ISOT_Calc: A versatile tool for parameter estimation in sorption isotherms

NASA Astrophysics Data System (ADS)

Beltrán, José L.; Pignatello, Joseph J.; Teixidó, Marc

2016-09-01

Geochemists and soil chemists commonly use parametrized sorption data to assess transport and impact of pollutants in the environment. However, this evaluation is often hampered by a lack of detailed sorption data analysis, which implies further non-accurate transport modeling. To this end, we present a novel software tool to precisely analyze and interpret sorption isotherm data. Our developed tool, coded in Visual Basic for Applications (VBA), operates embedded within the Microsoft Excel™ environment. It consists of a user-defined function named ISOT_Calc, followed by a supplementary optimization Excel macro (Ref_GN_LM). The ISOT_Calc function estimates the solute equilibrium concentration in the aqueous and solid phases (Ce and q, respectively). Hence, it represents a very flexible way in the optimization of the sorption isotherm parameters, as it can be carried out over the residuals of q, Ce, or both simultaneously (i.e., orthogonal distance regression). The developed function includes the most usual sorption isotherm models, as predefined equations, as well as the possibility to easily introduce custom-defined ones. Regarding the Ref_GN_LM macro, it allows the parameter optimization by using a Levenberg-Marquardt modified Gauss-Newton iterative procedure. In order to evaluate the performance of the presented tool, both function and optimization macro have been applied to different sorption data examples described in the literature. Results showed that the optimization of the isotherm parameters was successfully achieved in all cases, indicating the robustness and reliability of the developed tool. Thus, the presented software tool, available to researchers and students for free, has proven to be a user-friendly and an interesting alternative to conventional fitting tools used in sorption data analysis.

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

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

Chang, J.C.S.

1993-01-01

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

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.

Effects of aged sorption on pesticide leaching to groundwater simulated with PEARL.

PubMed

Boesten, Jos J T I

2017-01-15

Leaching to groundwater is an important element of the regulatory risk assessment of pesticides in western countries. Including aged sorption in this assessment is relevant because there is ample evidence of this process and because it leads to a decrease in simulated leaching. This work assesses the likely magnitude of this decrease for four groundwater scenarios used for regulatory purpose in the EU (from the UK, Portugal, Austria and Greece) and for ranges of aged-sorption parameters and substance properties using the PEARL model. Three aged-sorption parameters sets were derived from literature, representing approximately 5th, 50th and 95th percentile cases for the magnitude of the effect of aged sorption on leaching concentrations (called S, M and L, respectively). The selection of these percentile cases was based only on the f NE parameter (i.e. the ratio of the aged sorption and the equilibrium sorption coefficients) because leaching was much more affected by the uncertainty in this parameter than by the uncertainty in the desorption rate coefficient of these sites (k d ). For the UK scenario, the annual flux concentration of pesticide leaching at 1m depth decreased by typically a factor of 5, 30 and >1000 for the S, M and L parameter sets, respectively. This decrease by a factor of 30 for the M parameter set appeared to be approximately valid also for the other three scenarios. Decreasing the Freundlich exponent N from 0.9 into 0.7 for the M parameter set, increased this factor of 30 into a factor of typically 1000, considering all four scenarios. The aged-sorption sites were close to their equilibrium conditions during the leaching simulations for two of the four scenarios (for all substances considered and the M parameter set), but this was not the case for the other two scenarios. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Molecular surface area based predictive models for the adsorption and diffusion of disperse dyes in polylactic acid matrix.

PubMed

Xu, Suxin; Chen, Jiangang; Wang, Bijia; Yang, Yiqi

2015-11-15

Two predictive models were presented for the adsorption affinities and diffusion coefficients of disperse dyes in polylactic acid matrix. Quantitative structure-sorption behavior relationship would not only provide insights into sorption process, but also enable rational engineering for desired properties. The thermodynamic and kinetic parameters for three disperse dyes were measured. The predictive model for adsorption affinity was based on two linear relationships derived by interpreting the experimental measurements with molecular structural parameters and compensation effect: ΔH° vs. dye size and ΔS° vs. ΔH°. Similarly, the predictive model for diffusion coefficient was based on two derived linear relationships: activation energy of diffusion vs. dye size and logarithm of pre-exponential factor vs. activation energy of diffusion. The only required parameters for both models are temperature and solvent accessible surface area of the dye molecule. These two predictive models were validated by testing the adsorption and diffusion properties of new disperse dyes. The models offer fairly good predictive ability. The linkage between structural parameter of disperse dyes and sorption behaviors might be generalized and extended to other similar polymer-penetrant systems. Copyright © 2015 Elsevier Inc. All rights reserved.

Mini-columns for Conducting Breakthrough Experiments. Design and Construction

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

Dittrich, Timothy M.; Reimus, Paul William; Ware, Stuart Douglas

Experiments with moderately and strongly sorbing radionuclides (i.e., U, Cs, Am) have shown that sorption between experimental solutions and traditional column materials must be accounted for to accurately determine stationary phase or porous media sorption properties (i.e., sorption site density, sorption site reaction rate coefficients, and partition coefficients or K d values). This report details the materials and construction of mini-columns for use in breakthrough columns to allow for accurate measurement and modeling of sorption parameters. Material selection, construction techniques, wet packing of columns, tubing connections, and lessons learned are addressed.

Parameter and observation importance in modelling virus transport in saturated porous media - Investigations in a homogenous system

USGS Publications Warehouse

Barth, Gilbert R.; Hill, M.C.

2005-01-01

This paper evaluates the importance of seven types of parameters to virus transport: hydraulic conductivity, porosity, dispersivity, sorption rate and distribution coefficient (representing physical-chemical filtration), and in-solution and adsorbed inactivation (representing virus inactivation). The first three parameters relate to subsurface transport in general while the last four, the sorption rate, distribution coefficient, and in-solution and adsorbed inactivation rates, represent the interaction of viruses with the porous medium and their ability to persist. The importance of four types of observations to estimate the virus-transport parameters are evaluated: hydraulic heads, flow, temporal moments of conservative-transport concentrations, and virus concentrations. The evaluations are conducted using one- and two-dimensional homogeneous simulations, designed from published field experiments, and recently developed sensitivity-analysis methods. Sensitivity to the transport-simulation time-step size is used to evaluate the importance of numerical solution difficulties. Results suggest that hydraulic conductivity, porosity, and sorption are most important to virus-transport predictions. Most observation types provide substantial information about hydraulic conductivity and porosity; only virus-concentration observations provide information about sorption and inactivation. The observations are not sufficient to estimate these important parameters uniquely. Even with all observation types, there is extreme parameter correlation between porosity and hydraulic conductivity and between the sorption rate and in-solution inactivation. Parameter estimation was accomplished by fixing values of porosity and in-solution inactivation.

