), triclosan, and benzotriazole was observed in aerobic activated sludge from both treatment plants; however, anoxic biotransformation of these three compounds was seen only in anoxic activated sludge from NV. Carbamazepine was recalcitrant in all three redox regimes and both sources of activated sludge. Atenolol and DEET had greater biotransformation rates in activated sludge with a higher SRT (23 days), while trimethoprim had a higher biotransformation rate in activated sludge with a lower SRT (8 days). The remaining compounds did not show any dependence on SRT. Lyophilized, heat inactivated sludge solids were used to determine the sorption-distribution coefficients. Triclosan was the most sorptive compound followed by carbamazepine, sulfamethoxazole, DEET, and benzotriazole. The sorption-distribution coefficients were similar across redox conditions and sludge sources. The biotransformation rates and sorption-distribution coefficients determined in this study can be used to improve fate prediction of the target TOrCs in BNR treatment systems. Copyright © 2018. Published by Elsevier B.V.

Sorption of albendazole in sediments and soils: Isotherms and kinetics.

PubMed

Mutavdžić Pavlović, Dragana; Glavač, Antonija; Gluhak, Mihaela; Runje, Mislav

2018-02-01

Albendazole is a broad-spectrum anthelmintic drug effective against gastrointestinal parasites in humans and animals. Despite the fact that it has been detected in environment (water, sediment and soil), there is no information on its fate in the environment. So, in order to understand the sorption process of albendazole in environment, the sorption mechanism and kinetic properties were investigated through sorption equilibrium and sorption rate experiments. For that purpose, batch sorption of albendazole on five sediment samples and five soil samples from Croatia's region with different physico-chemical properties was investigated. Except physico-chemical properties of used environmental solid samples, the effects of various parameters such as contact time, initial concentration, ionic strength and pH on the albendazole sorption were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Langmuir sorption models were applied to describe the equilibrium isotherms. The estimated K d values varied from 29.438 to 104.43 mLg -1 at 0.01 M CaCl 2 and for natural pH value of albendazole solution (pH 6.6). Experimental data showed that the best agreement was obtained with the linear model (R 2  > 0.99), while the rate of albendazole sorption is the best described with the kinetic model of pseudo-second-order. Obtained results point to a medium or even strong sorption of albendazole for soil or sediment particles, which is particularly dependent on the proportion of organic matter, pH, copper and zinc in them. Copyright © 2017 Elsevier Ltd. All rights reserved.

Welded tuff porosity characterization using mercury intrusion, nitrogen and ethylene glycol monoethyl ether sorption and epifluorescence microscopy

USGS Publications Warehouse

Reddy, M.M.; Claassen, H.C.; Rutherford, D.W.; Chiou, C.T.

1994-01-01

Porosity of welded tuff from Snowshoe Mountain, Colorado, was characterized by mercury intrusion porosimetry (MIP), nitrogen sorption porosimetry, ethylene glycol monoethyl ether (EGME) gas phase sorption and epifluorescence optical microscopy. Crushed tuff of two particle-size fractions (1-0.3 mm and less than 0.212 mm), sawed sections of whole rock and crushed tuff that had been reacted with 0.1 N hydrochloric acid were examined. Average MIP pore diameter values were in the range of 0.01-0.02??m. Intrusion volume was greatest for tuff reacted with 0.1 N hydrochloric acid and least for sawed tuff. Cut rock had the smallest porosity (4.72%) and crushed tuff reacted in hydrochloric acid had the largest porosity (6.56%). Mean pore diameters from nitrogen sorption measurements were 0.0075-0.0187 ??m. Nitrogen adsorption pore volumes (from 0.005 to 0.013 cm3/g) and porosity values (from 1.34 to 3.21%) were less than the corresponding values obtained by MIP. More than half of the total tuff pore volume was associated with pore diameters < 0.05??m. Vapor sorption of EGME demonstrated that tuff pores contain a clay-like material. Epifluorescence microscopy indicated that connected porosity is heterogeneously distributed within the tuff matix; mineral grains had little porosity. Tuff porosity may have important consequences for contaminant disposal in this host rock. ?? 1994.

Sorption of Lincomycin by Manure-Derived Biochars from Water

PubMed Central

Liu, Cheng-Hua; Chuang, Ya-Hui; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.; Gonzalez, Javier M.; Johnston, Cliff T.; Lehmann, Johannes; Zhang, Wei

2018-01-01

The presence of antibiotics in agroecosystems raises concerns about the proliferation of antibiotic-resistant bacteria and adverse effects to human health. Soil amendment with biochars pyrolized from manures may be a win-win strategy for novel manure management and antibiotics abatement. In this study, lincomycin sorption by manure-derived biochars was examined using batch sorption experiments. Lincomycin sorption was characterized by two-stage kinetics with fast sorption reaching quasi-equilibrium in the first 2 d, followed by slow sorption over 180 d. The fast sorption was primarily attributed to surface adsorption, whereas the long-term slow sorption was controlled by slow diffusion of lincomycin into biochar pore structures. Two-day sorption experiments were performed to explore effects of biochar particle size, solid/water ratio, solution pH, and ionic strength. Lincomycin sorption to biochars was greater at solution pH 6.0 to 7.5 below the dissociation constant of lincomycin (7.6) than at pH 9.9 to 10.4 above its dissociation constant. The enhanced lincomycin sorption at lower pH likely resulted from electrostatic attraction between the positively charged lincomycin and the negatively charged biochar surfaces. This was corroborated by the observation that lincomycin sorption decreased with increasing ionic strength at lower pH (6.7) but remained constant at higher pH (10). The long-term lincomycin sequestration by biochars was largely due to pore diffusion plausibly independent of solution pH and ionic composition. Therefore, manure-derived biochars had lasting lincomycin sequestration capacity, implying that biochar soil amendment could significantly affect the distribution, transport, and bioavailability of lincomycin in agroecosystems. PMID:27065399

Sorption of metals on humic acid

NASA Astrophysics Data System (ADS)

Kerndorff, H.; Schnitzer, M.

1980-11-01

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg≫ Fe≫ Pb≫ CuAl ≫ Ni ≫ CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO 2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation Y = 100/[1 + exp - (A + BX)], where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.

Residual methyl methacrylate monomer, water sorption, and water solubility of hypoallergenic denture base materials.

PubMed

Pfeiffer, Peter; Rosenbauer, Ernst-Ulrich

2004-07-01

Denture base materials have the potential to cause irritation and allergic reaction to the oral mucosa. Water sorption and water solubility of denture base resins affect dimensional behavior and denture stability. A correlation between residual monomer and water sorption exists. This in vitro study compared the amount of residual monomer, quantity of water sorption, and solubility of 4 denture base materials purported to be hypoallergenic with those of a polymethyl methacrylate-based (PMMA) heat-polymerizing acrylic resin. The denture base resins Sinomer (heat-polymerized, modified methacrylate), Polyan (thermoplastic, modified methacrylate), Promysan (thermoplastic, enterephthalate-based), and Microbase (microwave polymerized, polyurethane-based), which are purported to be hypoallergenic, and Paladon 65 (heat-polymerized, methacrylate, control group) were examined. Specimens of each material were tested for residual methyl methacrylate (MMA) monomer (% wt, n=3), amount of water sorption (microg/mm3, n=5) and water solubility (microg/mm3, n=5), according to ISO 1567:2000. The residual MMA monomer concentrations were determined by gas chromatography (GC). The data were analyzed with 1-way ANOVA and the Bonferroni-Dunn multiple comparisons post hoc analysis for each test variable (alpha=.05). Significantly lower residual MMA monomer was shown for Sinomer and Polyan compared to the PMMA control group (0.90 +/- 0.20% wt, P<.05). Sinomer contained 0.31% +/- 0.00% wt MMA monomer, and Polyan exhibited residual MMA monomer content of 0.44% +/- 0.01% wt. Promysan and Microbase did not contain detectable residual MMA. Water sorption of Promysan (16.21 +/- 0.96 microg/mm3) was significantly lower than Paladon 65 (23.04 +/- 3.13 microg/mm3, P<.0001), whereas water solubility of the hypoallergenic denture base materials (0.34-0.84 +/- 0.05-0.09 microg/mm3) was not significantly lower than the PMMA material (0.40 +/- 0.06 microg/mm3, P>.05). Except for Sinomer, the tested

Polyacrylamide sorption opportunity on interlayer and external pore surfaces of contaminant barrier clays.

PubMed

Inyang, Hilary I; Bae, Sunyoung

2005-01-01

Physico-chemical interactions among polymer molecules in aqueous solution and clay mineralogical/textural characteristics influence the sorption of polymer molecules on clay barrier minerals. Amendment of potentially unstable barrier clays with aqueous polymers can improve barrier material resistance to environmental stresses during service. In this research, the ability of molecular coils of polyacrylamide (PAM) to overlap in solution and to enter interlayer space in Na-montmorillonite (specific surface=31.82+/-0.22 m2 g(-1)) and kaolinite (specific surface=18+/-2 m2 g(-1)) were analyzed theoretically and experimentally, using solution viscosity measurements, and X-ray diffractometry. Experimental data on two theoretical indices: relative size ratio (RSR); and molecular availability (Ma) that are formulated to scale polymer molecular sorption on clay interlayer, indicate that the sorption of PAM A (Mw=4000000) and PAM B (Mw=7000000) does not produce any significant change in the d-spacing of both clay minerals. Although the negative Ma values of -3.51 g l(-1) for PAM A and -3.88 g l(-1) for PAM B indicate high levels of entanglement of polymer molecular coils in solution, sorption data confirm that the entangled coils are still able to sorb onto Na-montmorillonite highly and kaolinite to a lesser extent.

Material Demand Studies: Materials Sorption of Vaporized Hydrogen Peroxide

DTIC Science & Technology

2010-06-01

SORPTION OF VAPORIZED HYDROGEN PEROXIDE Lawrence R. Procell Zoe A. Hess David G. Gehring Joseph T. Lynn Philip W. Bartram Teri Lalain RESEARCH AND...2010 2. REPORT TYPE Final 3. DATES COVERED (From - To) Nov 2003 - Jul 2005 4. TITLE AND SUBTITLE Material Demand Studies: Materials Sorption of...of office surfaces 33 \\i MATERIAL DEMAND STUDIES: MATERIALS SORPTION OF VAPORIZED HYDROGEN PEROXIDE 1. BACKGROUND The Material Demand effort was

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

PubMed Central

Wilson, Lee D.; Mohamed, Mohamed H.; Berhaut, Christopher L.

2011-01-01

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X copolymers (< 101 m2/g), and granular activated carbon (GAC ~103 m2/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material. PMID:28824156

Mechanistic understanding of tetracycline sorption on waste tire powder and its chars as affected by Cu(2+) and pH.

PubMed

Lian, Fei; Song, Zhengguo; Liu, Zhongqi; Zhu, Lingyan; Xing, Baoshan

2013-07-01

The sorption characteristics of tetracycline (TC) by waste tire powder and its chars were investigated to explore the potential of using waste tires as effective sorbents for removal of TC from aqueous solution. Naphthalene (NAPH), a typical hydrophobic organic compound, was selected as asorbate for comparison. TC displayed much lower sorption affinity to tire powder than NAPH. However, it exhibited similar adsorption affinity as NAPH on the pyrolyzed tire chars, which was mainly attributed to π-π electron-donor-acceptor interactions of TC with the graphite surface of chars. TC and Cu(2+) could mutually facilitate the sorption of each other on both tire powder and pyrolyzed chars in a wide pH range. This could be explained by the metallic complexation and/or surface-bridging mechanisms (i.e., Cu- or TC-bridging). However, Cu(2+) and NAPH depressed the sorption of each other on tire powder and displayed negligible impact to each other on the highly pyrolyzed chars. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sorption and Transport of Sildenafil in Natural Soils

NASA Astrophysics Data System (ADS)

Boudinot, F. G.; Vulava, V. M.

2013-12-01

Pharmaceutical Chemicals (PCs) mainly enter our ecosystems from discharges of treated wastewater and have direct effects on the ecological health of that area. Sildenafil citrate (Viagra) is one such PC, whose presence has been reported in stream waters. Although one study has shown that sildenafil is not harmful in bacterial and fungal environments, there remains much unknown about its fate elsewhere in ecosystems. Sildenafil is a complex organic molecule with two amino functional groups that result in pKa's of 7.27 and 5.97. It also has a high solubility of 3.5 g/L. Given that sildenafil consumption (and concurrently disposal) is on the rise, it is essential that its behavior in the natural environment be better understood. The goal of this study was to quantify the sorption and transport behavior of sildenafil in differing natural soils with varying compositions. Pristine A- and B- horizon soil samples from several soil series were collected in a managed forest near Charleston, SC and used for these studies. The soils were characterized for physical and chemical properties: soil organic matter content ranged between 0.6-7.6%, clay content between 6-20%, and soil pH between 4-5. These soils were then used to perform kinetic reaction, sorption, and column transport experiments. Batch kinetic experiments showed a fast reaction rate in both clay-rich and organic-rich soils and an equilibration time of less than 24 hours. Batch reactor sorption experiments provided data for sorption isotherms (plot of sildenafil in solution, C vs. sildenafil sorbed in soil, q) which were nonlinear. The isotherms were fit using Freundlich model (q=KfCn, where Kf and n are fitting parameters). Sildenafil sorbed more strongly to clay-rich soils compared with organic-rich soils with less clay. It is hypothesized that permanent negative charge on clay mineral surfaces form ionic bonds with positively charged amines in sildenafil in acidic pHs. Transport experiments were conducted using

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality.

PubMed

Amstaetter, Katja; Eek, Espen; Cornelissen, Gerard

2012-04-01

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N(2) and CO(2) adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15Šthan the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources. Copyright © 2012 Elsevier Ltd. All rights reserved.

Status Of Sorption Cryogenic Refrigeration

NASA Technical Reports Server (NTRS)

Jones, Jack A.

1988-01-01

Report reviews sorption refrigeration. Developed for cooling infrared detectors, cryogenic research, and other advanced applications, sorption refrigerators have few moving parts, little vibration, and lifetimes of 10 years or more. Describes types of sorption stages, multistage and hybrid refrigeration systems, power requirements, cooling capacities, and advantages and disadvantages of various stages and systems.

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.

The sorption of silver by poorly crystallized manganese oxides

USGS Publications Warehouse

Anderson, B.J.; Jenne, E.A.; Chao, T.T.

1973-01-01

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized ??-MnO2. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnOx at pH 7) while the ??-MnO2 showed the least (0.3 moles silver/ mole MnOx at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium. ?? 1973.

Sorption behaviour of perfluoroalkyl substances in soils.

PubMed

Milinovic, Jelena; Lacorte, Silvia; Vidal, Miquel; Rigol, Anna

2015-04-01

The sorption behaviour of three perfluoroalkyl substances (PFASs), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS), was studied in six soils with contrasting characteristics, especially in the organic carbon content. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions spiked with increasing concentrations of the target PFAS. The sorption reversibility of PFASs was also tested for some of the samples. Liquid chromatography coupled to tandem mass spectrometry was used to quantify the target PFASs in the solutions. Both the Freundlich and linear models were appropriate to describe the sorption behaviour of PFASs in soils, and enabled us to derive solid-liquid distribution coefficients (Kd) for each compound in each soil. Kd values increased from 19 to 295 mL g(-1) for PFOS, from 2.2 to 38 mL g(-1) for PFOA and from 0.4 to 6.8 mL g(-1) for PFBS, and were positively correlated with the organic carbon content of the soil. KOC values obtained from the correlations were 710, 96 and 17 mL g(-1) for PFOS, PFOA and PFBS, respectively. Whereas Kd values decreased in the sequence PFOS>PFOA>PFBS, desorption yields were lower than 13% for PFOS, from 24 to 58% for PFOA, and from 32 to 60% for PFBS. This shows that the physicochemical characteristics of PFASs, basically their hydrophobicity, controlled their sorption behaviour in soils, with PFOS being the most irreversibly sorbed PFAS. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of the atrazine sorption process on Andisol and Ultisol volcanic ash-derived soils: kinetic parameters and the contribution of humic fractions.

PubMed

Báez, María E; Fuentes, Edwar; Espinoza, Jeannette

2013-07-03

Atrazine sorption was studied in six Andisol and Ultisol soils. Humic and fulvic acids and humin contributions were established. Sorption on soils was well described by the Freundlich model. Kf values ranged from 2.2-15.6 μg(1-1/n)mL(1/n)g⁻¹. The relevance of humic acid and humin was deduced from isotherm and kinetics experiments. KOC values varied between 221 and 679 mLg⁻¹ for these fractions. Fulvic acid presented low binding capacity. Sorption was controlled by instantaneous equilibrium followed by a time-dependent phase. The Elovich equation, intraparticle diffusion model, and a two-site nonequilibrium model allowed us to conclude that (i) there are two rate-limited phases in Andisols related to intrasorbent diffusion in organic matter and retarded intraparticle diffusion in the organo-mineral complex and that (ii) there is one rate-limited phase in Ultisols attributed to the mineral composition. The lower organic matter content of Ultisols and the slower sorption rate and mechanisms involved must be considered to assess the leaching behavior of atrazine.

Sorption of hydrogen by silica aerogel at low-temperatures

NASA Astrophysics Data System (ADS)

Dolbin, A. V.; Khlistyuck, M. V.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Martsenuk, V. E.; Veselova, N. V.; Kaliuzhnyi, I. A.; Storozhko, A. V.

2018-02-01

The programmed thermal desorption method is used at temperatures of 7-95 K to study the sorption and subsequent desorption of hydrogen by a sample of silica aerogel. Physical sorption of hydrogen owing to the weak van-der-Waals interaction of hydrogen molecules with the silicon dioxide walls of the pores of the sample was observed over the entire temperature range. The total capacity of the aerogel sample for hydrogen was ˜1.5 mass %. It was found that when the sample temperature was lowered from 95 to 60 K, the characteristic sorption times for hydrogen by the silica aerogel increase; this is typical of thermally activated diffusion (Ea ≈ 408 K). For temperatures of 15-45 K the characteristic H2 sorption times depended weakly on temperature, presumably because of the predominance of a tunnel mechanism for diffusion over thermally activated diffusion. Below 15 K the characteristic sorption times increase somewhat as the temperature is lowered; this may be explained by the formation of a monolayer of H2 molecules on the surface of the aerogel grains.

Evidence of micropore filling for sorption of nonpolar organic contaminants by condensed organic matter.

PubMed

Ran, Yong; Yang, Yu; Xing, Baoshan; Pignatello, Joseph J; Kwon, Seokjoo; Su, Wei; Zhou, Li

2013-01-01

Although microporosity and surface area of natural organic matter (NOM) are crucial for mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have been underestimated by the N adsorption technique. We investigated the CO-derived internal hydrophobic microporosity () and specific surface area (SSA) obtained on dry samples and related them to sorption behaviors of NOCs in water for a wide range of condensed NOM samples. The is obtained from the total CO-derived microporosity by subtracting out the contribution of the outer surfaces of minerals and NOM using N adsorption-derived parameters. The correlation between or CO-SSA and fractional organic carbon content () is very significant, demonstrating that much of the microporosity is associated with internal NOM matrices. The average and CO-SSA are, respectively, 75.1 μL g organic carbon (OC) and 185 m g OC from the correlation analysis. The rigid aliphatic carbon significantly contributes to the microporosity of the Pahokee peat. A strong linear correlation is demonstrated between / and the OC-normalized sorption capacity at the liquid or subcooled liquid-state water solubility calculated via the Freundlich equation for each of four NOCs (phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,2-dichlorobenzene). We concluded that micropore filling ("adsorption") contributes to NOC sorption by condensed NOM, but the exact contribution requires knowing the relationship between the dry-state, CO-determined microporosity and the wet-state, NOC-available microporosity of the organic matter. The findings offer new clues for explaining the nonideal sorption behaviors of NOCs. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Sorption of agrochemical model compounds by sorbent materials containing beta-cyclodextrin.

PubMed

Wilson, Lee D; Mohamed, Mohamed H; Guo, Rui; Pratt, Dawn Y; Kwon, Jae Hyuck; Mahmud, Sarker T

2010-04-01

Polymeric sorbent materials that incorporate beta-cyclodextrin (CD) have been prepared and their sorption behavior toward two model agrochemical contaminant compounds, p-nitrophenol (PNP) and methyl chloride examined. The sorption of PNP was studied in aqueous solution using ultraviolet-visible (UV-Vis) spectroscopy, whereas the sorption of methyl chloride from the gas phase was studied using a Langmuir adsorption method. The sorption results for PNP in solution were compared between granular activated carbon (GAC), modified GAC, CD copolymers, and CD-based mesoporous silica hybrid materials. Nitrogen porosimetry at 77 K was used to estimate the surface area and pore structure properties of the sorbent materials. The sorbents displayed variable surface areas as follows: copolymers (36.2-157 m(2)/g), CD-silica materials (307-906 m(2)/g), surface modified GAC (657 m(2)/g), and granular activated carbon (approximately 10(3) m(2)/g). The sorption capacities for PNP and methyl chloride with the different sorbents are listed in descending order as follows: GAC > copolymers > surface modified GAC > CD-silica hybrid materials. In general, the differences in the sorption properties of the sorbents were related to the following: (i) surface area of the sorbent, (ii) CD content and accessibility, (iii) and the chemical nature of the sorbent material.

Investigation of metal ions sorption of brown peat moss powder

NASA Astrophysics Data System (ADS)

Kelus, Nadezhda; Blokhina, Elena; Novikov, Dmitry; Novikova, Yaroslavna; Chuchalin, Vladimir

2017-11-01

For regularities research of sorptive extraction of heavy metal ions by cellulose and its derivates from aquatic solution of electrolytes it is necessary to find possible mechanism of sorption process and to choice a model describing this process. The present article investigates the regularities of aliovalent metals sorption on brown peat moss powder. The results show that sorption isotherm of Al3+ ions is described by Freundlich isotherm and sorption isotherms of Na+ i Ni2+ are described by Langmuir isotherm. To identify the mechanisms of brown peat moss powder sorption the IR-spectra of the initial brown peat moss powder samples and brown peat moss powder samples after Ni (II) sorption were studied. Metal ion binding mechanisms by brown peat moss powder points to ion exchange, physical adsorption, and complex formation with hydroxyl and carboxyl groups.

Sorption of imazaquin in soils with positive balance of charges.

PubMed

Rocha, Wadson S D; Regitano, Jussara B; Alleoni, Luis R F; Tornisielo, Valdemar L

2002-10-01

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.

Estimating the sorption of pharmaceuticals based on their pharmacological distribution.

PubMed

Williams, Mike; Ong, Poh L; Williams, Desmond B; Kookana, Rai S

2009-12-01

Pharmaceuticals released into aquatic systems are expected to sorb to sediments to varying degrees. Their sorption is likely to influence their fate and, ultimately, the risk they pose to aquatic organisms. This has led to the European Medicines Agency requiring an assessment of affinity to solids, using batch sorption methods, for the environmental risk assessment (ERA) of new human medicines. However, a large body of data is generated before pharmaceuticals are released onto the market, including their extent of distribution throughout the human body, measured by the volume of distribution (VD). In the present study, batch sorption experiments were undertaken using 12 different soils and sediments to determine whether VD was a good indicator of experimental Kd values for 21 pharmaceuticals. The r2 values obtained from the regressions ranged from 0.39 to 0.76 (with a median value of 0.5) and all regressions were found to be significant. The use of this more comprehensive set of soils and sediments was consistent with previous studies comparing VD and Kd, despite the Kd values of the selected pharmaceuticals varying greatly between soils. The relationship between Kd and VD was greatly improved when zwitterionic antibiotics and carbamazepine were not included, possibly due to complex sorption or pharmacokinetic behavior. There are likely to be a number of factors affecting the sorption of pharmaceuticals that cannot be explained by VD. However, further work may elucidate how these factors can be accounted for, enabling VD to be effectively used to facilitate the ERA of human pharmaceuticals with already available information.

Macroscopic and spectroscopic investigations on Eu(III) and Cm(III) sorption onto bayerite (β-Al(OH)3) and corundum (α-Al2O3).

PubMed

Kupcik, Tomas; Rabung, Thomas; Lützenkirchen, Johannes; Finck, Nicolas; Geckeis, Horst; Fanghänel, Thomas

2016-01-01

The interaction of trivalent Cm and Eu with the aluminum hydroxide bayerite (β-Al(OH)3) and the aluminum oxide corundum (α-Al2O3) was investigated by batch sorption experiments and time resolved laser fluorescence spectroscopy (TRLFS). The experimental methods for both polymorphs show similar pH dependent sorption behavior at trace metal ion concentrations (∼10(-7) M), i.e. similar Eu sorption edges and nearly identical Cm speciation between pH=3 and 13. In this pH range the Cm aquo ion as well as the Cm(III) surface species surface⋯Cm(OH)x(H2O)(5-x) (x=0, 1, 2) can be distinguished by TRLFS. The similar sorption data point to a (surface) transformation of the thermodynamically unstable Al2O3 surface into bayerite, in agreement with the similar isoelectric points obtained for both minerals (pH(IEP)=8.6-8.8). The pH dependent surface charge is most likely due to the protonation/deprotonation of singly coordinated Al-OH surface groups, prevailing on the edge planes of the rod-like bayerite crystals and the surface of the colloidal Al2O3 particles. These surface groups are also believed to act as ligands for lanthanide/actinide(III) surface complexation. In contrast to the similar sorption behavior at trace metal ion concentrations, discrepancies are observed at higher Eu levels. While similar sorption edges occur up to 7×10(-7) M Eu for corundum, the pH edge on bayerite is gradually shifted to higher pH values in this Eu concentration range. The latter behavior may be related either to the existence of multiple sorption sites with different sorption affinities, or to the influence of an additional amorphous Al-phase, forming in the course of the bayerite synthesis. Copyright © 2015 Elsevier Inc. All rights reserved.

Sorption of Eu(III) on attapulgite studied by batch, XPS, and EXAFS techniques.

PubMed

Fan, Q H; Tan, X L; Li, J X; Wang, X K; Wu, W S; Montavon, G

2009-08-01

The effects of pH, ionic strength, and temperature on sorption of Eu(III) on attapulgite were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The results indicated that the sorption of Eu(III) on attapulgite was strongly dependent on pH and ionic strength, and independent of temperature. In the presence of FA/HA, Eu(III) sorption was enhanced at pH < 4, decreased at pH range of 4-6, and then increased again at pH > 7. The X-ray photoelectron spectroscopy (XPS) analysis suggested that the sorption of Eu(III) might be expressed as is identical to X3Eu0, is identical to S(w)OHEu3+, and is identical to SOEu-OOC-/HA in the ternary Eu/HN/attapulgite system. The extended X-ray absorption fine structure (EXAFS) analysis of Eu-HA complexes indicated that the distances of d(Eu-O) decreased from 2.415 to 2.360 angstroms with increasing pH from 1.76 to 9.50, whereas the coordination number (N) decreased from approximately 9.94 to approximately 8.56. Different complexation species were also found for the different addition sequences of HA and Eu(III) to attapulgite suspension. The results are important to understand the influence of humic substances on Eu(III) behavior in the natural environment.

Cadmium sorption and extractability in tropical soils with variable charge.

PubMed

Colzato, Marina; Alleoni, Luís Reynaldo Ferracciú; Kamogawa, Marcos Yassuo

2018-05-14

The availability of cadmium (Cd) for plants and its impact in the environment depends on Cd sorption in soil colloids. The study of Cd sorption in soil and its fractionation is an interesting tool for the evaluation of Cd affinity with soil pools. The objective with this study was to evaluate Cd sorption and desorption in tropical soils with variable charge (three Oxisols), in a Mollisol and in two Entisols with diverse physical, chemical, and mineralogical attributes. We used a thermodynamic approach to evaluate Cd sorption and performed a chemical fractionation of Cd in the six soils. Data from Cd sorption fit the Langmuir model (r > 0.94), and the sorption capacity ranged from 0.33 to 11.5 mmol kg -1 . The Gibbs standard free energy was positively correlated to Cd sorption capacity (r = 0.74, except for the Quartzipsamments), and it was more favorable in soils with great sorption capacity. Distribution of Cd among fractions was not affected (t test, α = 0.05) by initial concentration, and there was a predominance of Cd extractable in 0.1 mol L -1 CaCl 2 .

Moisture sorption isotherms and thermodynamic properties of bovine leather

NASA Astrophysics Data System (ADS)

Fakhfakh, Rihab; Mihoubi, Daoued; Kechaou, Nabil

2018-04-01

This study was aimed at the determination of bovine leather moisture sorption characteristics using a static gravimetric method at 30, 40, 50, 60 and 70 °C. The curves exhibit type II behaviour according to the BET classification. The sorption isotherms fitting by seven equations shows that GAB model is able to reproduce the equilibrium moisture content evolution with water activity for moisture range varying from 0.02 to 0.83 kg/kg d.b (0.9898 < R2 < 0.999). The sorption isotherms exhibit hysteresis effect. Additionally, sorption isotherms data were used to determine the thermodynamic properties such as isosteric heat of sorption, sorption entropy, spreading pressure, net integral enthalpy and entropy. Net isosteric heat of sorption and differential entropy were evaluated through direct use of moisture isotherms by applying the Clausius-Clapeyron equation and used to investigate the enthalpy-entropy compensation theory. Both sorption enthalpy and entropy for desorption increase to a maximum with increasing moisture content, and then decrease sharply with rising moisture content. Adsorption enthalpy decreases with increasing moisture content. Whereas, adsorption entropy increases smoothly with increasing moisture content to a maximum of 6.29 J/K.mol. Spreading pressure increases with rising water activity. The net integral enthalpy seemed to decrease and then increase to become asymptotic. The net integral entropy decreased with moisture content increase.

Partially-irreversible sorption of formaldehyde in five polymers

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Sorption equilibrium of mercury onto ground-up tree fern.

PubMed

Ho, Yuh-Shan; Wang, Chung-Chi

2008-08-15

The sorption behavior of mercury at different temperatures onto ground-up tree fern was investigated. The experimental results were fitted to two two-parameter isotherms, the Freundlich and Langmuir isotherms, as well as to two three-parameter isotherms, the Redlich-Peterson and Sips isotherms to obtain the characteristic parameters of each model. A comparison of best-fitting was performed using the coefficient of determination and Chi-square test. Both the Langmuir and Redlich-Peterson isotherms were found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of mercury ions onto ground-up tree fern was 26.5 mg/g at 298 K. It was noted that an increase in temperature resulted in a higher mercury ion loading per unit weight of the tree fern. In addition, various thermodynamic parameters, such as DeltaG degrees, DeltaH degrees, and DeltaS degrees, were calculated and compared with the sorption of mercury by other sorbents.

Continuous measurements of N2O emissions from arable fields

NASA Astrophysics Data System (ADS)

Wallman, Magdalena; Lammirato, Carlo; Rütting, Tobias; Delin, Sofia; Weslien, Per; Klemedtsson, Leif

2017-04-01

Agriculture represents 59 % of the anthropogenic nitrous oxide (N2O) emissions, according to the IPCC (Ciais et al. 2013). N2O emissions are typically irregular and vary widely in time and space, which makes it difficult to get a good representation of the emissions (Henault et al. 2012), particularly if measurements have low frequency and/or cover only a short time period. Manual measurements are, for practical reasons, often short-term and low-frequent, or restricted to periods where emissions are expected to be high, e.g. after fertilizing. However, the nature of N2O emissions, being largely unpredictable, calls for continuous or near-continuous measurements over long time periods. So far, rather few long-term, high resolution measurements of N2O emissions from arable fields are reported; among them are Flessa et al. (2002) and Senapati et al. (2016). In this study, we have a two-year data set (2015-2017) with hourly measurements from ten automatic chambers, covering unfertilized controls as well as different nitrogen fertilizer treatments. Grain was produced on the field, and effects of tillage, harvest and other cropping measures were covered. What we can see from the experiment is that (a) the unfertilized control plots seem to follow the same emission pattern as the fertilized plots, at a level similar to the standard mineral fertilized plots (120 kg N ha-1 yr-1) and (b) freeze/thaw emissions are comparable in size to emissions after fertilizing. These two findings imply that the importance of fertilizing to the overall N2O emissions from arable soils may be smaller than previously expected. References: Ciais, P., C. Sabine, G. Bala, L. Bopp, V. Brovkin, J. Canadell et al. 2013: Carbon and Other Biogeochemical Cycles. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung et

Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption.