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.

Lead and vanadium removal from a real industrial wastewater by gravitational settling/sedimentation and sorption onto Pinus sylvestris sawdust.

PubMed

Kaczala, F; Marques, M; Hogland, W

2009-01-01

Batch sorption with untreated Pinus sylvestris sawdust after settling/sedimentation phase to remove vanadium and lead from a real industrial wastewater was investigated using different adsorbent doses, initial pH, and contact time. The development of pH along the sorption test and a parallel investigation of metals release from sawdust in distilled water were carried out. In order to evaluate kinetic parameters and equilibrium isotherms, Lagergren first-order, pseudo-second-order, intra-particle diffusion and Freundlich models were explored. When the initial pH was reduced from 7.4 to 4.0, the sorption efficiency increased from 32% to 99% for Pb and from 43% to 95% for V. Whereas, V removal was positively correlated with the adsorbent dose, Pb removal was not. The sorption process was best described by pseudo-second-order kinetics. According to Freundlich parameters (K(f) and n) sawdust presented unfavourable intensity for sorption of V.

Is organic matter alone sufficient to predict isoproturon sorption in calcareous soils?

PubMed

El Arfaoui, Achouak; Sayen, Stéphanie; Paris, Michaël; Keziou, Amor; Couderchet, Michel; Guillon, Emmanuel

2012-08-15

Eleven soils collected from Champagne-Ardenne area (France) were used to investigate isoproturon sorption in laboratory conditions. Our results identified the organic matter (OM) and the ratio of calcite content to OM content (Rt) as the main two parameters governing isoproturon retention in soils. While organic matter favored pesticide sorption, calcite had an antagonistic effect since it limited isoproturon retention. The Rt ratio of calcite content to organic matter content in soils appeared to be a parameter that should be considered in predictive models in addition to OM in regions presenting calcareous soils. Adsorption of isoproturon as a function of Rt and OM was successfully described through a simple empirical model. Copyright © 2012 Elsevier B.V. All rights reserved.

A nonlinear isotherm model for sorption of anionic dyes on cellulose fibers: a case study.

PubMed

Xu, Changhai; Tang, Wenjuan; Du, Jinmei

2014-02-15

The sorption data of an anionic dye on cellulose fiber are often correlated with a log-linear model to determine the internal accessible volume of the fiber to the anionic dye (V, L/kg) and as such the standard affinity of the anionic dye to the fiber (-Δμ°, J/mol), but without taking into account the influence of ionized carboxyl groups due to cellulose oxidation ([COO(-)]f, mol/kg). In this study, a nonlinear isotherm model was derived by incorporating [COO(-)]f, V and -Δμ° as three model parameters. A set of classical sorption data of C. I. Direct Blue 1 on bleached cotton was correlated with the nonlinear isotherm model. The nonlinear curve fitting analysis showed that the nonlinear isotherm model was in excellent agreement with the sorption data and robust to determine the values of [COO(-)]f, V and -Δμ° for describing the sorption behaviors of anionic dyes on cellulose fibers. Copyright © 2013 Elsevier Ltd. All rights reserved.

Moisture Sorption-desorption Characteristics and the Corresponding Thermodynamic Properties of Carvedilol Phosphate.

PubMed

Allada, Ravikiran; Maruthapillai, Arthanareeswari; Palanisamy, Kamaraj; Chappa, Praveen

2017-01-01

Carvedilol phosphate (CDP) is a nonselective beta-blocker used for the treatment of heart failures and hypertension. In this work, moisture sorption-desorption characteristics and thermodynamic properties of CDP have been investigated. The isotherms were determined using dynamic vapor sorption analyzer at different humidity conditions (0%-90% relative humidity) and three pharmaceutically relevant temperatures (20°C, 30°C, and 40°C). The experimental sorption data determined were fitted to various models, namely, Brunauer-Emmett-Teller; Guggenheim-Anderson-De Boer (GAB); Peleg; and modified GAB. Isosteric heats of sorption were evaluated through the direct use of sorption isotherms by means of the Clausius-Clapeyron equation. The sorption model parameters were determined from the experimental sorption data using nonlinear regression analysis, and mean relative percentage deviation (P), correlation (Correl), root mean square error, and model efficiency were considered as the criteria to select the best fit model. The sorption-desorption isotherms have sigmoidal shape - confirming to Type II isotherms. Based on the statistical data analysis, modified GAB model was found to be more adequate to explain sorption characteristics of CDP. It is noted that the rate of adsorption and desorption is specific to the temperature at which it was being studied. It is observed that isosteric heat of sorption decreased with increasing equilibrium moisture content. The calculation of the thermodynamic properties was further used to draw an understanding of the properties of water and energy requirements associated with the sorption behavior. The sorption-desorption data and the set of equations are useful in the simulation of processing, handling, and storage of CDP and further behavior during manufacture and storage of CDP formulations.

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.

Re-evaluation of the sorption behaviour of Bromide and Sulfamethazine under field conditions using leaching data and modelling methods

NASA Astrophysics Data System (ADS)

Gassmann, Matthias; Olsson, Oliver; Höper, Heinrich; Hamscher, Gerd; Kümmerer, Klaus

2016-04-01

The simulation of reactive transport in the aquatic environment is hampered by the ambiguity of environmental fate process conceptualizations for a specific substance in the literature. Concepts are usually identified by experimental studies and inverse modelling under controlled lab conditions in order to reduce environmental uncertainties such as uncertain boundary conditions and input data. However, since environmental conditions affect substance behaviour, a re-evaluation might be necessary under environmental conditions which might, in turn, be affected by uncertainties. Using a combination of experimental data and simulations of the leaching behaviour of the veterinary antibiotic Sulfamethazine (SMZ; synonym: sulfadimidine) and the hydrological tracer Bromide (Br) in a field lysimeter, we re-evaluated the sorption concepts of both substances under uncertain field conditions. Sampling data of a field lysimeter experiment in which both substances were applied twice a year with manure and sampled at the bottom of two lysimeters during three subsequent years was used for model set-up and evaluation. The total amount of leached SMZ and Br were 22 μg and 129 mg, respectively. A reactive transport model was parameterized to the conditions of the two lysimeters filled with monoliths (depth 2 m, area 1 m²) of a sandy soil showing a low pH value under which Bromide is sorptive. We used different sorption concepts such as constant and organic-carbon dependent sorption coefficients and instantaneous and kinetic sorption equilibrium. Combining the sorption concepts resulted in four scenarios per substance with different equations for sorption equilibrium and sorption kinetics. The GLUE (Generalized Likelihood Uncertainty Estimation) method was applied to each scenario using parameter ranges found in experimental and modelling studies. The parameter spaces for each scenario were sampled using a Latin Hypercube method which was refined around local model efficiency maxima. Results of the cumulative SMZ leaching simulations suggest a best conceptualization combination of instantaneous sorption to organic carbon which is consistent with the literature. The best Nash-Sutcliffe efficiency (Neff) was 0.96 and the 5th and 95th percentile of the uncertainty estimation were 18 and 27 μg. In contrast, both scenarios of kinetic Br sorption had similar results (Neff =0.99, uncertainty bounds 110-176 mg and 112-176 mg) but were clearly better than instantaneous sorption scenarios. Therefore, only the concept of sorption kinetics could be identified for Br modelling whereas both tested sorption equilibrium coefficient concepts performed equally well. The reasons for this specific case of equifinality may be uncertainties of model input data under field conditions or an insensitivity of the sorption equilibrium method due to relatively low adsorption of Br. Our results show that it may be possible to identify or at least falsify specific sorption concepts under uncertain field conditions using a long-term leaching experiment and modelling methods. Cases of environmental fate concept equifinality arouse the possibility of future model structure uncertainty analysis using an ensemble of models with different environmental fate concepts.