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

Kinetic characteristic of phenanthrene sorption in aged soil amended with biochar

NASA Astrophysics Data System (ADS)

Kim, Chanyang; Kim, Yong-Seong; Hyun, Seunghun

2015-04-01

Biochar has been recently highlighted as an amendment that affects yield of the crops by increasing pH, cation exchange capacity and water retention, and reduces the lability of contaminants by increasing sorption capacity in the soil system. Biochar's physico-chemical properties, high CEC, surfaces containing abundant micropores and macropores, and various types of functional groups, play important roles in enhancing sorption capacity of contaminants. Aging through a natural weathering process might change physico-chemical properties of biochar amended in soils, which can affect the sorption behavior of contaminants. Thus, in this study, the sorption characteristics of phenanthrene (PHE) on biochar-amended soils were studied with various types of chars depending on aging time. To do this, 1) soil was amended with sludge waste char (SWC), wood char (WC), and municipal waste char (MWC) during 0, 6, and 12 month. Chars were applied to soil at 1% and 2.5% (w/w) ratio. 2) Several batch kinetic and equilibrium studies were conducted. One-compartment first order and two-compartment first order model apportioning the fraction of fast and slow sorbing were selected for kinetic models. Where, qt is PHE concentration in biochar-amended soils at each time t, qeis PHE concentration in biochar-amended soils at equilibrium. ff is fastly sorbing fraction and (1-ff) is slowly sorbing fraction. k is sorption rate constant from one-compartment first order model, k1 and k2 are sorption rate constant from two-compartment first order model, t is time (hr). The equilibrium sorption data were fitted with Fruendlich and Langmuir equation. 3) Change in physico-chemical properties of biochar-amended soils was investigated with aging time. Batch equilibrium sorption results suggested that sorbed amount of PHE on WC was greater than SWC and MWC. The more char contents added to soil, the greater sorption capacity of PHE. Sorption equilibrium was reached after 4 hours and equilibrium pH ranged

LEAD SORPTION ON RUTHENIUM OXIDE: A MACROSCOPIC AND SPECTROSCOPIC STUDY

EPA Science Inventory

The sorption and desorption of Pb on RuO2 xH2O were examined kinetically and thermodynamically via spectroscopic and macroscopic investigations. X-ray absorption spectroscopy (XAS) was employed to determine the sorption mechanism with regard to identity of nearest atomic neighbo...

Actinide Sorption in Rainier Mesa Tunnel Waters from the Nevada Test Site

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

Zhao, P; Zavarin, M; Leif, R

2007-12-17

The sorption behavior of americium (Am), plutonium (Pu), neptunium (Np), and uranium (U) in perched Rainier Mesa tunnel water was investigated. Both volcanic zeolitized tuff samples and groundwater samples were collected from Rainier Mesa, Nevada Test Site, NV for a series of batch sorption experiments. Sorption in groundwater with and without the presence of dissolved organic matter (DOM) was investigated. Am(III) and Pu(IV) are more soluble in groundwater that has high concentrations of DOM. The sorption K{sub d} for Am(III) and Pu(IV) on volcanic zeolitized tuff was up to two orders of magnitude lower in samples with high DOM (15more » to 19 mg C/L) compared to samples with DOM removed (< 0.4 mg C/L) or samples with naturally low DOM (0.2 mg C/L). In contrast, Np(V) and U(VI) sorption to zeolitized tuff was much less affected by the presence of DOM. The Np(V) and U(VI) sorption Kds were low under all conditions. Importantly, the DOM was not found to significantly sorb to the zeolitized tuff during these experiment. The concentration of DOM in groundwater affects the transport behavior of actinides in the subsurface. The mobility of Am(III) and Pu(IV) is significantly higher in groundwater with elevated levels of DOM resulting in potentially enhanced transport. To accurately model the transport behavior of actinides in groundwater at Rainier Mesa, the low actinide Kd values measured in groundwater with high DOM concentrations must be incorporated in predictive transport models.« less

Long-term sorption of halogenated organic chemicals by aquifer material. 1. Equilibrium

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

Ball, W.P.; Roberts, P.V.

1991-07-01

The sorption of tetrachloroethene (PCE) and 1,2,4,5-tetrachlorobenzene (TeCB) was studied on sandy aquifer material from Borden, ON, by using a batch methodology designed to accurately measure sorption over long equilibration periods. Autoclaving was effective in inhibiting biotransformation, and use of fire-sealed glass ampules precluded volatilization losses. Data analysis techniques were developed to accurately account for partitioning to sample headspace and other losses. Sorption isotherms for PCE and TeCB with Borden solids deviated from linearity when a 4-5 order of magnitude range in aqueous concentration was considered. However, in the dilute range (<50 {mu}/l), the deviations from linearity were inconsequential. Themore » sorption of TeCB was approximately 40 times stronger than for PCE, in qualitative accordance with TeCB's approximately 100-fold greater octanol-water partitioning coefficient. For a given solute, the distribution coefficients differed by a factor of 30 among the various size fractions, being greatest for the largest grains. For most Borden solids, the long-term sorption of PCE and TeCB exceeded by more than 1 order of magnitude the predictions of generalized correlations based on hydrophobic partitioning into organic matter. This difference is believed to be partially the result of mineral contributions to sorption, but may also reflect unattainment of equilibrium in previously regressed results - in this study, contact times on the order of tens to hundreds of days were required. For Borden solids, pulverization of solid samples was shown to be a viable expedient to obviate the need for excessively long equilibrations.« less

Migration and sorption phenomena in packaged foods.

PubMed

Gnanasekharan, V; Floros, J D

1997-10-01

Rapidly developing analytical capabilities and continuously evolving stringent regulations have made food/package interactions a subject of intense research. This article focuses on: (1) the migration of package components such as oligomers and monomers, processing aids, additives, and residual reactants in to packaged foods, and (2) sorption of food components such as flavors, lipids, and moisture into packages. Principles of diffusion and thermodynamics are utilized to describe the mathematics of migration and sorption. Mathematical models are developed from first principles, and their applicability is illustrated using numerical simulations and published data. Simulations indicate that available models are system (polymer-penetrant) specific. Furthermore, some models best describe the early stages of migration/sorption, whereas others should be used for the late stages of these phenomena. Migration- and/or sorption-related problems with respect to glass, metal, paper-based and polymeric packaging materials are discussed, and their importance is illustrated using published examples. The effects of migrating and absorbed components on food safety, quality, and the environment are presented for various foods and packaging materials. The impact of currently popular packaging techniques such as microwavable, ovenable, and retortable packaging on migration and sorption are discussed with examples. Analytical techniques for investigating migration and sorption phenomena in food packaging are critically reviewed, with special emphasis on the use and characteristics of food-simulating liquids (FSLs). Finally, domestic and international regulations concerning migration in packaged foods, and their impact on food packaging is briefly presented.

Effects of humic acids on the aggregation and sorption of nano-TiO2.

PubMed

Li, Yanjie; Yang, Chen; Guo, Xuetao; Dang, Zhi; Li, Xiaoqin; Zhang, Qian

2015-01-01

In this study, humic acids (HAs) from three sources, peat, sediment and straw, used to coat nano-TiO2 were investigated. The results indicated that HAs isolated from peat were aromatic-rich, whereas those isolated from sediment and straw were aliphatic-rich. The nano-TiO2 sedimentation experiments indicated that the presence of aromatic-rich HAs was more capable of stabilizing nano-TiO2 particles than was the presence of aliphatic-rich HAs. This result is because the deionized phenolic groups in the HAs were preferentially adsorbed on the nano-TiO2 surfaces, which generated a higher charge density on the nano-TiO2 surfaces and caused stronger repulsive forces among particles. Furthermore, the aromatic-rich TiO2-HA complexes exhibited a greater sorption capacity than the aliphatic-rich TiO2-HAs complexes and nonlinear phenanthrene sorption because of their higher affinity and the condensed state of aromatic fractions. Note that natural organic matters, such as humic acids, in aquatic environments can not only increase the stability of nanoparticles but can also influence the mobility of hydrophobic organic compounds (HOCs). Copyright © 2014. Published by Elsevier Ltd.

Effect of Cosolutes on the Sorption of Phenanthrene onto Mineral Surface of River Sediments and Kaolinite

PubMed Central

2014-01-01

Sorption of phenanthrene onto the natural sediment with low organic carbon content (OC%), organic-free sediment, and kaolinite was investigated through isotherm experiments. Effects of cosolutes (pyrene, 4-n-nonyphenol (NP), and humic acid (HA)) on phenanthrene sorption were also studied by comparing apparent solid-water distribution coefficients (K d app) of phenanthrene. Two addition sequences, including “cosolute added prior to phenanthrene” and “cosolute and phenanthrene added simultaneously,” were adopted. The Freundlich model fits phenanthrene sorption on all 3 sorbents well. The sorption coefficients on these sorbents were similar, suggesting that mineral surface plays an important role in the sorption of hydrophobic organic contaminants on low OC% sediments. Cosolutes could affect phenanthrene sorption on the sorbents, which depended on their properties, concentrations, and addition sequences. Pyrene inhibited phenanthrene sorption. Sorbed NP inhibited phenanthrene sorption at low levels and promoted sorption at high levels. Similar to NP, effect of HA on phenanthrene sorption onto the natural sediment depended on its concentrations, whereas, for the organic-free sediment and kaolinite, preloading of HA at high levels led to an enhancement in phenanthrene K d app while no obvious effect was observed at low HA levels; dissolved HA could inhibit phenanthrene sorption on the two sorbents. PMID:25147865

Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.

PubMed

Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A

2007-02-15

Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was <1.5% relative to the solubility in pure water. This decrease of solubility is insufficient to account for the observed increase of sorption by K-smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.

Time-Dependent CO[subscript 2] Sorption Hysteresis in a One-Dimensional Microporous Octahedral Molecular Sieve

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

Espinal, Laura; Wong-Ng, Winnie; Kaduk, James A.

2014-09-24

The development of sorbents for next-generation CO{sub 2} mitigation technologies will require better understanding of CO{sub 2}/sorbent interactions. Among the sorbents under consideration are shape-selective microporous molecular sieves with hierarchical pore morphologies of reduced dimensionality. We have characterized the non-equilibrium CO{sub 2} sorption of OMS-2, a well-known one-dimensional microporous octahedral molecular sieve with manganese oxide framework. Remarkably, we find that the degree of CO{sub 2} sorption hysteresis increases when the gas/sorbent system is allowed to equilibrate for longer times at each pressure step. Density functional theory calculations indicate a 'gate-keeping' role of the cation in the tunnel, only allowing CO{submore » 2} molecules to enter fully into the tunnel via a highly unstable transient state when CO{sub 2} loadings exceed 0.75 mmol/g. The energy barrier associated with the gate-keeping effect suggests an adsorption mechanism in which kinetic trapping of CO{sub 2} is responsible for the observed hysteretic behavior.« less

Impact of Interfacial Roughness on the Sorption Properties of Nanocast Polymers

DOE PAGES

Sridhar, Manasa; Gunugunuri, Krishna R.; Hu, Naiping; ...

2016-03-16

Nanocasting is an emerging method to prepare organic polymers with regular, nanometer pores using inorganic templates. This report assesses the impact of imperfect template replication on the sorption properties of such polymer castings. Existing X-ray diffraction data show that substantial diffuse scattering exists in the small-angle region even though TEM images show near perfect lattices of uniform pores. To assess the origin of the diffuse scattering, the morphology of the phenol - formaldehyde foams (PFF) was investigated by small-angle X-ray scattering (SAXS). The observed diffuse scattering is attributed to interfacial roughness due to fractal structures. Such roughness has a profoundmore » impact on the sorption properties. Conventional pore- filling models, for example, overestimate protein sorption capacity. A mathematical framework is presented to calculate sorption properties based on observed morphological parameters. The formalism uses the surface fractal dimension determined by SAXS in conjunction with nitrogen adsorption isotherms to predict lysozyme sorption. The results are consistent with measured lysozyme loading.« less

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

PubMed

Wilson, Lee D; Mohamed, Mohamed H; Berhaut, Christopher L

2011-08-29

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 10¹ m²/g), CDI-X copolymers (< 10¹ m²/g), and granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Metsulfuron-methyl sorption/desorption behavior on volcanic ash-derived soils. effect of phosphate and pH.

PubMed

Cáceres, Lizethly; Fuentes, Roxana; Escudey, Mauricio; Fuentes, Edwar; Báez, María E

2010-06-09

Metsulfuron-methyl sorption/desorption behavior was studied through batch sorption experiments in three typical volcanic ash-derived soils belonging to Andisol and Ultisol orders. Their distinctive physical and chemical properties are acidic pH and variable surface charge. Organic matter content and mineral composition affected in different ways sorption of metsulfuron-methyl (K(OC) ranging from 113 to 646 mL g(-1)): organic matter and iron and aluminum oxides mainly through hydrophilic rather than hydrophobic interactions in Andisols, and Kaolinite group minerals, as major constituents of Ultisols, and iron and aluminum oxides only through hydrophilic interactions. The Freundlich model described metsulfuron-methyl behavior in all cases (R(2) > 0.992). K(f) values (3.1-14.4 microg(1-1/n) mL(1/n) g(-1)) were higher than those reported for different class of soils including some with variable charge. Hysteresis was more significant in Ultisols. A strong influence of pH and phosphate was established for both kinds of soil, intensive soil fertilization and liming being the most probable scenario for leaching of metsulfuron-methyl, particularly in Ultisols.

Sorption of sulphamethoxazole by the biochars derived from rice straw and alligator flag.

PubMed

Li, Tingqiang; Han, Xuan; Liang, Chengfeng; Shohag, M J I; Yang, Xiaoe

2015-01-01

The sorption ability of sulphamethoxazole (SMX) by biochar derived from rice straw (RS) and alligator flag (AF) at 600°C was studied to assess the ability of biochar as adsorbent to remove SMX from aqueous solution. The results indicated that sorption of SMX by biochars was well described using the Langmuir equation (R2>0.94), and the maximum sorption parameter (Q) of RS (3650 mg kg(-1)) was much higher than that of AF (1963 mg kg(-1)). Temperature had no effect on SMX sorption by biochars, while thermodynamics analysis indicated that the sorption of SMX on both biochars was a spontaneous physical process. The d 250 RS (diameter of RS sieved through 250 µm) and d 150 AF (diameter of AF sieved through 150 µm) showed excellent sorption ability for SMX. The sorption amount of RS was larger than that of AF when pH<7, whereas, the sorption amount of AF surpassed RS when pH≥7. The presence of Cu2+ and/or Cd2+ ion at low concentrations (20 mg L(-1)) significantly (P<0.05) increased the sorption of SMX on both RS and AF. Our study confirms that biochar derived from the wetland plants could be used as effective adsorbents to remove SMX from aqueous solution.

Comparative evaluation of sorption kinetics and isotherms of pyrene onto microplastics.

PubMed

Wang, Wenfeng; Wang, Jun

2018-02-01

Concerns regarding microplastics pollution and their potential to concentrate and transport organic contaminants in aquatic environments are growing in recent years. Sorption of organic chemicals by microplastics may affect the distribution and bioavailability of the chemicals. Here sorption process of pyrene (Pyr), a frequently encountered polycyclic aromatic hydrocarbon in aquatic environments, on three types of mass-produced plastic particles (high-density polyethylene (PE), polystyrene (PS) and polyvinylchloride (PVC)), was investigated by comparative analysis of different sorption kinetic and isotherm models. Optimum kinetic and isotherm models were predicted by the linear least-squares regression method. The pseudo-second-order kinetic model was more appropriate in describing the entire sorption process (R 2  > 0.99). Sorption rates of Pyr onto microplastics were mainly controlled by intraparticle diffusion. PE exhibited the highest affinity for Pyr, followed by PS and PVC. The sorption equilibrium data were best fitted to the Langmuir isotherm (R 2  > 0.99), indicating monolayer coverage of Pyr onto the microplastics. Copyright © 2017 Elsevier Ltd. All rights reserved.

Removal of selected pharmaceuticals from aqueous solution using magnetic chitosan: sorption behavior and mechanism.

PubMed

Zhang, Yalei; Shen, Zhe; Dai, Chaomeng; Zhou, Xuefei

2014-11-01

A novel-modified magnetic chitosan adsorbent was used to remove selected pharmaceuticals, i.e., diclofenac (DCF) and clofibric acid (CA) and carbamazepine (CBZ), from aqueous solutions. The characterization of magnetic chitosan was achieved by scanning electron and transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, vibrating sample magnetometer, and nitrogen sorption analysis. The magnetic chitosan had effective sorption affinity for DCF and CA but no sorption of CBZ was observed. The sorption capacities of CA and DCF in the individual solutions were 191.2 and 57.5 mg/g, respectively. While in mixed solution, DCF showed higher sorption affinity. Sorption kinetics indicated a quick equilibrium reached within 2 min. Lower solution pH values were found to be advantageous for the adsorption process. The sorption efficacy of CA declined significantly with increasing inorganic salt concentration. However, sorption performance of DCF was stable under different ionic strength conditions.

Sorption kinetics of Hg and HgCl[sub 2] on Kirkwood-Cohansey aquifer sediments from the New Jersey Coastal Plain

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

MacLeod, C.; Peterson, J.

1992-01-01

Anomalously high Hg concentrations have been detected from domestic wells in the Kirkwood-Cohansey Aquifer System, New Jersey Coastal Plain. Mercury concentrations ranging from 0.2--83.0 [mu]g/l in relatively shallow wells ([lt] 100 feet) have been detected. Concentrations in excess of 2.0 [mu]g/l, (the USEPA Drinking Water Standard) have been detected in wells where the Cohansey Sand is overlain by the Bridgeton Formation; a fluvial iron-rich sand with some gravelly channel deposits containing goethite and gibbsite nodules. In this study, Bridgeton Fm. sediments were used to determine the sorption kinetics for solutions containing HgCl[sub 2] and for solutions containing dissolved elemental Hgmore » in order to assess the potential for the Bridgeton sediments to act as a conduit for Hg mobilized from the surface. Results of batch equilibrium experiments suggest that dissolved elemental Hg sorbs to Bridgeton sediments by a risk-order kinetic process. Sorption of the Hg proceeded exponentially and equilibrium was reached within 14 hours. The sorption kinetics for the HgCl[sub 2] solutions, however, appear to be of a second or higher order. For this compound sorption to the sediments begins exponentially, but after 6 hours desorption into the water begins to predominate followed by a slower exponential sorption step that requires nearly 36 hours to reach equilibrium. These experiments illustrate the necessity of determining the distribution coefficients of possible source compounds when attempting to evaluate mobilization potential of a contaminant in the unsaturated zone. Moreover, these data also suggest that HgCl[sub 2], a seed dressing for corn, medial bacteriacide, and embalming fluid ingredient, is more mobile in the environment than dissolved elemental Hg. Consequently, the ground water contamination potential appears to be greater for HgCl[sub 2] than for elemental Hg.« less

Can soil drying affect the sorption of pesticides in soil?

NASA Astrophysics Data System (ADS)

Chaplain, Véronique; Saint, Philippe; Mamy, Laure; Barriuso, Enrique

2010-05-01

The sorption of pesticides in soils mainly controls their further dispersion into the environment. Sorption is usually related to the physico-chemical properties of molecules but it also depends on the hydrophobic features of soils. However, the hydrophobicity of soils changes with wetting and drying cycles and this can be enhanced with climate change. The objective of this study was to measure by using controlled artificial soils the influence of the hydrophobic characteristic of soils on the retention of a model pesticide. Artificial soils consisted in silica particles covered by synthetic cationic polymers. Polymers were characterized by the molar ratio of monomers bearing an alkyl chain of 12C. Two polymers were used, with 20 and 80 % ratios, and the same degree of polymerization. In addition, porous and non-porous particles were used to study the accessibility notion and to measure the influence of diffusion on pesticide sorption kinetics. Lindane was chosen as model molecule because its adsorption is supposed mainly due to hydrophobic interactions. Results on polymers adsorption on silica showed that it was governed by electrostatic interactions, without any dependency of the hydrophobic ratio. Polymers covered the entire surface of porous particles. Kinetic measurements showed that lindane sorption was slowed in porous particles due to the molecular diffusion inside the microporosity. The adsorption of lindane on covered silica particles corresponded to a partition mechanism described by linear isotherms. The slope was determined by the hydrophobic ratio of polymers: the sorption of lindane was highest in the most hydrophobic artificial soil. As a result, modification in soil hydrophobicity, that can happen with climate change, might affect the sorption and the fate of pesticides. However additional experiments are needed to confirm these first results. Such artificial soils should be used as reference materials to compare the reactivity of pesticides, to

Using polyacrylate-coated SPME fibers to quantify sorption of polar and ionic organic contaminants to dissolved organic carbon.

PubMed

Haftka, Joris J-H; Scherpenisse, Peter; Jonker, Michiel T O; Hermens, Joop L M

2013-05-07

A passive sampling method using polyacrylate-coated solid-phase microextraction (SPME) fibers was applied to determine sorption of polar and ionic organic contaminants to dissolved organic carbon (DOC). The tested contaminants included pharmaceuticals, industrial chemicals, hormones, and pesticides and represented neutral, anionic, and cationic structures. Prior to the passive sampler application, sorption of the chemicals to the fibers was characterized. This was needed in order to accurately translate concentrations measured in fibers to freely dissolved aqueous concentrations during the sorption tests with DOC. Sorption isotherms of neutral compounds to the fiber were linear, whereas isotherms of basic chemicals covered a nonlinear and a linear range. Sorption of acidic and basic compounds to the fiber was pH-dependent and was dominated by sorption of the neutral sorbate species. Fiber- and DOC-water partition coefficients of neutral compounds were both linearly related to octanol-water partition coefficients (log Kow). The results of this study show that polyacrylate fibers can be used to quantify sorption to DOC of neutral and ionic contaminants, having multiple functional groups and spanning a wide hydrophobicity range (log Kow = 2.5-7.5).

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 (0.812)<0.99). The sorption and desorption reactions, however, did not provide the same isotherms, indicating that hysteresis occurred in Cd sorption-desorption processes. The extent of hysteresis was quantified based on the differences obtained from sorption and desorption isotherms regarding the amount of Cd sorbed, the Freundlich exponent, and the Cd distribution coefficient. The results revealed that, sepiolite possessed the most hysteretic behavior among the minerals studied. Calcite showed much smaller hysteresis compared to the other two silicate clays at low Cd surface load, but its hysteresis indices significantly increased, and exceeded that of palygorskite, as the amount of Cd in the systems increased. The average amount of Cd released after five desorption steps, was 13.8%, 2.2% and 3.6% for the palygorskite, sepiolite and calcite, respectively, indicating that a large portion of Cd was irreversibly retained by the minerals.

Sorption of lambda-cyhalothrin, cypermethrin, deltamethrin and fenvalerate to quartz, corundum, kaolinite and montmorillonite.

PubMed

Oudou, H Chaaieri; Hansen, H C Bruun

2002-12-01

Sorption to mineral surfaces may be important for retention and degradation of hydrophobic pesticides in subsoils and aquifers poor in organic matter. In this work the title pyrethroids have been used to investigate selective interactions with the surfaces of four minerals. Sorption of the four pyrethroids was quantified in batch experiments with initial pyrethroid concentrations of 1-100 microg/l. Sorption to centrifuge tubes used in the batch experiments accounted for 25-60% of total sorption. Net sorption was obtained from total sorption after subtracting the amounts of pyrethroids sorbed to centrifuge tubes used. All isotherms could be fitted by the Freundlich equation with n ranging between 0.9 and 1.1. Bonding affinities per unit surface area decreased in the order: corundum > quartz > montmorillonite approximately equal kaolinite. A similar sequence as found for the total surface tension of the minerals. All minerals showed the same selectivity order with respect to sorption affinity of the four pyrethroids: lambda-cyhalothrin > deltamethrin > cypermethrin > fenvalerate, which shows that the most hydrophobic compound is sorbed most strongly. Stereochemical properties of the four pyrethroid formulations may also contribute to the selectivity pattern.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

2004-02-01

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength

Sorption of pharmaceuticals and personal care products to polyethylene debris.

PubMed

Wu, Chenxi; Zhang, Kai; Huang, Xiaolong; Liu, Jiantong

2016-05-01

Presence of plastic debris in marine and freshwater ecosystems is increasingly reported. Previous research suggested plastic debris had a strong affiliation for many pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and heavy metals. In this study, the sorption behavior of pharmaceuticals and personal care products (PPCPs), including carbamazepine (CBZ), 4-methylbenzylidene camphor (4MBC), triclosan (TCS), and 17α-ethinyl estradiol (EE2), to polyethylene (PE) debris (250 to 280 μm) was investigated. The estimated linear sorption coefficients (K d) are 191.4, 311.5, 5140, and 53,225 L/kg for CBZ, EE2, TCS, and 4MBC, and are related to their hydrophobicities. Increase of salinity from 0.05 to 3.5 % did not affect the sorption of 4MBC, CBZ, and EE2 but enhanced the sorption of TCS, likely due to the salting-out effect. Increase of dissolved organic matter (DOM) content using Aldrich humic acid (HA) as a proxy reduced the sorption of 4MBC, EE2, and TCS, all of which show a relatively strong affiliation to HA. Results from this work suggest that microplastics may play an important role in the fate and transport of PPCPs, especially for those hydrophobic ones.

Thermonuclear Reaction Rate of T(t,2n) α Measured in ICF Plasmas

NASA Astrophysics Data System (ADS)

Brune, C. R.; Casey, D. T.; Caggiano, J. A.; Hatarik, R.; McNabb, D. P.; Sayre, D. B.; Smalyuk, V. A.; Bacher, A. D.; Frenje, J. A.; Gatu-Johnson, M.; Zylstra, A. B.; Couder, M.

2014-09-01

Measurements of charged-particle reactivity have been performed in inertial confinement fusion experiments at the National Ignition Facility. Time-of-flight detectors were used to measure neutrons from the T(t,2n) and T(d,n) reactions produced by implosions with tritium-filled targets (0.1% deuterium). Along with the measured target fuel composition and reactant ion temperature, the well-known T(d,n) reactivity was used to convert the measured neutron yields into a T(t,2n) reactivity. The ion temperature was determined to be 3.3(3) keV, corresponding to an effective energy of 16 keV. In comparison to accelerator measurements of the low-energy T(t,2n) cross section, the source of all previous data, our experiment has resulted in T(t,2n) data with better statistics and lower backgrounds.

Selective carbon dioxide sorption by a new breathing three-dimensional Zn-MOF with Lewis basic nitrogen-rich channels.

PubMed

Kim, Hyun-Chul; Huh, Seong; Lee, Do Nam; Kim, Youngmee

2018-04-03

Lewis basic heteroatoms orderly located inside the well-defined channels of metal-organic frameworks (MOFs) are potentially ideal active sites for selective gas sorption and catalysis. To develop functional MOFs with Lewis basic sites inside channels, a new C2h-symmetric dicarboxylate-based bridging ligand, 3,3'-(pyrazine-2,5-diyl)dibenzoic acid (3,3'-PDBA), was prepared by a Suzuki coupling reaction. Subsequently, two new Zn-MOFs containing the C2h-symmetric 3,3'-PDBA bridging ligand and two different bis(pyridyl)-based pillars, 1,2-bis(4-pyridyl)ethane (bpa) or 1,2-bis(4-pyridyl)ethylene (bpe), were prepared through a thermal reaction in N,N-dimethylformamide (DMF). The resulting two Zn-MOFs of the general formula of three-dimensional (3D) [Zn2(μ4-3,3'-PDBA)2(μ2-bpa)]3·(DMF)5(H2O)13 (1) or 3D-like 2D [Zn2(μ4-3,3'-PDBA)2(μ2-bpe)]·(H2O) (2) displayed primitive cubic pcu net and 2D sql net, respectively. Both Zn-MOFs 1 and 2 contain uncoordinated Lewis basic pyrazinyl nitrogen atoms in the frameworks. The solvent-free 1 with flexible bpa linkers only showed a potential porosity of 15.9% by PLATON analysis. Zn-MOF 1 with openly accessible Lewis basic sites exhibited selective sorption of CO2 over N2, H2, and CH4 at low temperature. The adsorption and desorption isotherms for CO2 sorption at 196 K showed phenomenal hysteretic behaviour indicative of a breathing process through an adsorbate-discriminatory gate-opening process toward CO2 at a low gas pressure.

Gas sorption in poly-(2,6-dimethyl-1,4-phenylene)oxide containing nanoporous crystalline phases

NASA Astrophysics Data System (ADS)

Galizia, M.; Daniel, C.; Fasano, G.; Guerra, G.; Mensitieri, G.

2012-07-01

In this contribution is presented an analysis of mass transport properties of low molecular weight compounds in amorphous PPO and in semi-crystalline PPO obtained by treating with benzene and carbon tetrachloride the amorphous sample. It is found that semi-crystalline samples are endowed with larger gas sorption capacity and diffusivity as compared to the amorphous ones: this behaviour has been attributed to the nanoporous nature of the crystalline phases induced by treatment with solvents. In particular, sorption experiments, carried out at 30°C with methane, carbon dioxide, propane and propylene, have shown that both semi-crystalline PPOs display rather interesting features which make them suitable for use as membrane materials in gas separation processes, in view of the relatively high values of solubility and diffusivity. Moreover, these peculiar sorption and mass transport properties have been found to be virtually unaffected by thermal ageing: in fact, sorption experiments conducted on amorphous and semi-crystalline PPO after treatment at 65°C for three months showed that sorption properties of aged samples are the same as for the untreated samples. This is an important feature to assure the stability of performances in membrane applications.

Experimental and modeling study of the uranium (VI) sorption on goethite.

PubMed

Missana, Tiziana; García-Gutiérrez, Miguel; Maffiotte, Cesar

2003-04-15

Acicular goethite was synthesized in the laboratory and its main physicochemical properties (composition, microstructure, surface area, and surface charge) were analyzed as a previous step to sorption experiments. The stability of the oxide, under the conditions used in sorption studies, was also investigated. The sorption of U(VI) onto goethite was studied under O(2)- and CO(2)-free atmosphere and in a wide range of experimental conditions (pH, ionic strength, radionuclide, and solid concentration), in order to assess the validity of different surface complexation models available for the interpretation of sorption data. Three different models were used to fit the experimental data. The first two models were based on the diffuse double layer concept. The first one (Model 1) considered two different monodentate complexes with the goethite surface and the second (Model 2) a single binuclear bidentate complex. A nonelectrostatic (NE) approach was used as a third model and, in that case, the same species considered in Model 1 were used. The results showed that all the models are able to describe the sorption behavior fairly well as a function of pH, electrolyte concentration, and U(VI) concentration. However, Model 2 fails in the description of the uranium sorption behavior as a function of the sorbent concentration. This demonstrates the importance of checking the validity of any surface complexation model under the widest possible range of experimental conditions.

Using satellite measurements of N2O to remove dynamical variability from HCl measurements

NASA Astrophysics Data System (ADS)

Stolarski, Richard S.; Douglass, Anne R.; Strahan, Susan E.

2018-04-01

Column HCl measurements show deviations from the expected slow decline following the regulation of chlorine-containing compounds by the Montreal Protocol. We use the simultaneous measurements of N2O and HCl by the Microwave Limb Sounder (MLS) instrument on the Aura satellite to examine this problem. We find that the use of N2O measurements at a specific altitude to represent the impact of dynamical variability on HCl results in a derived linear trend in HCl that is negative (ranging from -2.5 to 5.3 % decade-1) at all altitudes between 68 and 10 hPa. These trends are at or near 2σ statistical significance at all pressure levels between 68 and 10 hPa. This shows that analysis of simultaneous measurements of several constituents is a useful approach to identify small trends from data records that are strongly influenced by dynamical interannual variability.

Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

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

Jagadamma, Sindhu; Mayes, Melanie; Phillips, Jana Randolph

Physico-chemical sorption of dissolved organic carbon (DOC) on soil minerals is one of the major processes of organic carbon (OC) stabilization in soils, especially in deeper layers. The attachment of C on soil solids is related to the reactivity of the soil minerals and the chemistry of the sorbate functional groups, but the sorption studies conducted without controlling microbial activity may overestimate the sorption potential of soil. This study was conducted to examine the sorptive characteristics of a diverse functional groups of simple OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols,more » Ultisols and Alfisols) with and without biological degradative processes. Equilibrium batch experiments were conducted using 0-100 mg C L-1 at a solid-solution ratio of 1:60 for 48 hrs and the sorption parameters were calculated by Langmuir model fitting. The amount of added compounds that remained in the solution phase was detected by high performance liquid chromatography (HPLC) and total organic C (TOC) analysis. Soil sterilization was performed by -irradiation technique and experiments were repeated to determine the contribution of microbial degradation to apparent sorption. Overall, Ultisols did not show a marked preference for apparent sorption of any of the model compounds, as indicated by a narrower range of maximum sorption capacity (Smax) of 173-527 mg kg soil-1 across compounds. Mollisols exhibited a strong preference for apparent sorption of oxalic acid (Smax of 5290 mg kg soil-1) and sinapyl alcohol (Smax of 2031 mg kg soil-1) over the other compounds. The propensity for sorption of oxalic acid is mainly attributed to the precipitation of insoluble Ca-oxalate due to the calcareous nature of most Mollisol subsoils and its preference for sinapyl alcohol could be linked to the polymerization of this lignin monomer on 2:2 mineral dominated soils. The reactivity of Alfisols to DOC

Sorption of Liquids on Impurities in Polymers, As Affected by the Sorption History

NASA Astrophysics Data System (ADS)

Ageev, E. P.; Strusovskaya, N. L.; Matushkina, N. N.

2018-02-01

An unusual effect is observed that occurs during the sorption of liquids by polymers: The sorption flux directed from the liquid into the polymer bulk transfers only the sorbate, while the spontaneously established backward flux carries a sorbate‒impurity complex into the liquid. It is shown that this effect can be used to remove hydrophilic impurities from a hydrophobic polymer. It is assumed that delocalized (and mobile) sorbent particles participate in this phenomenon and include them in the proposed mechanism of sorption. The inversion of gradient of chemical potential upon the formation of delocalized particles determines the backward material flow.

Dynamic Triple-Mode Sorption and Outgassing in Materials.

PubMed

Sharma, Hom N; Harley, Stephen J; Sun, Yunwei; Glascoe, Elizabeth A

2017-06-07

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C-70 °C) by varying the water activity (0.0-0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis, especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.

Dynamic Triple-Mode Sorption and Outgassing in Materials

DOE PAGES

Sharma, Hom N.; Harley, Stephen J.; Sun, Yunwei; ...