A Mathematical Model for Simulating Remediation of Groundwater Contaminated by Heavy Metals using Bio-Carriers with Dead Baccilus sp. B1 and Polysulfone

NASA Astrophysics Data System (ADS)

Seo, H.; Wang, S.; Lee, M.

2010-12-01

The remediation of groundwater contaminated by heavy metals, organic contaminants, etc. using various types of bio-carriers has been widely studied as a novel technology in the literature. In this study, a series of batch experiments were conducted to investigated the fundamental characteristics in the removal process using bio-carriers (beads) with dead Bacillus sp. B1 and polysulfone. Through equilibrium and kinetic sorption experiments, sorption efficiencies for lead and copper under various conditions such as pH, temperature, contaminant concentration, etc. were examined and sorption parameters including maximum sorption capacities were obtained for model applications. Experimental data showed that equilibrium sorption patterns for Pb2+and Cu2+on bio-carrier beads follows Langmuir sorption isotherm and that the sorption dynamics can be described with a pseudo-second-order kinetics. One dimensional advective-dispersive-reactive transport model was also developed for simulating and analyzing the remediation processes. The HSDM (homogeneous surface diffusion model) were incorporated in the model to take into account the mass transfer and sorption mechanisms around/inside the bio-carrier beads. Applying the proposed model, numerical column experiments were carried out and the simulation results reasonably described temporal and spatial distribution of Pb2+and Cu2+in a fixed-bed flow-through sorption column. Experimental and numerical results showed that the main mechanism of the bio-carrier to remove heavy metals is the sorption on/inside of the bio-carriers and the bio-carriers can function as excellent biosorbents for the removal of heavy metal ions from groundwater.

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.

Development and characterization of a new encapsulating agent from orange juice by-products.

PubMed

Kaderides, Kyriakos; Goula, Athanasia M

2017-10-01

The replacement of maltodextrins as carriers for the spray drying of sticky and sugar based bioactives is an important development for the food industry. In this work, orange juice industry by-product was used to obtain a high dietary fiber powder to be used as carrier material. This powder was characterized with respect to its physical and chemical properties related to the process of encapsulation by spray drying. Adsorption isotherms of orange waste powder were determined at 30, 45, and 60°C. The data were fitted to several models including two-parameter (BET, Halsey, Smith, and Oswin), three-parameter (GAB), and four-parameter (Peleg) relationships. The GAB model best fitted the experimental data. The isosteric heat of sorption was determined from the equilibrium sorption data using the Clausius-Clapeyron equation. Isosteric heats of sorption were found to decrease exponentially with increasing moisture content. The enthalpy-entropy compensation theory was applied to the sorption isotherms and indicated an enthalpy controlled sorption process. Glass transition temperatures (T g ) of orange waste powder conditioned at various water activities were determined and a strong plasticizing effect of water on T g was found. These data were satisfactory correlated by the Gordon and Taylor model. The critical water activity and moisture content for the orange waste powder were 0.82 and 0.18g water/g solids, respectively, at a storage temperature of 25°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

Impact of kerogen heterogeneity on sorption of organic pollutants. 2. Sorption equilibria

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

Yang, C.; Yu, Z.Q.; Xiao, B.H.

2009-08-15

Phenanthrene and naphthalene sorption isotherms were measured for three different series of kerogen materials using completely mixed batch reactors. Sorption isotherms were nonlinear for each sorbate-sorbent system, and the Freundlich isotherm equation fit the sorption data well. The Freundlich isotherm linearity parameter n ranged from 0.192 to 0.729 for phenanthrene and from 0.389 to 0.731 for naphthalene. The n values correlated linearly with rigidity and aromaticity of the kerogen matrix, but the single-point, organic carbon-normalized distribution coefficients varied dramatically among the tested sorbents. A dual-mode sorption equation consisting of a linear partitioning domain and a Langmuir adsorption domain adequately quantifiedmore » the overall sorption equilibrium for each sorbent-sorbate system. Both models fit the data well, with r{sup 2} values of 0.965 to 0.996 for the Freundlich model and 0.963 to 0.997 for the dual-mode model for the phenanthrene sorption isotherms. The dual-mode model fitting results showed that as the rigidity and aromaticity of the kerogen matrix increased, the contribution of the linear partitioning domain to the overall sorption equilibrium decreased, whereas the contribution of the Langmuir adsorption domain increased. The present study suggested that kerogen materials found in soils and sediments should not be treated as a single, unified, carbonaceous sorbent phase.« less

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 isotherm and kinetic modeling of aniline on Cr-bentonite.

PubMed

Zheng, Hong; Liu, Donghong; Zheng, Yan; Liang, Shuping; Liu, Zhe

2009-08-15

In this paper, the sorption characteristics of aniline on Cr-bentonite prepared using synthetic wastewater containing chromium was investigated in a batch system at 30 degrees C. The effects of relevant parameters, such as pH value of solution, adsorbent dosage and initial aniline concentration were examined. The experimental data were analyzed by the Langmuir and Freundlich, and Temkin models of sorption. The sorption isotherm data were fitted well to Langmuir isotherm and the monolayer sorption capacity was found to be 21.60 mg/g at 30 degrees C. Dubinin-Redushkevich (D-R) isotherm was applied to describe the nature of aniline uptake and it was found that it occurred chemically. The kinetic data obtained at different concentrations were analyzed using a pseudo first-order, pseudo second-order kinetic equation and intraparticle diffusion model. The experimental data fitted very well the pseudo second-order kinetic model. Intraparticle diffusion affects aniline uptake. The results indicate that there is significant potential for Cr-bentonite as an adsorbent material for aniline removal from aqueous solutions.

Sorption characteristic of uranium(VI) ion onto K-feldspar.

PubMed

Gao, Xiaoqing; Bi, Mingliang; Shi, Keliang; Chai, Zhifang; Wu, Wangsuo

2017-10-01

The effect of pH, contact time, temperature, ionic strength and initial U(VI) concentration on U(VI) sorption onto K-feldspar was investigated using batch techniques. The sorption kinetics was evaluated and the activation energy was obtained based on the rate constants at different temperature. Graphical correlations of sorption isotherm models have been evaluated and applied for U(VI) uptake by K-feldspar. Various thermodynamic parameters, such as, Gibb's free energy, entropy and enthalpy of the on-going sorption process have been calculated and the possible sorption mechanism of U(VI) was deduced. The results are expected to help better understand the migration of uranium in the host materials of granite. Copyright © 2017 Elsevier Ltd. All rights reserved.

A sorption model for alkalis in cement-based materials - Correlations with solubility and electrokinetic properties

NASA Astrophysics Data System (ADS)

Henocq, Pierre

2017-06-01

In cement-based materials, radionuclide uptake is mainly controlled by calcium silicate hydrates (C-S-H). This work presents an approach for defining a unique set of parameters of a surface complexation model describing the sorption behavior of alkali ions on the C-S-H surface. Alkali sorption processes are modeled using the CD-MUSIC function integrated in the Phreeqc V.3.0.6 geochemical code. Parameterization of the model was performed based on (1) retention, (2) zeta potential, and (3) solubility experimental data from the literature. This paper shows an application of this model to sodium ions. It was shown that retention, i.e. surface interactions, and solubility are closely related, and a consistent sorption model for radionuclides in cement-based materials requires a coupled surface interaction/chemical equilibrium model. In case of C-S-H with low calcium-to-silicon ratios, sorption of sodium ions on the C-S-H surface strongly influences the chemical equilibrium of the C-S-H + NaCl system by significantly increasing the aqueous calcium concentration. The close relationship between sorption and chemical equilibrium was successfully illustrated by modeling the effect of the solid-to-liquid ratio on the calcium content in solution in the case of C-S-H + NaCl systems.

Sorption of small molecules in polymeric media

NASA Astrophysics Data System (ADS)

Camboni, Federico; Sokolov, Igor M.

2016-12-01

We discuss the sorption of penetrant molecules from the gas phase by a polymeric medium within a model which is very close in spirit to the dual sorption mode model: the penetrant molecules are partly dissolved within the polymeric matrix, partly fill the preexisting voids. The only difference with the initial dual sorption mode situation is the assumption that the two populations of molecules are in equilibrium with each other. Applying basic thermodynamics principles we obtain the dependence of the penetrant concentration on the pressure in the gas phase and find that this is expressed via the Lambert W-function, a different functional form than the one proposed by dual sorption mode model. The Lambert-like isotherms appear universally at low and moderate pressures and originate from the assumption that the internal energy in a polymer-penetrant-void ternary mixture is (in the lowest order) a bilinear form in the concentrations of the three components. Fitting the existing data shows that in the domain of parameters where the dual sorption mode model is typically applied, the Lambert function, which describes the same behavior as the one proposed by the gas-polymer matrix model, fits the data equally well.

Application of the method of temporal moments to interpret solute transport with sorption and degradation

NASA Astrophysics Data System (ADS)

Pang, Liping; Goltz, Mark; Close, Murray

2003-01-01

In this note, we applied the temporal moment solutions of [Das and Kluitenberg, 1996. Soil Sci. Am. J. 60, 1724] for one-dimensional advective-dispersive solute transport with linear equilibrium sorption and first-order degradation for time pulse sources to analyse soil column experimental data. Unlike most other moment solutions, these solutions consider the interplay of degradation and sorption. This permits estimation of a first-order degradation rate constant using the zeroth moment of column breakthrough data, as well as estimation of the retardation factor or sorption distribution coefficient of a degrading solute using the first moment. The method of temporal moment (MOM) formulae was applied to analyse breakthrough data from a laboratory column study of atrazine, hexazinone and rhodamine WT transport in volcanic pumice sand, as well as experimental data from the literature. Transport and degradation parameters obtained using the MOM were compared to parameters obtained by fitting breakthrough data from an advective-dispersive transport model with equilibrium sorption and first-order degradation, using the nonlinear least-square curve-fitting program CXTFIT. The results derived from using the literature data were also compared with estimates reported in the literature using different equilibrium models. The good agreement suggests that the MOM could provide an additional useful means of parameter estimation for transport involving equilibrium sorption and first-order degradation. We found that the MOM fitted breakthrough curves with tailing better than curve fitting. However, the MOM analysis requires complete breakthrough curves and relatively frequent data collection to ensure the accuracy of the moments obtained from the breakthrough data.

Prediction of the sorption capacities and affinities of organic chemicals by XAD-7.

PubMed

Yang, Kun; Qi, Long; Wei, Wei; Wu, Wenhao; Lin, Daohui

2016-01-01

Macro-porous resins are widely used as adsorbents for the treatment of organic contaminants in wastewater and for the pre-concentration of organic solutes from water. However, the sorption mechanisms for organic contaminants on such adsorbents have not been systematically investigated so far. Therefore, in this study, the sorption capacities and affinities of 24 organic chemicals by XAD-7 were investigated and the experimentally obtained sorption isotherms were fitted to the Dubinin-Ashtakhov model. Linear positive correlations were observed between the sorption capacities and the solubilities (SW) of the chemicals in water or octanol and between the sorption affinities and the solvatochromic parameters of the chemicals, indicating that the sorption of various organic compounds by XAD-7 occurred by non-linear partitioning into XAD-7, rather than by adsorption on XAD-7 surfaces. Both specific interactions (i.e., hydrogen-bonding interactions) as well as nonspecific interactions were considered to be responsible for the non-linear partitioning. The correlation equations obtained in this study allow the prediction of non-linear partitioning using well-known chemical parameters, namely SW, octanol-water partition coefficients (KOW), and the hydrogen-bonding donor parameter (αm). The effect of pH on the sorption of ionizable organic compounds (IOCs) could also be predicted by combining the correlation equations with additional equations developed from the estimation of IOC dissociation rates. The prediction equations developed in this study and the proposed non-linear partition mechanism shed new light on the selective removal and pre-concentration of organic solutes from water and on the regeneration of exhausted XAD-7 using solvent extraction.

Relation between some two- and three-parameter isotherm models for the sorption of methylene blue onto lemon peel.