2017-06-07

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C–70 °C) by varying the water activity (0.0–0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis,more » especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.« less

Dynamic Triple-Mode Sorption and Outgassing in Materials

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

Sharma, Hom N.; Harley, Stephen J.; Sun, Yunwei

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C–70 °C) by varying the water activity (0.0–0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis,more » especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.« less

Experimental determination of sorption in fractured flow systems

NASA Astrophysics Data System (ADS)

Zimmerman, Mitchell D.; Bennett, Philip C.; Sharp, John M.; Choi, Wan-Joo

2002-09-01

Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated ˜2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.

Relation of organic contaminant equilibrium sorption and kinetic uptake in plants

USGS Publications Warehouse

Li, H.; Sheng, G.; Chiou, C.T.; Xu, O.

2005-01-01

Plant uptake is one of the environmental processes that influence contaminant fate. Understanding the magnitude and rate of plant uptake is critical to assessing potential crop contamination and the development of phytoremediation technologies. We determined (1) the partition-dominated equilibrium sorption of lindane (LDN) and hexachlorobenzene (HCB) by roots and shoots of wheat seedlings, (2) the kinetic uptake of LDN and HCB by roots and shoots of wheat seedlings, (3) the kinetic uptake of HCB, tetrachloroethylene (PCE), and trichloroethylene (TCE) by roots and shoots of ryegrass seedlings, and (4) the lipid, carbohydrate, and water contents of the plants. Although the determined sorption and the plant composition together suggest the predominant role of plant lipids for the sorption of LDN and HCB, the predicted partition with lipids of LDN and HCB using the octanol-water partition coefficients is notably lower than the measured sorption, due presumably to underestimation of the plant lipid contents and to the fact that octanol is less effective as a partition medium than plant lipids. The equilibrium sorption or the estimated partition can be viewed as the kinetic uptake limits. The uptakes of LDN, PCE, and TCE from water at fixed concentrations increased with exposure time in approach to steady states. The uptake of HCB did not reach a plateau within the tested time because of its exceptionally high partition coefficient. In all of the cases, the observed uptakes were lower than their respective limits, due presumably to contaminant dissipation in and limited water transpiration by the plants. ?? 2005 American Chemical Society.

Sorption and precipitation of Mn2+ by viable and autoclaved Shewanella putrefaciens: Effect of contact time

NASA Astrophysics Data System (ADS)

Chubar, Natalia; Visser, Tom; Avramut, Cristina; de Waard, Helen

2013-01-01

The sorption of Mn(II) by viable and inactivated cells of Shewanella putrefaciens, a non-pathogenic, facultative anaerobic, gram-negative bacterium characterised as a Mn(IV) and Fe(III) reducer, was studied under aerobic conditions, as a function of pH, bacterial density and metal loading. During a short contact time (3-24 h), the adsorptive behaviour of live and dead bacteria toward Mn(II) was sufficiently similar, an observation that was reflected in the studies on adsorption kinetics at various metal loadings, effects of pH, bacteria density, isotherms and drifting of pH during adsorption. Continuing the experiment for an additional 2-30 days demonstrated that the Mn(II) sorption by suspensions of viable and autoclaved cells differed significantly from one another. The sorption to dead cells was characterised by a rapid equilibration and was described by an isotherm. In contrast, the sorption (uptake) to live bacteria exhibited a complex time-dependent uptake. This uptake began as adsorption and ion exchange processes followed by bioprecipitation, and it was accompanied by the formation of polymeric sugars (EPS) and the release of dissolved organic substances. FTIR, EXAFS/XANES and XPS demonstrated that manganese(II) phosphate was the main precipitate formed in 125 ml batches, which is the first evidence of the ability of microbes to synthesise manganese phosphates. XPS and XANES spectra did not detect Mn(II) oxidation. Although the release of protein-like compounds by the viable bacteria increased in the presence of Mn2+ (and, by contrast, the release of carbohydrates did not change), electrochemical analyses did not indicate any aqueous complexation of Mn(II) by the organic ligands.

Technical Note: Simultaneous measurement of sedimentary N2 and N2O production and a modified 15N isotope pairing technique

NASA Astrophysics Data System (ADS)

Hsu, T.-C.; Kao, S.-J.

2013-12-01

Dinitrogen (N2) and/or nitrous oxide (N2O) are produced through denitrification, anaerobic ammonium oxidation (anammox) or nitrification in sediments, of which entangled processes complicate the absolute rate estimations of gaseous nitrogen production from individual pathways. The classical isotope pairing technique (IPT), the most common 15N nitrate enrichment method to quantify denitrification, has recently been modified by different researchers to (1) discriminate between the N2 produced by denitrification and anammox or to (2) provide a more accurate denitrification rate under considering production of both N2O and N2. In case 1, the revised IPT focused on N2 production being suitable for the environments of a low N2O-to-N2 production ratio, while in case 2, anammox was neglected. This paper develops a modified method to refine previous versions of IPT. Cryogenic traps were installed to separately preconcentrate N2 and N2O, thus allowing for subsequent measurement of the two gases generated in one sample vial. The precision is better than 2% for N2 (m/z 28, m/z 29 and m/z 30), and 1.5% for N2O (m/z 44, m/z 45 and m/z 46). Based on the six m/z peaks of the two gases, the 15N nitrate traceable processes including N2 and N2O from denitrification and N2 from anammox were estimated. Meanwhile, N2O produced by nitrification was estimated via the production rate of unlabeled 44N2O. To validate the applicability of our modified method, incubation experiments were conducted using sediment cores taken from the Danshuei Estuary in Taiwan. Rates of the aforementioned nitrogen removal processes were successfully determined. Moreover, N2O yield was as high as 66%, which would significantly bias previous IPT approaches if N2O was not considered. Our modified method not only complements previous versions of IPT but also provides more comprehensive information to advance our understanding of nitrogen dynamics of the water-sediment interface.

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.

Measuring and Modeling Surface Sorption Dynamics of Organophosphate Flame Retardants in Chambers

EPA Science Inventory

Understanding the sorption mechanisms for organophosphate flame retardants (OPFRs) on impervious surfaces is important if we are to improve our understanding of the fate and transport of OPFRs in indoor environments. Traditional Langmuir and Freundlich models are widely adopted t...

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.

Capacity and mechanisms of ammonium and cadmium sorption on different wetland-plant derived biochars.

PubMed

Cui, Xiaoqiang; Hao, Hulin; Zhang, Changkuan; He, Zhenli; Yang, Xiaoe

2016-01-01

The objective of this study was to investigate the relationship between Cd(2+)/NH4(+) sorption and physicochemical properties of biochars produced from different wetland plants. Biochars from six species of wetland plants (i.e., Canna indica, Pennisetum purpureum Schum, Thalia dealbata, Zizania caduciflora, Phragmites australis and Vetiveria zizanioides) were obtained at 500°C and characterized, and their sorption for ammonium and cadmium was determined. There were significant differences in elemental composition, functional groups and specific surface area among the biochars derived from different wetland plant species. Sorption of ammonium and cadmium on the biochars could be described by a pseudo second order kinetic model, and the simple Langmuir model fits the isotherm data better than the Freundlich or Temkin model. The C. indica derived biochar had the largest sorption capacity for NH4(+) and Cd(2+), with a maximum sorption of 13.35 and 125.8mgg(-1), respectively. P. purpureum Schum derived biochar had a similar maximum sorption (119.3mgg(-1)) for Cd(2+). Ammonium sorption was mainly controlled by cation exchange, surface complexation with oxygen-containing functional groups and the formation of magnesium ammonium phosphate compounds, whereas for Cd(2+) sorption, the formation of cadmium phosphate precipitates, cation exchange and binding to oxygen-containing groups were the major possible mechanisms. In addition, the sorption of ammonium and cadmium was not affected by surface area and microporosity of the biochars. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Sorption of lead onto two gram-negative marine bacteria in seawater

USGS Publications Warehouse

Harvey, Ronald W.; Leckie, James O.

1985-01-01

Laboratory adsorption experiments performed at environmentally significant lead (Pb) and cell concentrations indicate that the marine bacteria examined have significant binding capacities for Pb. However, the behavior governing Pb sorption onto gram-negative bacteria in seawater may be quite complex. The sorption kinetics appear to involve two distinct phases, i.e., a rapid removal of Pb from solution within the first few minutes, followed by a slow but nearly constant removal over many hours. Also, the average binding coefficient, calculated for Pb sorption onto bacteria and a measure of binding intensity, increases with decreasing sorption density (amounts of bacteria-associated Pb per unit bacterial surface) at low cell concentrations (105 cells ml−1), but decreases with decreasing sorption density at higher cell concentrations (107 cells ml−1). The latter effect is apparently due to the production of significant amounts of extra-cellular organics at high cell concentrations that compete directly with bacterial surfaces for available lead. Lead toxicity and active uptake by marine bacteria did not appear significant at the Pb concentrations used.

Phenanthrene sorption with heterogeneous organic matter in a landfill aquifer material

USGS Publications Warehouse

Karapanagioti, H.K.; Sabatini, D.A.; Kleineidam, S.; Grathwohl, P.; Ligouis, B.

1999-01-01

Phenanthrene was used as a model chemical to study the sorption properties of Canadian River Alluvium aquifer material. Both equilibrium and kinetic sorption processes were evaluated through batch studies. The bulk sample was divided into subsamples with varying properties such as particle size, organic content, equilibration time, etc. in order to determine the effect of these properties on resulting sorption parameters. The data have been interpreted and the effect of experimental variables was quantified using the Freundlich isotherm model and a numerical solution of Fick's 2nd law in porous media. Microscopic organic matter characterization proved to be a valuable tool for explaining the results. Different organic matter properties and sorption mechanisms were observed for each soil subsample. Samples containing coal particles presented high Koc values. Samples with organic matter dominated by organic coatings on quartz grains presented low Koc values and contained a high percentage of fast sorption sites. The numerical solution of Fick's 2ndlaw requires the addition of two terms (fast and slow) in order to fit the kinetics of these heterogeneous samples properly. These results thus demonstrate the need for soil organic matter characterization in order to predict and explain the sorption properties of a soil sample containing heterogeneous organic matter and also the difficulty and complexity of modeling sorption in such samples.

Glyphosate sorption/desorption on biochars - interactions of physical and chemical processes.

PubMed

Hall, Kathleen E; Spokas, Kurt A; Gamiz, Beatriz; Cox, Lucia; Papiernik, Sharon K; Koskinen, William C

2018-05-01

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 to 900 °C to elucidate fundamental mechanisms. Glyphosate (1 mg L -1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g -1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl 2 solution; however, up to 86% of the bound glyphosate was released with a K 2 HPO 4 solution. Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Synthesis and applications of eco-magnetic nano-hydroxyapatite chitosan composite for enhanced fluoride sorption.

PubMed

Pandi, Kalimuthu; Viswanathan, Natrayasamy

2015-12-10

Adsorption is a significant reaction occurs between adsorbent/water interface for controlling the pollutants in the aqueous environment. In this regard, an eco-magnetic biosorbent was prepared by uniform deposition of magnetic Fe3O4 particles on the surface of nano-hydroxyapatite (n-HAp)/chitosan (CS) nanocomposite namely Fe3O4@n-HApCS composite as versatile sorbent for fluoride sorption. The resulting Fe3O4@n-HApCS nanocomposite was characterized by FTIR and SEM with EDAX techniques. The defluoridation capacity (DC) was found to depend on the contact time, pH, co-existing anions, initial fluoride concentration and temperature. The sorption isotherm was investigated by Freundlich, Langmuir and Temkin isotherm models using the batch method. The thermodynamic parameters revealed the feasibility, spontaneity and endothermic nature of fluoride sorption. The results of this research work designated that Fe3O4@n-HApCS composite having the excellent defluoridation capacity than the individual components and interesting to note that the easy magnetic separation of Fe3O4@n-HApCS composite from aqueous medium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of chemical and mechanical polishing on water sorption and solubility of denture base acrylic resins.

PubMed

Rahal, Juliana Saab; Mesquita, Marcelo Ferraz; Henriques, Guilherme Elias Pessanha; Nóbilo, Mauro Antonio Arruda

2004-01-01

Influence of polishing methods on water sorption and solubility of denture base acrylic resins was studied. Eighty samples were divided into groups: Classico (CL), and QC 20 (QC) - hot water bath cured; Acron MC (AC), and Onda Cryl (ON) - microwave cured; and submitted to mechanical polishing (MP) - pumice slurry, chalk powder, soft brush and felt cone in a bench vise; or chemical polishing (CP) - heated monomer fluid in a chemical polisher. The first desiccation process was followed by storage in distilled water at 37 +/- 1 degrees C for 1 h, 1 day, 1, 2, 3 and 4 weeks. Concluding each period, water sorption was measured. After the fourth week, a second desiccation process was done to calculate solubility. Data were submitted to analysis of variance, followed by Tukey test (psorption (%) and solubility (%), respectively, were: CL-MP: 1.92 and 0.02; CL-CP: 1.98 and 0.52; QC-MP: 2.31 and -0.05; QC-CP: 2.32 and 0.25; AC-MP: 2.45 and -0.07; AC-CP: 2.43 and 0.41; ON-MP: 2.32 and -0.06; ON-CP: 2.34 and 0.27. Mechanical polishing promoted significantly lower solubility of acrylic resins; initially, water sorption values were higher for chemically polished samples, however, after 4 weeks all groups were similar.

Cross-Plane Seebeck Coefficient Measurement of Misfit Layered Compounds (SnSe)n(TiSe2)n (n = 1,3,4,5).

PubMed

Li, Zhen; Bauers, Sage R; Poudel, Nirakar; Hamann, Danielle; Wang, Xiaoming; Choi, David S; Esfarjani, Keivan; Shi, Li; Johnson, David C; Cronin, Stephen B

2017-03-08

We report cross-plane thermoelectric measurements of misfit layered compounds (SnSe) n (TiSe 2 ) n (n = 1,3,4,5), approximately 50 nm thick. Metal resistance thermometers are fabricated on the top and bottom of the (SnSe) n (TiSe 2 ) n material to measure the temperature difference and heat transport through the material directly. By varying the number of layers in a supercell, n, we vary the interface density while maintaining a constant global stoichiometry. The Seebeck coefficient measured across the (SnSe) n (TiSe 2 ) n samples was found to depend strongly on the number of layers in the supercell (n). When n decreases from 5 to 1, the cross-plane Seebeck coefficient decreases from -31 to -2.5 μV/K, while the cross-plane effective thermal conductivity decreases by a factor of 2, due to increased interfacial phonon scattering. The cross-plane Seebeck coefficients of the (SnSe) n (TiSe 2 ) n are very different from the in-plane Seebeck coefficients, which are higher in magnitude and less sensitive to the number of layers in a supercell, n. We believe this difference is due to the different carrier types in the n-SnSe and p-TiSe 2 layers and the effect of tunneling on the cross-plane transport.

Sorption and desorption of carbamazepine, naproxen and triclosan in a soil irrigated with raw wastewater: estimation of the sorption parameters by considering the initial mass of the compounds in the soil.

PubMed

Durán-Álvarez, Juan C; Prado-Pano, Blanca; Jiménez-Cisneros, Blanca

2012-06-01

In conventional sorption studies, the prior presence of contaminants in the soil is not considered when estimating the sorption parameters because this is only a transient state. However, this parameter should be considered in order to avoid the under/overestimation of the soil sorption capacity. In this study, the sorption of naproxen, carbamazepine and triclosan was determined in a wastewater irrigated soil, considering the initial mass of the compounds. Batch sorption-desorption tests were carried out at two soil depths (0-10 cm and 30-40 cm), using either 10 mM CaCl(2) solution or untreated wastewater as the liquid phase. Data were satisfactorily fitted to the initial mass model. For the two soils, release of naproxen and carbamazepine was observed when the CaCl(2) solution was used, but not in the soil/wastewater system. The compounds' release was higher in the topsoil than in the 30-40 cm soil. Sorption coefficients (K(d)) for CaCl(2) solution tests showed that in the topsoil, triclosan (64.9 L kg(-1)) is sorbed to a higher extent than carbamazepine and naproxen (5.81 and 2.39 L kg(-1), respectively). In the 30-40 cm soil, carbamazepine and naproxen K(d) values (11.4 and 4.41 L kg(-1), respectively) were higher than those obtained for the topsoil, while the triclosan K(d) value was significantly lower than in the topsoil (19.2 L kg(-1)). Differences in K(d) values were found when comparing the results obtained for the two liquid phases. Sorption of naproxen and carbamazepine was reversible for both soils, while sorption of triclosan was found to be irreversible. This study shows the sorption behavior of three pharmaceuticals in a wastewater irrigated soil, as well as the importance of considering the initial mass of target pollutants in the estimation of their sorption parameters. Copyright © 2012 Elsevier Ltd. All rights reserved.

Wettability, water sorption and water solubility of seven silicone elastomers used for maxillofacial prostheses.

PubMed

Hulterström, Anna Karin; Berglund, Anders; Ruyter, I Eystein

2008-01-01

The wettability, water sorption and solubility of silicone elastomers used for maxillofacial prostheses were studied. The hypothesis was, that a material that has absorbed water would show an increase in the wettability and thus also the surface free energy of the material. Seven silicone elastomers, both addition- and condensation type polymers, were included. Five specimens of each material were subjected to treatment according to ISO standards 1567:1999 and 10477: 2004 for water sorption and solubility. The volumes of the specimens were measured according to Archimedes principle. The contact angle was measured with a contact angle goniometer at various stages of the sorption/solubility test. Wettability changed over the test period, but not according to theory. The addition type silicones showed little or no sorption and solubility, but two of the condensation type polymers tested had a significant sorption and solubility. This study showed that condensation type polymers may show too large volumetric changes when exposed to fluids, and therefore should no longer be used in prosthetic devices. The results of this study also suggests that it might be of interest to test sorption and solubility of materials that are to be implanted, since most of the materials had some solubility.

Characteristics of and sorption to biochars derived from waste material

NASA Astrophysics Data System (ADS)

Sun, Huichao; Kah, Melanie; Sigmund, Gabriel; Hofmann, Thilo

2015-04-01

Biochars can exhibit a high sorption potential towards heavy metals and organic contaminants in various environmental matrices (e.g., water, soil). They have therefore been proposed for environmental remediation purposes to sequester contaminants. To date, most studies have focused on the physicochemical and sorption properties of mineral phases poor biochars, which are typically produced from plant residues. Only little knowledge is available for biochars derived from human and animal waste material, which are typically characterized by high mineral contents (e.g., sewage sludge, manure). Using human and animal waste as source material to produce biochars would support the development of attractive combined strategies for waste management and remediation. The potential impact of mineral phases on the physicochemical and sorption properties of biochars requires further studies so that the potential as sorbent material can be evaluated. With this purpose, different source material biochars were produced at 200°C, 350°C and 500°C, to yield a series of biochars representing a range of mineral content. The derived biochars from wood shavings (<1% ash), sewage sludge (50-70% ash) and pig manure (30-60% ash), as well as a commercial biochar derived from grain husks (40% ash), were extensively characterized (e.g., element composition, surface area, porosity, Fourier transform infrared spectroscopy). The contents of potentially toxic elements (i.e., heavy metals and polycyclic aromatic hydrocarbons) of all materials were within the guidelines values proposed by the International Biochar Initiative, indicating their suitability for environmental application. Single point sorption coefficients for the model sorbate pyrene were measured to investigate the effect of mineral content, feedstock, pyrolysis temperature, particle size fractions and acid demineralization on sorption behavior. Overall, sorption of pyrene was strong for all materials (4 < Log Kd < 6.5 L

Synthesis, characterization and trivalent arsenic sorption potential of Ce-Al nanostructured mixed oxide

NASA Astrophysics Data System (ADS)

Bhattacharya, S.; Gupta, K.; Ghosh, U. C.

2017-04-01

Arsenic contamination in the ground water has serious health consequences in many parts of the world. The surface sorption method for arsenic mitigation has been widely investigated due to its simple method, inexpensive operation, highly efficient and low content of by-products. In the present study, nanostructured hydrated cerium aluminum oxide (NHCAO) was synthesized and characterized and its arsenic (III) sorption behavior from the aqueous solution was studied. The material was characterized in SEM, FE-SEM, TEM, AFM, XRD, and FT-IR. Batch method was used for the kinetics of As (III) sorption on nanoparticles at 303 (± 1.6) K and at pH 7.0 (± 0.2). The experiments on isotherm subject were performed individually at 288K, 303K, 318K temperatures at pH 7.0 (± 0.2) using the batch sorption method. In the kinetics study of arsenic (III) sorption, the sorption percentage was observed to remain nearly unchanged up to pH 9.0, thereafter only slight reduction in sorption percentage. The equilibrium sorption results were tested using the models of Langmuir and the Freundlich isotherm. The Langmuir model is the most fitted model for the sorption reaction. NHCAO was highly efficient in As(III) removal out of the water in the extensive range of pH and could be used for arsenic removal from contaminated water.

Cobalt sorption onto anaerobic granular sludge: isotherm and spatial localization analysis.

PubMed

van Hullebusch, Eric D; Gieteling, Jarno; Zhang, Min; Zandvoort, Marcel H; Daele, Wim Van; Defrancq, Jacques; Lens, Piet N L

2006-01-24

This study investigated the effect of different feeding regimes on the cobalt sorption capacity of anaerobic granular sludge from a full-scale bioreactor treating paper mill wastewater. Adsorption experiments were done with non-fed granules in monometal (only Co) and competitive conditions (Co and Ni in equimolar concentrations). In order to modify the extracellular polymeric substances and sulfides content of the granules, the sludge was fed for 30 days with glucose (pH 7, 30 degrees C, organic loading rate=1.2 g glucose l(-1) day-1) in the presence (COD/SO4(2-)=1) or absence of sulfate. The partitioning of the sorbed cobalt between the exchangeable, carbonates, organic matter/sulfides and residual fractions was determined using a sequential extraction procedure (modified Tessier). Experimental equilibrium sorption data for cobalt were analysed by the Langmuir, Freundlich and Redlich-Peterson isotherm equations. The total Langmuir maximal sorption capacity of the sludge fed with glucose and sulfate loaded with cobalt alone displayed a significantly higher maximal cobalt sorption (Qmax =18.76 mg g-1 TSS) than the sludge fed with glucose alone (Qmax =13.21 mg g-1 TSS), essentially due to an increased sorption capacity of the exchangeable (30-107%) and organic/sulfides fractions (70-30%). Environmental scanning electron microscopy coupled with an energy dispersive X-ray analysis of granular cross-sections showed that mainly iron minerals (i.e. iron sulfides) were involved in the cobalt accumulation. Moreover, the sorbed cobalt was mainly located at the edge of the granules. The sorption characteristics of the exchangeable and carbonates fractions fitted well to the Redlich-Peterson model (intermediate multi-layer sorption behaviour), whereas the sorption characteristics of the organic matter/sulfides and residual fractions fitted well to the Langmuir model (monolayer sorption behaviour). The organic matter/sulfides fraction displayed the highest affinity for cobalt

Lead sorption-desorption from organic residues.

PubMed

Duarte Zaragoza, Victor M; Carrillo, Rogelio; Gutierrez Castorena, Carmen M

2011-01-01

Sorption and desorption are mechanisms involved in the reduction of metal mobility and bioavailability in organic materials. Metal release from substrates is controlled by desorption. The capacity of coffee husk and pulp residues, vermicompost and cow manure to adsorb Pb2+ was evaluated. The mechanisms involved in the sorption process were also studied. Organic materials retained high concentrations of lead (up to 36,000 mg L(-1)); however, the mechanisms of sorption varied according to the characteristics of each material: degree of decomposition, pH, cation exchange capacity and percentage of organic matter. Vermicompost and manure removed 98% of the Pb from solution. Lead precipitated in manure and vermicompost, forming lead oxide (PbO) and lead ferrite (PbFe4O7). Adsorption isotherms did not fit to the typical Freundlich and Langmuir equations. Not only specific and non-specific adsorption was observed, but also precipitation and coprecipitation. Lead desorption from vermicompost and cow manure was less than 2%. For remediation of Pb-polluted sites, the application of vermicompost and manure is recommended in places with alkaline soils because Pb precipitation can be induced, whereas coffee pulp residue is recommended for acidic soils where Pb is adsorbed.

Chemical and mineralogical composition of the Mongolian rural soils and their uranium sorption behavior.

PubMed

Tserenpil, Sh; Maslov, O D; Norov, N; Liu, Q C; Fillipov, M F; Theng, Benny K G; Belov, A G

2013-04-01

Distribution of uranium (VI) between soil solids and solutions is a key parameter in assessing the risk to the biosphere of disposing uranium-rich waste products from nuclear plants as well as uranium (U) ore mining. Both of these topics have recently been brought to public attention in Mongolia. Regional background levels of soil elements are an important dataset for accessing the actual environmental situation and monitoring pollution levels. Little information, however, is available on background concentrations of various elements in Mongolian soils. Thirteen rural soils were sampled from six provinces in Mongolia, and the concentrations of macro-, micro- and trace elements were measured. The values obtained served as a reference (baseline) for uncontaminated soils. The soils were characterized with slightly acidic to strongly alkaline pH values. With the exception of the sample from a western province, all the soils investigated contained little organic matter. The content of soil elements did not vary widely among geographical regions. The concentration of most micro elements was within the range of worldwide soil values but the value for Zn tended to be moderately higher. The U (VI) sorption into the soils was investigated using the batch technique and the (237)U radionuclide tracer, produced by the photo fission reaction (238)U(γ, n) (237)U at an electron accelerator. The (237)U distribution coefficient (K(d)), derived from the sorption isotherms, was related to solution pH and varying from 9 to 2547 mL g(-1) when the pH ranged between 3 and 7.7. The sorption process was interpreted in terms of the formation of different U (VI) species at given concentrations, calculated using the Speciation program with and without carbonate in the system. The U sorption isotherm displayed two general patterns: one where sorption decreased as solution pH increased, showing a maximum at pH 3, and another pattern revealed an adsorption maximum at pH 5 and then decreased up

Composite polymeric beads containing N,N,N',N'-tetraoctyldiglycolamide for actinide ion uptake from nitric acid feeds: Batch uptake, kinetic modelling and column studies.

PubMed

Gujar, R B; Mohapatra, P K; Lakshmi, D Shanthana; Figoli, A

2015-11-27

Polyethersulphone (PES) based composite polymeric beads (CPB) containing TODGA (N,N,N',N'-tetraoctyldiglycolamide) as the extractant were prepared by conventional phase inversion technique and were tested for the uptake of actinide ions such as Am(3+), UO2(2+), Pu(4+), Np(4+) and fission product ions such as Eu(3+) and Sr(2+). The CPBs containing 2.5-10wt.% TODGA were characterized by various physical methods and their porosity, size, surface morphology, surface area and the degradation profile by thermogravimetry were analyzed. The batch uptake studies involved kinetics of metal ion sorption, uptake as a function of nitric acid concentration, kinetic modelling and adsorption isotherms and most of the studies involved the Am(3+) ions. The batch saturation sorption capacities for Eu(3+) loading at 3M HNO3 were determined to be 6.6±0.02, 9.1±0.02 and 22.3±0.04mgg(-1) of CRBs with 2.5wt.%, 5wt.% and 10wt.% TODGA, respectively. The sorption isotherm analysis with Langmuir, D-R and Freundlisch isotherms indicated chemisorption monolayer mechanism. Chromatographic studies indicated breakthrough of Eu(3+) (using a solution containing Eu carrier) after about 0.75 bed volume (3.5-4mL). Elution of the loaded Eu was carried out using 0.01M EDTA as the eluent. Copyright © 2015 Elsevier B.V. All rights reserved.

Sorption of dodecyltrimethylammonium chloride (DTAC) to agricultural soils.

PubMed

Xiang, Lei; Sun, Teng-Fei; Zheng, Mei-Jie; Li, Yan-Wen; Li, Hui; Wong, Ming-Hung; Cai, Quan-Ying; Mo, Ce-Hui

2016-08-01

Quaternary ammonium compounds (QACs) used as cationic surfactants are intensively released into environment to be pollutants receiving more and more concerns. Sorption of dodecyltrimethylammonium chloride (DTAC), one of commonly used alkyl QACs, to five types of agricultural soils at low concentrations (1-50mg/L) was investigated using batch experiments. DTAC sorption followed pseudo-second-order kinetics and reached reaction equilibrium within 120min. Both Freundlich model and Langmuir model fitted well with DTAC isotherm data with the latter better. DTAC sorption was spontaneous and favorable, presenting a physical sorption dominated by ion exchanges. Sorption distribution coefficient and sorption affinity demonstrated that soil clay contents acted as a predominant phase of DTAC sorption. DTAC could display a higher mobility and potential accumulation in crops in the soils with lower clay contents and lower pH values. Sorption of DTAC was heavily affected by ions in solution with anion promotion and cation inhibition. Copyright © 2016. Published by Elsevier B.V.

Six-month color change and water sorption of 9 new-generation flowable composites in 6 staining solutions.

PubMed

Arregui, Maria; Giner, Luis; Ferrari, Marco; Vallés, Marta; Mercadé, Montserrat

2016-11-28

Color match and water sorption are two factors that affect restorative materials. Discoloration is essential in the lifespan of restorations. The aim of this study was to evaluate color change and water sorption of nine flowable composites at multiple time points over 6 months. 60 samples of each composite were divided into two groups (Color Change and Water Sorption/Solubility). Each Color Change group was divided into six subgroups, which were immersed in distilled water (DW), coffee (CF), Coca-Cola (CC), red wine (RW), tea (TE) and orange juice (OJ). The color was measured at the baseline, 1, 2, 3 and 4 weeks, and 3 and 6 months and color change values (ΔE) were calculated. Each Water Sorption [WS]/Solubility [WL] group was tested according to ISO 4049:2009. The data were evaluated using two-way ANOVA, Fisher's post-hoc test and Pearson's correlation test. The composite with the lowest ΔE differed for each solution: Filtek™ Bulk Fill in DW (∆E = 0.73 (0.17-1.759)); Vertise Flow in CF (∆E = 14.75 (7.91-27.41)), in TE (∆E = 7.27 (2.81-24.81)) and OJ (∆E = 3.17 (0.87-9.92)); Tetric EvoFlow® in CC (∆E = 1.27 (0.45-4.02)); and Filtek™ Supreme XTE in RW (∆E = 8.88 (5.23-19.59)). RW caused the most discoloration (∆E = 23.62 (4.93-51.36)). Vertise Flow showed the highest water sorption (WS = 69.10 ± 7.19). The Pearson test showed statistically significant positive correlations between water sorption and solubility and between water sorption and ∆E; the positive solubility-∆E correlation was not statistically significant. The findings suggest that water sorption is one factor associated with the ability of composites to discolor; however, discoloration is a multifactorial problem.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

PubMed

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

Modeling and Uncertainty Quantification of Vapor Sorption and Diffusion in Heterogeneous Polymers

DOE PAGES

Sun, Yunwei; Harley, Stephen J.; Glascoe, Elizabeth A.

2015-08-13

A high-fidelity model of kinetic and equilibrium sorption and diffusion is developed and exercised. The gas-diffusion model is coupled with a triple-sorption mechanism: Henry’s law absorption, Langmuir adsorption, and pooling or clustering of molecules at higher partial pressures. Sorption experiments are conducted and span a range of relative humidities (0-95%) and temperatures (30-60°C). Kinetic and equilibrium sorption properties and effective diffusivity are determined by minimizing the absolute difference between measured and modeled uptakes. Uncertainty quantification and sensitivity analysis methods are described and exercised herein to demonstrate the capability of this modeling approach. Water uptake in silica-filled and unfilled poly(dimethylsiloxane) networksmore » is investigated; however, the model is versatile enough to be used with a wide range of materials and vapors.« less

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.

Sorption of lead by settling pond soils after reclamation treatments

NASA Astrophysics Data System (ADS)

Asensio, Verónica; Forján, Rubén; Vega, Flora A.; Andrade, Luisa; Covelo, Emma F.

2013-04-01

The reclamation of degraded soils adding waste amendments can add significant concentrations of Pb. Because of this, it is important to know the sorption capacity of Pb by the soils where wastes with high concentrations of this metal are applied. To determine the sorption capacity of Pb by mine soils, before and after reclamation treatments, four different sites were selected at a settling pond mine zone: an untreated one as the control sample (B1), a vegetated one with pines for 21 years (B2v), a vegetated with eucalyptus for 6 years (B3v) and an amended with sewage sludges and paper mill residues for 5 months (B4w). All soils had one horizon except B4w, where twice were sampled (B4Aw and B4Bw). The B4Bw is considered analogous of the control soil. To evaluate the sorption capacity by the soils, sorption isotherms were constructed using single-metal solutions of Pb2+ nitrates (0.03, 0.05, 0.08, 0.1 and 0.5 mmol L-1) containing 0.01 M NaNO3 as background electrolyte (Vega et al., 2009). The overall capacity of the soil to sorb Pb was evaluated as the slope Kr (Vega et al., 2008). The obtained results show that the sorption isotherm of Pb by control soil (B1) and its analogous (B4Bw) are of L-type curve, whereas the sorption isotherms of the treated soils (B2v, B3v and B4Aw) are of H-type curve (Giles et al., 1974). The most of the obtained isotherms do not fit with the models of Langmuir or Freundlich, therefore sorption capacity was evaluated by Kr parameter. According to the obtained Kr parameter, B1 and B4Bw have the lowest Pb sorption capacity (Kr = 0.480 and 0.556, respectively), which increased two times after recently waste amending (B4Aw; Kr = 0.998). The vegetated sites (B2v and B3v) also have higher sorption capacity than B1, but lower than B4Aw (Kr = 0.692 and 0.725, respectively). The highest sorption capacity of Pb by the amended soil is due to its characteristics such as high pH and organic carbon content. This is corroborated by the significantly

Graphical determination of metal bioavailability to soil invertebrates utilizing the Langmuir sorption model

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

Donkin, S.G.