PubMed

Kumar, K Vasanth; Porkodi, K

2006-12-01

Equilibrium uptake of methylne blue onto lemon peel was fitted to the 2 two-parameter isotherm models namely Freundlich and Langmuir and 3 six-parameter isotherm models namely Redlich-Peterson, Toth, Radke-Prausnitz, Fritz-Schluender, Vieth-Sladek and Sips isotherms by non-linear method. A comparison between two-parameter and three-parameter isotherms was reported. The best fitting isotherm was the Sips isotherm followed by Langmuir isotherm and Redlich-Peterson isotherm equation. Redlich-Peterson isotherm is a special case of Langmuir isotherm when the Redlich-Peterson isotherm constant g was unity. Radke-Prausnitz, Toth, Vieth-Sladek isotherm were the same when the Toth isotherm constant, n(T) and the Radke-Prausnitz isotherm, m(RP) are equal to unity and when the Vieth-Sladek isotherm constant, K(VS) equals zero. The sorption capacity of lemon peel for methylene blue uptake was found to be 29 mg/g.

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.

Description of two-metal biosorption equilibria by Langmuir-type models

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

Chong, K.H.; Volesky, B.

A biosorbent prepared from Ascophyllum nodosum seaweed biomass, FCAN2, was examined for its sorption capacity. Equilibrium batch sorption studies were performed using two-metal systems containing either (Cu+Zn), (Cu+Cd), or (Zn+Cd). In the evaluation of the two-metal sorption system performance, simple isotherm curves had to be replaced by three-dimensional sorption isotherm surfaces. In order to describe the isotherm surfaces mathematically, three Langmuir-type models were evaluated. The apparent one-parameter Langmuir constant (b) was used to quantify FCAN2 ``affinity`` for one metal in the presence of another one. The uptake of Zn decreased drastically when Cu of Cd were present. The uptake ofmore » Cd was much more sensitive to the presence of Cu than to that of Zn. The presence of Cd and Zn alter the ``affinity`` of FCAN2 for Cu the least at high Cu equilibrium concentrations. The mathematical model of the two-metal sorption system enabled quantitative estimation of one-metal (bio)sorption inhibition due to the influence of a second metal.« less

Water Sorption Isotherm of Pea Starch Edible Films and Prediction Models.

PubMed

Saberi, Bahareh; Vuong, Quan V; Chockchaisawasdee, Suwimol; Golding, John B; Scarlett, Christopher J; Stathopoulos, Costas E

2015-12-24

The moisture sorption isotherm of pea starch films prepared with various glycerol contents as plasticizer was investigated at different storage relative humidities (11%-96% RH) and at 5 ± 1, 15 ± 1, 25 ± 1 and 40 ± 1 °C by using gravimetric method. The results showed that the equilibrium moisture content of all films increased substantially above a w = 0.6. Films plasticized with glycerol, under all temperatures and RH conditions (11%-96%), adsorbed more moisture resulting in higher equilibrium moisture contents. Reduction of the temperature enhanced the equilibrium moisture content and monolayer water of the films. The obtained experimental data were fitted to different models including two-parameter equations (Oswin, Henderson, Brunauer-Emmitt-Teller (BET), Flory-Huggins, and Iglesias-Chirife), three-parameter equations Guggenhiem-Anderson-deBoer (GAB), Ferro-Fontan, and Lewicki) and a four-parameter equation (Peleg). The three-parameter Lewicki model was found to be the best-fitted model for representing the experimental data within the studied temperatures and whole range of relative humidities (11%-98%). Addition of glycerol increased the net isosteric heat of moisture sorption of pea starch film. The results provide important information with estimating of stability and functional characteristics of the films in various environments.

One-Dimensional Transport with Inflow and Storage (OTIS): A Solute Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

1998-01-01

OTIS is a mathematical simulation model used to characterize the fate and transport of water-borne solutes in streams and rivers. The governing equation underlying the model is the advection-dispersion equation with additional terms to account for transient storage, lateral inflow, first-order decay, and sorption. This equation and the associated equations describing transient storage and sorption are solved using a Crank-Nicolson finite-difference solution. OTIS may be used in conjunction with data from field-scale tracer experiments to quantify the hydrologic parameters affecting solute transport. This application typically involves a trial-and-error approach wherein parameter estimates are adjusted to obtain an acceptable match between simulated and observed tracer concentrations. Additional applications include analyses of nonconservative solutes that are subject to sorption processes or first-order decay. OTIS-P, a modified version of OTIS, couples the solution of the governing equation with a nonlinear regression package. OTIS-P determines an optimal set of parameter estimates that minimize the squared differences between the simulated and observed concentrations, thereby automating the parameter estimation process. This report details the development and application of OTIS and OTIS-P. Sections of the report describe model theory, input/output specifications, sample applications, and installation instructions.

Water Sorption Isotherm of Pea Starch Edible Films and Prediction Models

PubMed Central

Saberi, Bahareh; Vuong, Quan V.; Chockchaisawasdee, Suwimol; Golding, John B.; Scarlett, Christopher J.; Stathopoulos, Costas E.

2015-01-01

The moisture sorption isotherm of pea starch films prepared with various glycerol contents as plasticizer was investigated at different storage relative humidities (11%–96% RH) and at 5 ± 1, 15 ± 1, 25 ± 1 and 40 ± 1 °C by using gravimetric method. The results showed that the equilibrium moisture content of all films increased substantially above aw = 0.6. Films plasticized with glycerol, under all temperatures and RH conditions (11%–96%), adsorbed more moisture resulting in higher equilibrium moisture contents. Reduction of the temperature enhanced the equilibrium moisture content and monolayer water of the films. The obtained experimental data were fitted to different models including two-parameter equations (Oswin, Henderson, Brunauer–Emmitt–Teller (BET), Flory–Huggins, and Iglesias–Chirife), three-parameter equations Guggenhiem–Anderson–deBoer (GAB), Ferro–Fontan, and Lewicki) and a four-parameter equation (Peleg). The three-parameter Lewicki model was found to be the best-fitted model for representing the experimental data within the studied temperatures and whole range of relative humidities (11%–98%). Addition of glycerol increased the net isosteric heat of moisture sorption of pea starch film. The results provide important information with estimating of stability and functional characteristics of the films in various environments. PMID:28231096

Modeling coupled sorption and transformation of 17β-estradiol-17-sulfate in soil-water systems

NASA Astrophysics Data System (ADS)

Bai, Xuelian; Shrestha, Suman L.; Casey, Francis X. M.; Hakk, Heldur; Fan, Zhaosheng

2014-11-01

Animal manure is the primary source of exogenous free estrogens in the environment, which are known endocrine-disrupting chemicals to disorder the reproduction system of organisms. Conjugated estrogens can act as precursors to free estrogens, which may increase the total estrogenicity in the environment. In this study, a comprehensive model was used to simultaneously simulate the coupled sorption and transformation of a sulfate estrogen conjugate, 17β-estradiol-17-sulfate (E2-17S), in various soil-water systems (non-sterile/sterile; topsoil/subsoil). The simulated processes included multiple transformation pathways (i.e. hydroxylation, hydrolysis, and oxidation) and mass transfer between the aqueous, reversibly sorbed, and irreversibly sorbed phases of all soils for E2-17S and its metabolites. The conceptual model was conceived based on a series of linear sorption and first-order transformation expressions. The model was inversely solved using finite difference to estimate process parameters. A global optimization method was applied for the inverse analysis along with variable model restrictions to estimate 36 parameters. The model provided a satisfactory simultaneous fit (R2adj = 0.93 and d = 0.87) of all the experimental data and reliable parameter estimates. This modeling study improved the understanding on fate and transport of estrogen conjugates under various soil-water conditions.

Retention and Migration of Chlorpyrifos in Aquatic Sediments and Soils

NASA Astrophysics Data System (ADS)

Gebremariam, S. Y.; Beutel, M.; Yonge, D.; Flury, M.; Harsh, J. B.

2010-12-01

The accurate description of the fate and transport of potentially toxic agricultural pesticides in sediments and soils is of great interest to environmental scientists and regulators. Of particular concern is the widely documented detection of agricultural pesticides and their byproducts in drinking water wells. This presentation discusses results of a study of the fate and transport of chlorpyrifos, a strongly hydrophobic organophosphate-pesticide, in sediments and soils collected from a range of aquatic environments. Using radio-labeled chlorpyrifos, this study is unique in its comprehensive nature and focus on aquatic sediments, for which studies involving pesticide fate and transport are limited. Study components include: (1) batch equilibrium experiments to evaluate sorption/desorption parameters; (2) kinetic and non-equilibrium sorption experiments using miniaturized flow-cells; (3) column experiments to understand patterns of pesticide break through; and (4) numerical modeling of chlorpyrifos transport through aquatic sediments and soils. Initial results show that chlorpyrifos sorption, when corrected for reversible sorption to container walls, exhibited two component sorption, a large irreversible fraction and a smaller reversible fraction that can act as a secondary source. In addition, of a wide range of soil parameters measured, organic carbon content exhibited the highest correlation with chlorpyrifos retention in cranberry field soils. Simulation models developed in this study, which account for hysteretic and nonlinear sorption, will help to better predict the fate of chlorpyrifos and other hydrophobic chemicals in sediments and soils.

Sorption of metolachlor and atrazine in fly ash amended soils: comparison of optimized isotherm models.

PubMed

Ghosh, Rakesh K; Singh, Neera

2012-01-01

Adsorption of metolachlor and atrazine was studied in the fly ash (Inderprastha and Badarpur)- amended Inceptisol and Alfisol soils using batch method. Results indicated that sorption of both the herbicides in soil+fly ash mixtures was highly nonlinear and sorption decreased with a higher herbicide concentration in the solution. Also, nonlinearity increased with an increase in the level of fly ash amendment from 0-5%. Three two-parameter monolayer isotherms viz. Langmuir, Temkin, Jovanovic and one imperical Freundlich models were used to fit the experimental data. Data analysis and comparison revealed that the Temkin and the Freundlich isotherms were best-suited to explain the sorption results and the observed and the calculated adsorption coefficient values showed less variability. The study suggested that sorption mechanism of metolachlor and atrazine involved the physical association at the sorbate surface and the nonlinearity in the sorption at higher pesticide or fly ash concentration was due to a decrease in the heat of adsorption and higher binding energy.

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

USGS Publications Warehouse

Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

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.

Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

PubMed

Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

2015-04-09

In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Uranium adsorption on weathered schist - Intercomparison of modeling approaches

USGS Publications Warehouse

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

2004-01-01

Experimental data for uranium adsorption on a complex weathered rock were simulated by twelve modelling teams from eight countries using surface complexation (SC) models. This intercomparison was part of an international project to evaluate the present capabilities and limitations of SC models in representing sorption by geologic materials. The models were assessed in terms of their predictive ability, data requirements, number of optimised parameters, ability to simulate diverse chemical conditions and transferability to other substrates. A particular aim was to compare the generalised composite (GC) and component additivity (CA) approaches for modelling sorption by complex substrates. Both types of SC models showed a promising capability to simulate sorption data obtained across a range of chemical conditions. However, the models incorporated a wide variety of assumptions, particularly in terms of input parameters such as site densities and surface site types. Furthermore, the methods used to extrapolate the model simulations to different weathered rock samples collected at the same field site tended to be unsatisfactory. The outcome of this modelling exercise provides an overview of the present status of adsorption modelling in the context of radionuclide migration as practised in a number of countries worldwide.

Robust Means for Estimating Black Carbon-Water Sorption Coefficients of Organic Contaminants in Sediments

DTIC Science & Technology

2015-07-01

multiple lines of reasoning should be used to build confidence in what we believe is going on at any particular site. Hence, it will certainly be more...site depends on its Kd value (Fernandez et al., 2009). Consequently, we need to understand factors that go into the Kd sorption parameter in order...models of sorption to GAC (Kamlet et al. 1985, Luehrs et al. 1996, Poole and Poole 1997, Shih and Gschwend 2009) and multi-walled carbon nanotubes ( MWCNT

Removal of dissolved organic carbon by aquifer material: Correlations between column parameters, sorption isotherms and octanol-water partition coefficient.

PubMed

Pradhan, Snigdhendubala; Boernick, Hilmar; Kumar, Pradeep; Mehrotra, Indu

2016-07-15

The correlation between octanol-water partition coefficient (KOW) and the transport of aqueous samples containing single organic compound is well documented. The concept of the KOW of river water containing the mixture of organics was evolved by Pradhan et al. (2015). The present study aims at determining the KOW and sorption parameters of synthetic aqueous samples and river water to finding out the correlation, if any. The laboratory scale columns packed with aquifer materials were fed with synthetic and river water samples. Under the operating conditions, the compounds in the samples did not separate, and all the samples that contain more than one organic compound yielded a single breakthrough curve. Breakthrough curves simulated from sorption isotherms were compared with those from the column runs. The sorption parameters such as retardation factor (Rf), height of mass transfer zone (HMTZ), rate of mass transfer zone (RMTZ), breakpoint column capacity (qb) and maximum column capacity (qx) estimated from column runs, sorption isotherms and models developed by Yoon-Nelson, Bohart-Adam and Thomas were in agreement. The empirical correlations were found between the KOW and sorption parameters. The transport of the organics measured as dissolved organic carbon (DOC) through the aquifer can be predicted from the KOW of the river water and other water samples. The novelty of the study is to measure KOW and to envisage the fate of the DOC of the river water, particularly during riverbank filtration. Statistical analysis of the results revealed a fair agreement between the observed and computed values. Copyright © 2016 Elsevier Ltd. All rights reserved.

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

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.

Experimentally determined soil organic matter-water sorption coefficients for different classes of natural toxins and comparison with estimated numbers.