1997-09-01

A new method of performing soil toxicity tests with free-living nematodes exposed to several metals and soil types has been adapted to the Langmuir sorption model in an attempt at bridging the gap between physico-chemical and biological data gathered in the complex soil matrix. Pseudo-Langmuir sorption isotherms have been developed using nematode toxic responses (lethality, in this case) in place of measured solvated metal, in order to more accurately model bioavailability. This method allows the graphical determination of Langmuir coefficients describing maximum sorption capacities and sorption affinities of various metal-soil combinations in the context of real biological responses of indigenousmore » organisms. Results from nematode mortality tests with zinc, cadmium, copper, and lead in four soil types and water were used for isotherm construction. The level of agreement between these results and available literature data on metal sorption behavior in soils suggests that biologically relevant data may be successfully fitted to sorption models such as the Langmuir. This would allow for accurate prediction of soil contaminant concentrations which have minimal effect on indigenous invertebrates.« less

Insights into the attenuated sorption of organic compounds on black carbon aged in soil.

PubMed

Luo, Lei; Lv, Jitao; Chen, Zien; Huang, Rixiang; Zhang, Shuzhen

2017-12-01

Sorption of organic compounds on fresh black carbons (BCs) can be greatly attenuated in soil over time. We examined herein the changes in surface properties of maize straw-derived BCs (biochars) after aged in a black soil and their effects on the sorptive behaviors of naphthalene, phenanthrene and 1,3-dinitrobenzene. Dissolved fulvic and humic acids extracted from the soil were used to explore the role of dissolved organic carbon (DOC) in the aging of biochars. Chromatography analysis indicated that DOC molecules with relatively large molecular weight were preferentially adsorbed on the biochars during the aging processes. DOC sorption led to blockage of the biochar's micropores according to N 2 and CO 2 adsorption analyses. Surface chemistry of the biochars was also substantially modified, with more O-rich functional groups on the aged biochars compared to the original biochars, as evidenced by Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. The changes in both the physical and chemical surface properties of biochars by DOC led to significant attenuation of the sorption capacity and nonlinearity of the nonionic organic compounds on the aged biochars. Among the tested organic compounds, phenanthrene was the most attenuated in its sorption by the aging treatments, possibly because of its relatively large molecular size and hydrophobicity. The information can help gain a mechanistic understanding of interactions between BCs and organic compounds in soil environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Phenylurea herbicide sorption to biochars and agricultural soil

PubMed Central

WANG, DAOYUAN; MUKOME, FUNGAI N. D.; YAN, DENGHUA; WANG, HAO; SCOW, KATE M.; PARIKH, SANJAI J.

2016-01-01

Biochar is increasingly been used as a soil amendment to improve water holding capacity, reduce nutrient leaching, increase soil pH and also as a means to reduce contamination through sorption of heavy metals or organic pollutants. The sorption behavior of three phenylurea herbicides (monuron, diuron, linuron) on five biochars (Enhanced Biochar, Hog Waste, Turkey Litter, Walnut Shell and Wood Feedstock) and an agricultural soil (Yolo silt loam) was investigated using a batch equilibration method. Sorption isotherms of herbicides to biochars were well described by the Freundlich model (R2 = 0.93 -- 0.97). The adsorption KF values ranged from 6.94 to 1306.95 mg kg−1 and indicated the sorption of herbicides in the biochars and Yolo soil was in the sequence of linuron > diuron > monuron and walnut shell biochar > wood feedstock biochar > turkey litter biochar > enhanced biochar > hog waste biochar > Yolo soil. These data show that sorption of herbicides to biochar can have both positive (reduced off-site transport) and negative (reduced herbicide efficacy) implications and specific biochar properties, such as H/C ratio and surface area, should be considered together with soil type, agriculture chemical and climate condition in biochar application to agricultural soil to optimize the system for both agricultural and environmental benefits. PMID:26065514

Studies of anions sorption on natural zeolites.

PubMed

Barczyk, K; Mozgawa, W; Król, M

2014-12-10

This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption mechanism of Cd(II) from water solution onto chicken eggshell

NASA Astrophysics Data System (ADS)

Flores-Cano, Jose Valente; Leyva-Ramos, Roberto; Mendoza-Barron, Jovita; Guerrero-Coronado, Rosa María; Aragón-Piña, Antonio; Labrada-Delgado, Gladis Judith

2013-07-01

The mechanism and capacity of eggshell for sorbing Cd(II) from aqueous solution was examined in detail. The eggshell was characterized by several techniques. The eggshell was mainly composed of Calcite (CaCO3). The surface charge distribution was determined by acid-base titration and the point of zero charge (PZC) of the eggshell was found to be 11.4. The sorption equilibrium data were obtained in a batch adsorber, and the adsorption isotherm of Langmuir fitted the data quite well. The sorption capacity of eggshell increased while raising the pH from 4 to 6, this tendency was attributed to the electrostatic interaction between the Cd2+ in solution and the surface of the eggshell. Furthermore, the sorption capacity was augmented by increasing the temperature from 15 to 35 °C because the sorption was endothermic. The sorption of Cd(II) occurred mainly onto the calcareous layer of the eggshell, but slightly on the membrane layer. It was demonstrated that the sorption of Cd(II) was not reversible, and the main sorption mechanisms were precipitation and ion exchange. The precipitation of (Cd,Ca)CO3 on the surface of the eggshell was corroborated by SEM and XRD analysis.

First Measurements of 15N Fractionation in N2H+ toward High-mass Star-forming Cores

NASA Astrophysics Data System (ADS)

Fontani, F.; Caselli, P.; Palau, A.; Bizzocchi, L.; Ceccarelli, C.

2015-08-01

We report on the first measurements of the isotopic ratio 14N/15N in N2H+ toward a statistically significant sample of high-mass star-forming cores. The sources belong to the three main evolutionary categories of the high-mass star formation process: high-mass starless cores, high-mass protostellar objects, and ultracompact H ii regions. Simultaneous measurements of the 14N/15N ratio in CN have been made. The 14N/15N ratios derived from N2H+ show a large spread (from ∼180 up to ∼1300), while those derived from CN are in between the value measured in the terrestrial atmosphere (∼270) and that of the proto-solar nebula (∼440) for the large majority of the sources within the errors. However, this different spread might be due to the fact that the sources detected in the N2H+ isotopologues are more than those detected in the CN ones. The 14N/15N ratio does not change significantly with the source evolutionary stage, which indicates that time seems to be irrelevant for the fractionation of nitrogen. We also find a possible anticorrelation between the 14N/15N (as derived from N2H+) and the H/D isotopic ratios. This suggests that 15N enrichment could not be linked to the parameters that cause D enrichment, in agreement with the prediction by recent chemical models. These models, however, are not able to reproduce the observed large spread in 14N/15N, pointing out that some important routes of nitrogen fractionation could be still missing in the models. Based on observations carried out with the IRAM-30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).

Bifunctional 3D porous Cu(I) metal-organic framework with gas sorption and luminescent properties

NASA Astrophysics Data System (ADS)

Xing, Guang'en; Zhang, Yan; Cao, Xiulian

2017-10-01

A new Cu(I) metal-organic framework, namely [Cu(L)]2n·n(H2O) (1 HL = 5-(4-Pyridyl)-1H-tetrazole), has been successfully synthesized via the solvothermal reactions of CuI and 5-(4-Pyridyl)-1H-tetrazole ligand, and further characterized by elemental analysis, powder X-ray diffraction analysis, thermal analysis and single crystal X-ray structural analysis. The L- ligand displays a μ4-N2, N3, N4, N5 coordination mode bridging Cu(I) ions into a 3D porous framework with the opened 1D channels filled by the lattice water molecules. Gas sorption investigations indicated that compound 1 can selectively adsorb CO2 over N2 at 298 K, and luminescent properties investigations revealed that compound 1 features luminescent sensing function for nitrobenzene.

Sorption behaviour of nonylphenol and nonylphenol monoethoxylate in soils.

PubMed

Milinovic, J; Lacorte, S; Rigol, A; Vidal, M

2015-11-01

Sorption behaviour of two alkylphenolic compounds (APCs), nonylphenol (NP) and nonylphenol monoethoxylate (NP1EO), was studied in five soils with contrasting characteristics. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions containing different initial concentrations of NP or NP1EO. Linear fitting was generally appropriate for describing the sorption behaviour of NP and NP1EO in the soils, with the exception of two cases, for which the Freundlich model was more suitable for describing the sorption pattern of NP1EO. Solid-liquid distribution coefficients derived from sorption isotherms (Kd) varied from 24 to 1059 mL g(-1) for NP and from 51 to 740 mL g(-1) for NP1EO. For most soils, sorption Kd values were higher for NP than for NP1EO due to the higher hydrophobicity of NP. Sorption reversibility of NP and NP1EO was also tested from desorption isotherms. Desorption solid-liquid distribution coefficients (Kd,des), obtained from linear fitting, were between 130 and 1467 mL g(-1) for NP and between 24 and 1285 mL g(-1) for NP1EO. Kd,des values were higher than Kd values, which demonstrated that target compounds were irreversibly sorbed into soils, with the exception of the high desorption yield (45%) of NP1EO in the soil with the lowest content of organic matter. The fraction of soil organic carbon (FOC) was a key parameter that influenced the sorption of NP and NP1EO in soils, with logKOC values of 4.0 and 3.8, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Role of interlayer hydration in lincomycin sorption by smectite clays.

PubMed

Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

2009-08-15

Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

SORPTION OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN TO SOILS FROM WATER/METHANOL MIXTURES

EPA Science Inventory

Sorption of ¹⁴C-labeled 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to soils from water/methanol mixtures has been evaluated by batch shake testing. Uncontaminated soils from Times Beach, MO, were used in these experiments and ranged in fraction organic carbon (U...

SORPTION ON WASTEWATER SOLIDS: ELIMINATION OF BIOLOGICAL ACTIVITY

EPA Science Inventory

Sorption was found to be greatly affected by the biological activity in wastewater solids. wo experimental techniques, cyanide treatment and pasteurization, were developed for eliminating the biological activity during isotherm measurements. oth methods are effective; however, pa...

Milestone Report:3.2.2.26 Appliances, HVAC & Water Heating R&D-Select Sorption Technology

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

Ally, Moonis Raza

The purpose of this report is to select a sorption technology based on recent work completed on characterizing working pairs for both absorption and adsorption technologies based on Global Warming Potential (GWP) of less than 100 (relative to carbon dioxide, 100-year atmospheric life span) and zero Ozone Depletion Potential (ODP). From a total of eighty-three potential working pairs (absorption technology), there were only two candidate working pairs for the absorption technology, and 8 potential working pairs for adsorption technology. After screening these ten potential candidates on the basis of sizes of the desorber, absorber/adsorber, evaporator, condenser, and rectifier (where applicable),more » the ORNL-Georgia Tech study concluded that best working pairs are NH3-H2O for the most compact system in terms of heat transfer equipment surface area, and NH3-LiNO3 and MeOH-[mmin][DMP] where efficiency is most important. Based on a single-stage absorption and adsorption modeling using the Engineering Equation Solver (EES), the performance of both sorption systems was evaluated from known heat transfer correlations, and thermos-physical properties. Based on these results, the technology chosen is absorption technology. The selected technology is absorption for the reasons cited in Section 4.« less

Sorption of uranium (VI) on homoionic sodium smectite experimental study and surface complexation modeling.

PubMed

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2

Impact of bleaching agents on water sorption and solubility of resin luting cements.

PubMed

Torabi Ardakani, Mahshid; Atashkar, Berivan; Bagheri, Rafat; Burrow, Michael F

2017-08-01

The aim of the present study was to evaluate the effect of distilled water and home and office bleaching agents on the sorption and solubility of resin luting cements. A total of 18 disc-shaped specimens were prepared from each of four resin cements: G-CEM LinkAce, Panavia F, Rely X Unicem, and seT. Specimens were cured according to the manufacturers' instructions and randomly divided into three groups of six, where they were treated with either an office or home bleaching agent or immersed in distilled water (control). Water sorption and solubility were measured by weighing the specimens before and after immersion and desiccation. Data were analyzed using Pearson correlation coefficient, two-way analysis of variance (ANOVA) and Tukey's test. There was a significant, positive correlation between sorption and solubility. Two-way anova showed significant differences among all resin cements tested for either sorption or solubility. Water sorption and solubility of all cements were affected significantly by office bleaching, and even more by home bleaching agents. Sorption and solubility behavior of the studied cements were highly correlated and significantly affected by applying either office or home bleaching agents; seT showed the highest sorption and solubility, whereas Rely X Unicem revealed the lowest. © 2016 John Wiley & Sons Australia, Ltd.

The sorption properties of polymers with molecular imprints of chlorine-containing pesticides

NASA Astrophysics Data System (ADS)

Popov, S. A.; Dmitrienko, S. G.; Chumichkina, Yu. A.; Zolotov, Yu. A.

2009-04-01

Polymers with molecular imprints of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6-dichloro-2-methoxybenzoic acid (dicamba), and (RS)-1- p-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol and the corresponding blank polymers were synthesized using acrylamide as a functional monomer. The specific surface area of the resulting materials was estimated and their sorption properties were studied. It was found that the sorption characteristics of the polymers with molecular imprints of chlorine-containing pesticides depended on the nature of template molecules, functional monomer: template ratio in the polymerization mixture, and nature and content of solvents varied at the synthesis stage. According to the sorption isotherms, the difference in the sorption behavior of molecularly imprinted and blank polymers was observed over a wide range of chlorine-containing pesticide concentrations. The selectivity of the adsorbent with 2,4-D imprints was estimated for the example of structurally related compounds.

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: influence of Mn/Fe ratio, pH, Ca2+, and humic acid.

PubMed

Zhang, Gaosheng; Liu, Huijuan; Qu, Jiuhui; Jefferson, William

2012-01-15

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater. Copyright © 2011 Elsevier Inc. All rights reserved.

Potential for biodegradation and sorption of acetaminophen, caffeine, propranolol and acebutolol in lab-scale aqueous environments.

PubMed

Lin, Angela Yu-Chen; Lin, Chih-Ann; Tung, Hsin-Hsin; Chary, N Sridhara

2010-11-15

Sorption and combined sorption-biodegradation experiments were conducted in laboratory batch studies with 100 g soil/sediments and 500 mL water to investigate the fates in aqueous environments of acetaminophen, caffeine, propranolol, and acebutolol, four frequently used and often-detected pharmaceuticals. All four compounds have demonstrated significant potential for degradation and sorption in natural aqueous systems. For acetaminophen, biodegradation was found to be a primary mechanism for degradation, with a half-life (t(1/2)) for combined sorption-biodegradation of 2.1 days; in contrast, sorption alone was responsible only for a 30% loss of aqueous-phase acetaminophen after 15 days. For caffeine, both biodegradation and sorption were important (t(1/2) for combined sorption-biodegradation was 1.5 days). However, for propranolol and acebutolol, sorption was found to be the most significant removal mechanism and was not affected by biodegradation. Desorption experiments revealed that the sorption process was mostly irreversible. High values were found for K(d) for caffeine, propranolol, and acebutolol, ranging from 250 to 1900 L kg(-1), which explained their greater tendency for sorption onto sediments, compared to the more hydrophilic acetaminophen. Experimentally derived values for logK(oc) differed markedly from values calculated from correlation equations. This discrepancy was attributed to the fact that these equations are well suited for hydrophobic interactions but may fail to predict the sorption of polar and ionic compounds. These results suggest that mechanisms other than hydrophobic interactions played an important role in the sorption process. Copyright © 2010 Elsevier B.V. All rights reserved.

Laboratory Measurements of SO2 and N2 Absorption Spectra for Planetary Atmospheres

NASA Technical Reports Server (NTRS)

Stark, Glenn

2003-01-01

This laboratory project focuses on the following topics: 1) Measurement of SO2 ultraviolet absorption cross sections; and 2) N2 band and Line Oscillator Strengths and Line Widths in the 80 to 100 nm region. Accomplishments for these projects are summarized.

Isotope studies to the sorption behavior of atmospheric sulfate in humus layers of scots pine ecosystems.