PubMed

Schenzel, Judith; Goss, Kai-Uwe; Schwarzenbach, René P; Bucheli, Thomas D; Droge, Steven T J

2012-06-05

Although natural toxins, such as mycotoxins or phytoestrogens are widely studied and were recently identified as micropollutants in the environment, many of their environmentally relevant physicochemical properties have not yet been determined. Here, the sorption affinity to Pahokee peat, a model sorbent for soil organic matter, was investigated for 29 mycotoxins and two phytoestrogens. Sorption coefficients (K(oc)) were determined with a dynamic HPLC-based column method using a fully aqueous mobile phase with 5 mM CaCl(2) at pH 4.5. Sorption coefficients varied from less than 10(0.7) L/kg(oc) (e.g., all type B trichothecenes) to 10(4.0) L/kg(oc) (positively charged ergot alkaloids). For the neutral compounds the experimental sorption data set was compared with predicted sorption coefficients using various models, based on molecular fragment approaches (EPISuite's KOCWIN or SPARC), poly parameter linear free energy relationship (pp-LFER) in combination with predicted descriptors, and quantum-chemical based software (COSMOtherm)). None of the available models was able to adequately predict absolute K(oc) numbers and relative differences in sorption affinity for the whole set of neutral toxins, largely because mycotoxins exhibit highly complex structures. Hence, at present, for such compounds fast and consistent experimental techniques for determining sorption coefficients, as the one used in this study, are required.

Moisture Sorption–desorption Characteristics and the Corresponding Thermodynamic Properties of Carvedilol Phosphate

PubMed Central

Allada, Ravikiran; Maruthapillai, Arthanareeswari; Palanisamy, Kamaraj; Chappa, Praveen

2017-01-01

Aims: Carvedilol phosphate (CDP) is a nonselective beta-blocker used for the treatment of heart failures and hypertension. In this work, moisture sorption–desorption characteristics and thermodynamic properties of CDP have been investigated. Materials and Methods: The isotherms were determined using dynamic vapor sorption analyzer at different humidity conditions (0%–90% relative humidity) and three pharmaceutically relevant temperatures (20°C, 30°C, and 40°C). The experimental sorption data determined were fitted to various models, namely, Brunauer–Emmett–Teller; Guggenheim-Anderson-De Boer (GAB); Peleg; and modified GAB. Isosteric heats of sorption were evaluated through the direct use of sorption isotherms by means of the Clausius-Clapeyron equation. Statistical Analysis Used: The sorption model parameters were determined from the experimental sorption data using nonlinear regression analysis, and mean relative percentage deviation (P), correlation (Correl), root mean square error, and model efficiency were considered as the criteria to select the best fit model. Results: The sorption–desorption isotherms have sigmoidal shape – confirming to Type II isotherms. Based on the statistical data analysis, modified GAB model was found to be more adequate to explain sorption characteristics of CDP. It is noted that the rate of adsorption and desorption is specific to the temperature at which it was being studied. It is observed that isosteric heat of sorption decreased with increasing equilibrium moisture content. Conclusions: The calculation of the thermodynamic properties was further used to draw an understanding of the properties of water and energy requirements associated with the sorption behavior. The sorption–desorption data and the set of equations are useful in the simulation of processing, handling, and storage of CDP and further behavior during manufacture and storage of CDP formulations. PMID:28584488

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

PubMed

Ho, Yuh-Shan

2006-01-01

A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

USGS Publications Warehouse

Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

2013-01-01

Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

Magnetic CuHCNPAN nano composite as an efficient adsorbent for strontium uptake

NASA Astrophysics Data System (ADS)

Mobtaker, Hossein Ghasemi; Pakzad, Seyed Mohammadreza; Yousefi, Taher

2018-06-01

An excellent composite was synthesized for sorption of strontium from solution. The composite (CuHCNPAN) components were copper hexacyanoferrate, magnetite and PAN. The XRD method confirmed the formation and presence of two crystalline phases of magnetite and copper hexacyanoferrate in composite. Particle sizes were determined by XRD and SEM methods. It was found that the particles were nano size. Some other methods such as FT IR, BET and TG methods were also used to determine the properties of the composite. The composite was used for sorption of strontium from solution. It was found that the kinetic of strontium sorption by the composite could be modeled by pseudo-second order. Among the isotherms applied to modeling the sorption in various concentrations, the Langmuir isotherm was founded to be more appropriate to fitting the experimental data. An excellent correlation coefficient was obtained (R2 > 0.98). The qmax for sorption of strontium ions which was calculated by Langmuir model was 80 mg/g. The thermodynamic parameters were calculated by determination of sorption in various temperatures and using the Vant Hoff plot. ΔG°, ΔH°, and ΔS° were calculated as -19.15, 2.28 and 0.071 kJ/mol respectively.

Optimization of isotherm models for pesticide sorption on biopolymer-nanoclay composite by error analysis.

PubMed

Narayanan, Neethu; Gupta, Suman; Gajbhiye, V T; Manjaiah, K M

2017-04-01

A carboxy methyl cellulose-nano organoclay (nano montmorillonite modified with 35-45 wt % dimethyl dialkyl (C 14 -C 18 ) amine (DMDA)) composite was prepared by solution intercalation method. The prepared composite was characterized by infrared spectroscopy (FTIR), X-Ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). The composite was utilized for its pesticide sorption efficiency for atrazine, imidacloprid and thiamethoxam. The sorption data was fitted into Langmuir and Freundlich isotherms using linear and non linear methods. The linear regression method suggested best fitting of sorption data into Type II Langmuir and Freundlich isotherms. In order to avoid the bias resulting from linearization, seven different error parameters were also analyzed by non linear regression method. The non linear error analysis suggested that the sorption data fitted well into Langmuir model rather than in Freundlich model. The maximum sorption capacity, Q 0 (μg/g) was given by imidacloprid (2000) followed by thiamethoxam (1667) and atrazine (1429). The study suggests that the degree of determination of linear regression alone cannot be used for comparing the best fitting of Langmuir and Freundlich models and non-linear error analysis needs to be done to avoid inaccurate results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of diatomite and its application for the retention of radiocobalt: role of environmental parameters.