PubMed

Schulz, H; Neue, H-U

2005-03-01

The sorption potential for SO4(2-) in humus layer samples from field sites along a deposition gradient was determined experimentally in batch experiments. The Freundlich equation was used to quantify the sorption of added SO4(2-) in humus layer samples and to determine site-dependent sorption parameters. SO4(2-) sorption in humus layers is a concentration-dependent process. The linearity of isotherms reveals that SO4(2-) is reversibly bound in the organic surface layer, as long as soil solution concentrations remain above 26 to 44 mg SO4(2-) L(-1). Natural isotope variations of sulfur in SO4(2-) were analysed to investigate the degree of sorption of dissolved atmospheric and added SO4(2-). Both sulfate species differed significantly in their isotope composition. The pattern of delta34S values for SO4(2-) in all equilibrium solutions confirm the findings from sorption isotherms, showing a close relationship between the sulfur isotope ratios of SO4(2-) in soil solutions and the amount of SO4(2-) sorbed at the humus layer matrix. Stored atmospheric SO4(2-) in humus layers is released at sites where sulfate concentration in throughfall drops below 26 mg SO4(2-) L(-1). Concentration of soluble Fe decreased with increasing sulfate sorption, thus supporting the assumption that active Fe for example is important. Iron probably stabilizes the reactive surface of humus complexes and therefore has a positive influence on the SO4(2-) sorption in humus layers.

Sorption of organic chemicals at biogeochemical interfaces - calorimetric measurements

NASA Astrophysics Data System (ADS)

Krüger, J.; Lang, F.; Siemens, J.; Kaupenjohann, M.

2009-04-01

Biogeochemical interfaces in soil act as sorbents for organic chemicals, thereby controlling the degradation and mobility of these substances in terrestrial environments. Physicochemical properties of the organic chemicals and the sorbent determine sorptive interactions. We hypothesize that the sorption of hydrophobic organic chemicals ("R-determined" chemicals) is an entropy-driven partitioning process between the bulk aqueous phase and biogeochemical interface and that the attachment of more polar organic chemicals ("F-determined" chemicals) to mineral surfaces is due to electrostatic interactions and ligand exchange involving functional groups. In order to determine thermodynamic parameters of sorbate/sorbent interactions calorimetric titration experiments have been conducted at 20˚ C using a Nanocalorimeter (TAM III, Thermometric). Solutions of different organic substances ("R-determined" chemicals: phenanthrene, bisphenol A, "F-determined" chemicals: MCPA, bentazone) with concentrations of 100 mol l-1 were added to suspensions of pure minerals (goethite, muscovite, and kaolinite and to polygalacturonic acid (PGA) as model substance for biofilms in soil. Specific surface, porosity, N and C content, particle size and point of zero charge of the mineral were analyzed to characterize the sorbents. The obtained heat quantities for the initial injection of the organic chemicals to the goethite were 55 and 71 J for bisphenol A and phenanthrene ("R-determined representatives") and 92 and 105 J for MCPA and bentazone ("F-determined" representatives). Further experiments with muscovite, kaolinite and PGA are in progress to determine G and H of the adsorption process.

Biochar modification to enhance sorption of inorganics from water.

PubMed

Sizmur, Tom; Fresno, Teresa; Akgül, Gökçen; Frost, Harrison; Moreno-Jiménez, Eduardo

2017-12-01

Biochar can be used as a sorbent to remove inorganic pollutants from water but the efficiency of sorption can be improved by activation or modification. This review evaluates various methods to increase the sorption efficiency of biochar including activation with steam, acids and bases and the production of biochar-based composites with metal oxides, carbonaceous materials, clays, organic compounds, and biofilms. We describe the approaches, and explain how each modification alters the sorption capacity. Physical and chemical activation enhances the surface area or functionality of biochar, whereas modification to produce biochar-based composites uses the biochar as a scaffold to embed new materials to create surfaces with novel surface properties upon which inorganic pollutants can sorb. Many of these approaches enhance the retention of a wide range of inorganic pollutants in waters, but here we provide a comparative assessment for Cd 2+ , Cu 2+ , Hg 2+ , Pb 2+ , Zn 2+ , NH 4 + , NO 3 - , PO 4 3- , CrO 4 2- and AsO 4 3- . Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption of nonpolar aromatic contaminants by chlorosilane surface modified natural minerals.

PubMed

Huttenloch, P; Roehl, K E; Czurda, K

2001-11-01

The efficacy of the surface modification of natural diatomite and zeolite material by chlorosilanes is demonstrated. Chlorosilanes used were trimethylchlorosilane (TMSCI), tert-butyldimethylchlorosilane (TBDMSCI), dimethyloctadecylchlorosilane (DMODSCI), and diphenyldichlorosilane (DPDSCI) possessing different headgroups and chemical properties. Silanol groups of the diatomite and zeolite were modified by chemical reaction with the chlorosilanes resulting in a stable covalent attachment of the organosilanes to the mineral surface. The alteration of surface properties of the modified material was proved by measurements of water adsorption capacity, total organic carbon (TOC) content, and thermoanalytical data. The surface modified material showed great stability even when exposed to extremes in ionic strength, pH, and to pure organic solvents. Sorption of toluene, o-xylene, and naphthalene from water was greatly enhanced by the surface modification compared to the untreated materials which showed no measurable sorption of these compounds. The enhanced sorption was dependent on the organic carbon content as well as on chemical characteristics of the chlorosilanes used. Batch sorption experiments showed that the phenyl headgroups of DPDSCI have the best affinity for aromatic compounds. Removal from an aqueous solution of 10 mg/L of naphthalene, o-xylene, and toluene was 71%, 60%, and 30% for surface modified diatomite and 51%, 30%, and 16% for modified clinoptilolite, respectively. Sorption data were well described by the Freundlich isotherm equation, which indicated physical adsorption onto the lipophilic surface rather than partitioning into the surface organic phase. The chlorosilane modified materials have an apparent potential for application in environmental technologies such as permeable reactive barriers (PRB) or wastewater treatment.

Reducing bioavailability and phytotoxicity of 2,4-dinitrotoluene by sorption on K-smectite clay.

PubMed

Roberts, Michael G; Rugh, Clayton L; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2007-02-01

Smectite clays demonstrate high affinities for nitroaromatics that strongly depend on the exchangeable cation. The K-smectites have high affinities for nitroaromatics, but Ca-smectites do not. Here we evaluate the ability of K-smectite to attenuate the bioavailability and hence toxicity of 2,4-dinitrotoluene (2,4-DNT) to the aquatic plant duckweed. In the absence of K-smectite, 2,4-DNT was highly toxic to duckweed. Small amounts of K-smectite reduced toxicity substantially, presumably by reducing 2,4-DNT bioavailability via sorption.

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

PubMed

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

2010-07-01

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

Sorption of polar herbicides and herbicide metabolites by biochar-amended soil.

PubMed

Dechene, Annika; Rosendahl, Ingrid; Laabs, Volker; Amelung, Wulf

2014-08-01

Biochar-amended soil has been proven to possess superior sorption capacities for several environmental pollutants compared with pure soil. However, the role of biochar in the immobilization of polar pesticides and their metabolites has hardly been tested. The aim of this study was therefore to investigate the effect of a soil amendment with biochar on the sorption of selected polar herbicides and herbicide metabolites (log Kow 0.3-<2). To simulate worst-case sorption, a sandy soil (1.7% organic matter) was amended with 1.5% biochar (fresh or composted) to determine sorption/desorption isotherms of the test compounds. One herbicide (imazamox) and three herbicide metabolites (methyl-desphenyl-chloridazon, metazachlor oxalic acid, metazachlor sulfonic acid) were tested, i.e. three anionic and one neutral polar compound. The results showed that the presence of biochar increased the sorption capacity of the soil only in the case of the uncharged compound methyl-desphenyl-chloridazon, for which the average distribution coefficients in biochar-amended soils were higher than in pure soil by a factor of 2.1-2.5. However, this effect rather seemed to reflect the increased soil organic carbon content after the addition of biochar than a preferred sorption of methyl-desphenyl-chloridazon to biochar. In the case of the three anionic compounds imazamox, metazachlor oxalic acid and metazachlor sulfonic acid, biochar amendment did not increase the sorption capacity of the soil for these compounds, presumably as a result of its negative net charge. Similarly, desorption experiments did not show any significant effect of the biochar amendment on desorption. This suggests that the potential of using biochar to mitigate the leaching of the tested polar pesticides or metabolites is limited. Copyright © 2014 Elsevier Ltd. All rights reserved.

Maize, switchgrass, and ponderosa pine biochar added to soil increased herbicide sorption and decreased herbicide efficacy.

PubMed

Clay, Sharon A; Krack, Kaitlynn K; Bruggeman, Stephanie A; Papiernik, Sharon; Schumacher, Thomas E

2016-08-02

Biochar, a by-product of pyrolysis made from a wide array of plant biomass when producing biofuels, is a proposed soil amendment to improve soil health. This study measured herbicide sorption and efficacy when soils were treated with low (1% w/w) or high (10% w/w) amounts of biochar manufactured from different feedstocks [maize (Zea mays) stover, switchgrass (Panicum vigatum), and ponderosa pine (Pinus ponderosa)], and treated with different post-processing techniques. Twenty-four hour batch equilibration measured sorption of (14)C-labelled atrazine or 2,4-D to two soil types with and without biochar amendments. Herbicide efficacy was measured with and without biochar using speed of seed germination tests of sensitive species. Biochar amended soils sorbed more herbicide than untreated soils, with major differences due to biochar application rate but minor differences due to biochar type or post-process handling technique. Biochar presence increased the speed of seed germination compared with herbicide alone addition. These data indicate that biochar addition to soil can increase herbicide sorption and reduce efficacy. Evaluation for site-specific biochar applications may be warranted to obtain maximal benefits without compromising other agronomic practices.

Soil sorption of organic vapors and effects of humidity on sorptive mechanism and capacity

USGS Publications Warehouse

Chiou, C.T.; Shoup, T.D.

1985-01-01

Vapor sorption isotherms on dry Woodburn soil at 20-30??C were determined for benzene, chlorobenzene, p-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, and water as single vapors and for benzene, m-dichlorobenzene, and 1,2,4-trichlorobenzene as functions of relative humidity (RH). Isotherms for all compounds on dry soil samples are distinctively nonlinear, with water showing the greatest capacity. Water vapor sharply reduced the sorption capacities of organic compounds with the dry soil; on water-saturated soil, the reduction was about 2 orders of magnitude. The markedly higher sorption of organic vapors at subsaturation humidities is attributed to adsorption on the mineral matter, which predominates over the simultaneous uptake by partition into the organic matter. At about 90% RH, the sorption capacities of organic compounds become comparable to those in aqueous systems. The effect of humidity is attributed to adsorptive displacement by water of organics adsorbed on the mineral matter. A small residual uptake is attributed to the partition into the soil-organic phase that has been postulated in aqueous systems. The results are essentially in keeping with the model that was previously proposed for sorption on the soil from water and from organic solvents.Vapor sorption isotherms on dry Woodburn soil at 20-30 degree C were determined for benzene, chlorobenzene, p-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, and water as single vapors and for benzene, m-dichlorobenzene, and 1,2,4-trichlorobenzene as functions of relative humidity (RH). Isotherms for all compounds on dry soil samples are distinctively nonlinear, with water showing the greatest capacity. Water vapor sharply reduced the sorption capacities of organic compounds with the dry soil; on water-saturated soil, the reduction was about 2 orders of magnitude. The markedly higher sorption of organic vapors at subsaturation humidities is attributed to adsorption on the mineral matter

PCB Congener Sorption To Carbonaceous Sediment Components: Macroscopic Comparison And Characterization Of Sorption Kinetics And Mechanism

EPA Science Inventory

Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparati...

Pyrethroid sorption to Sacramento River suspended solids and bed sediments

PubMed Central

Fojut, Tessa L.; Young, Thomas M.

2011-01-01

Sorption of pyrethroid insecticides to solid materials will typically dominate the fate and transport of these hydrophobic compounds in aquatic environments. Batch reactor isotherm experiments were performed with bifenthrin and λ-cyhalothrin with suspended material and bed sediment collected from the Sacramento River, CA. These batch reactor experiments were performed with low spiking concentrations and a long equilibration time (28 d) to be more relevant to environmental conditions. Sorption to suspended material and bed sediment was compared to examine the role of differential sorption between these phases in the environmental transport of pyrethroids. The equilibrium sorption data were fit to the Freundlich isotherm model and fit with r2 > 0.87 for all experiments. Freundlich exponents ranged from 0.72 ± 0.19 to 1.07 ± 0.050, indicating sorption nonlinearity for some of the experimental conditions and linearity for others over the concentration range tested. The Freundlich capacity factors were larger for the suspended solids than for the bed sediments and the suspended material had a higher specific surface area and higher organic carbon content compared to the bed sediment. Calculated organic carbon-normalized distribution coefficients were larger than those previously reported in the literature by approximately an order of magnitude and ranged from 106.16 to 106.68 at an equilibrium aqueous concentration of 0.1 µg/L. Higher than expected sorption of pyrethroids to the tested materials may be explained by sorption to black carbon and/or mineral surfaces. PMID:21191877

Sorption of Cm(III) and Eu(III) onto clay minerals under saline conditions: Batch adsorption, laser-fluorescence spectroscopy and modeling

NASA Astrophysics Data System (ADS)

Schnurr, Andreas; Marsac, Rémi; Rabung, Thomas; Lützenkirchen, Johannes; Geckeis, Horst

2015-02-01

The present work reports experimental data for trivalent metal cation (Cm/Eu) sorption onto illite (Illite du Puy) and montmorillonite (Na-SWy-2) in NaCl solutions up to 4.37 molal (m) in the absence of carbonate. Batch sorption experiments were carried out for a given ionic strength at fixed metal concentration (mEu = 2 × 10-7 m, labeled with 152Eu for γ-counting) and at a constant solid to liquid ratio (S:L = 2 g/L) for 3 < pHm < 12 (pHm = -log mH+). The amount of clay sorbed Eu approaches almost 100% (with log KD > 5) for pHm > 8, irrespective of the NaCl concentration. Variations in Eu uptake are minor at elevated NaCl concentrations. Time-resolved laser fluorescence spectroscopy (TRLFS) studies on Cm sorption covering a wide range of NaCl concentrations reveal nearly identical fluorescence emission spectra after peak deconvolution, i.e. no significant variation of Cm surface speciation with salinity. Beyond the three surface complexes already found in previous studies an additional inner-sphere surface species with a fluorescence peak maximum at higher wavelength (λ ∼ 610 nm) could be resolved. This new surface species appears in the high pH range and is assumed to correspond to a clay/curium/silicate complex as already postulated in the literature for kaolinite. The 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model (2SPNE SC/CE) was applied to describe Eu sorption data by involving the Pitzer and SIT (specific ion interaction) formalism in the calculation of the activities of dissolved aqueous species. Good agreement of model and experiment is achieved for sorption data at pHm < 6 without the need of adjusting surface complexation constants. For pHm > 6 in case of illite and pHm > 8 in case of montmorillonite calculated sorption data systematically fall below experimental data with increasing ionic strength. Under those conditions sorption is almost quantitative and deviations must be discussed considering

Study of Np(V) Sorption by Ionic Exchange on Na, K, Ca and Mg-Montmorillonite

NASA Astrophysics Data System (ADS)

Benedicto, A.; Begg, J.; Zhao, P.; Kersting, A. B.; Zavarin, M.

2012-12-01

The transport behavior of actinides in soil and ground water are highly influenced by clay minerals due to their ubiquity in the environment, reactivity and colloidal properties. Neptunium(V) has been introduced in the environment as a result of nuclear weapons testing [e.g. 1, 2] and is a radionuclide of potential interest for safety assessment of high level radioactive waste disposal because its long half-life and high toxicity [3]. Surface complexation and ionic exchange have been identified as Np(V) sorption mechanisms onto montmorillonite. At pH below 5, Np(V) sorption is mainly attributed to ionic exchange. This study examines Np(V) ion exchange on Na, K, Ca and Mg forms of montmorillonite. Experiments were carried out using 237Np concentrations between 2 x 10-8 M and 5 x 10-6 M at three different ionic strengths 0.1, 0.01 and 0.001M. The pH was maintained at 4.5. Np(V) sorption to montmorillonite homoionized with monovalent cations (Na and K) demonstrated a markedly different behavior to that observed for montmorillonite homoionized with divalent cations (Ca and Mg). Np sorption to Na and K-montmorillonite was greater than Np sorption to Ca and Mg-montmorillonite. Isotherms with Na and K-montmorillonite showed a strong dependence on ionic strength: the percentage of Np adsorbed was near zero at 0.1M ionic strength, but increased to 30% at 0.001 M ionic strength. This suggests ionic exchange is the main Np adsorption mechanism under the experimental conditions investigated. Dependence on ionic strength was not observed in the Np sorption isotherms for Ca and Mg-montmorillonite indicating a low exchange capacity between Np and divalent cations. Modeling of the sorption experimental data will allow determination of the Na+↔NpO2+ and K+↔NpO2+ ionic exchange constants on montmorillonite. References: [1] A. R. Felmy; K. J. Cantrell; S. D. Conradson, Phys. Chem. Earth 2010, 35, 292-297 [2] D. K. Smith; D. L. Finnegan; S. M. Bowen, J. Environ. Radioact. 2003, 67