PubMed

Sheng, Guodong; Dong, Huaping; Li, Yimin

2012-11-01

Clay minerals have been extensively studied because of their strong sorption and complexation ability. In this work, diatomite was characterized by using acid-base titration. Retention of radionuclide (60)Co(II) from aqueous solution by sorption onto diatomite was investigated by using batch technique under various environmental conditions such as pH, ionic strength, humic acid (HA), fulvic acid (FA), and temperature. The results indicated that the sorption of Co(II) onto diatomite was strongly dependent on pH. At low pH value, the sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange with Na(+)/H(+) on diatomite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH value. The D-R model fitted the sorption isotherms better than the Langmuir and Freundlich models. The thermodynamic parameters (ΔH(0), ΔS(0) and ΔG(0)) calculated from the temperature-dependent sorption isotherms suggested that the sorption of Co(II) was an endothermic and spontaneous process. In addition, diatomite showed higher sorption capacity than that of lots of the sorbents reported in the literatures we surveyed. From the results of Co(II) removal by diatomite, the optimum reaction conditions can be obtained for the maximum removal of Co(II) from water. It is clear that the best pH values of the system to remove Co(II) from solution by using diatomite are 7-8. Considering the low cost and effective disposal of Co(II)-contaminated wastewaters, the best condition for Co(II) removal is at room temperature and solid content of 0.5 g/L. The results might be important for assessing the potential of practical application of diatomite in Co(II) and related radionuclide pollution management. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fate and transport of phenol in a packed bed reactor containing simulated solid waste

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

Saquing, Jovita M., E-mail: jmsaquing@gmail.com; Knappe, Detlef R.U., E-mail: knappe@ncsu.edu; Barlaz, Morton A., E-mail: barlaz@ncsu.edu

Highlights: Black-Right-Pointing-Pointer Anaerobic column experiments were conducted at 37 Degree-Sign C using a simulated waste mixture. Black-Right-Pointing-Pointer Sorption and biodegradation model parameters were determined from batch tests. Black-Right-Pointing-Pointer HYDRUS simulated well the fate and transport of phenol in a fully saturated waste column. Black-Right-Pointing-Pointer The batch biodegradation rate and the rate obtained by inverse modeling differed by a factor of {approx}2. Black-Right-Pointing-Pointer Tracer tests showed the importance of hydrodynamic parameters to improve model estimates. - Abstract: An assessment of the risk to human health and the environment associated with the presence of organic contaminants (OCs) in landfills necessitates reliable predictivemore » models. The overall objectives of this study were to (1) conduct column experiments to measure the fate and transport of an OC in a simulated solid waste mixture, (2) compare the results of column experiments to model predictions using HYDRUS-1D (version 4.13), a contaminant fate and transport model that can be parameterized to simulate the laboratory experimental system, and (3) determine model input parameters from independently conducted batch experiments. Experiments were conducted in which sorption only and sorption plus biodegradation influenced OC transport. HYDRUS-1D can reasonably simulate the fate and transport of phenol in an anaerobic and fully saturated waste column in which biodegradation and sorption are the prevailing fate processes. The agreement between model predictions and column data was imperfect (i.e., within a factor of two) for the sorption plus biodegradation test and the error almost certainly lies in the difficulty of measuring a biodegradation rate that is applicable to the column conditions. Nevertheless, a biodegradation rate estimate that is within a factor of two or even five may be adequate in the context of a landfill, given the extended retention time and the fact that leachate release will be controlled by the infiltration rate which can be minimized by engineering controls.« less

A review of model applications for structured soils: b) Pesticide transport.

PubMed

Köhne, John Maximilian; Köhne, Sigrid; Simůnek, Jirka

2009-02-16

The past decade has seen considerable progress in the development of models simulating pesticide transport in structured soils subject to preferential flow (PF). Most PF pesticide transport models are based on the two-region concept and usually assume one (vertical) dimensional flow and transport. Stochastic parameter sets are sometimes used to account for the effects of spatial variability at the field scale. In the past decade, PF pesticide models were also coupled with Geographical Information Systems (GIS) and groundwater flow models for application at the catchment and larger regional scales. A review of PF pesticide model applications reveals that the principal difficulty of their application is still the appropriate parameterization of PF and pesticide processes. Experimental solution strategies involve improving measurement techniques and experimental designs. Model strategies aim at enhancing process descriptions, studying parameter sensitivity, uncertainty, inverse parameter identification, model calibration, and effects of spatial variability, as well as generating model emulators and databases. Model comparison studies demonstrated that, after calibration, PF pesticide models clearly outperform chromatographic models for structured soils. Considering nonlinear and kinetic sorption reactions further enhanced the pesticide transport description. However, inverse techniques combined with typically available experimental data are often limited in their ability to simultaneously identify parameters for describing PF, sorption, degradation and other processes. On the other hand, the predictive capacity of uncalibrated PF pesticide models currently allows at best an approximate (order-of-magnitude) estimation of concentrations. Moreover, models should target the entire soil-plant-atmosphere system, including often neglected above-ground processes such as pesticide volatilization, interception, sorption to plant residues, root uptake, and losses by runoff. The conclusions compile progress, problems, and future research choices for modelling pesticide displacement in structured soils.

Modeling the production, decomposition, and transport of dissolved organic carbon in boreal soils

USGS Publications Warehouse

Fan, Zhaosheng; Neff, Jason C.; Wickland, Kimberly P.

2010-01-01

The movement of dissolved organic carbon (DOC) through boreal ecosystems has drawn increased attention because of its potential impact on the feedback of OC stocks to global environmental change in this region. Few models of boreal DOC exist. Here we present a one-dimensional model with simultaneous production, decomposition, sorption/desorption, and transport of DOC to describe the behavior of DOC in the OC layers above the mineral soils. The field-observed concentration profiles of DOC in two moderately well-drained black spruce forest sites (one with permafrost and one without permafrost), coupled with hourly measured soil temperature and moisture, were used to inversely estimate the unknown parameters associated with the sorption/desorption kinetics using a global optimization strategy. The model, along with the estimated parameters, reasonably reproduces the concentration profiles of DOC and highlights some important potential controls over DOC production and cycling in boreal settings. The values of estimated parameters suggest that humic OC has a larger potential production capacity for DOC than fine OC, and most of the DOC produced from fine OC was associated with instantaneous sorption/desorption whereas most of the DOC produced from humic OC was associated with time-dependent sorption/desorption. The simulated DOC efflux at the bottom of soil OC layers was highly dependent on the component and structure of the OC layers. The DOC efflux was controlled by advection at the site with no humic OC and moist conditions and controlled by diffusion at the site with the presence of humic OC and dry conditions.

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.

Thermodynamics of Cadmium Sorption on Different Soils of West Bengal, India

PubMed Central

Paul, Ranjit Kumar; Das, D. K.; Boruah, Romesh K.; Sonar, Indira

2014-01-01

A sorption study was conducted on different soils collected from five agroecological zones of West Bengal, India, to understand the soil environmental behavior and fate of cadmium. For this purpose batch adsorption experiments were carried out at the native soil pH and at three different temperatures (25°C, 35°C, and 45°C). The adsorption data fitted by a linear least squares technique to the different sorption isotherms. Most data obtained give the good fit to both Freundlich and modified Langmuir isotherms, but they are not consistent with the linear Langmuir adsorption model. Thermodynamic parameters, namely, thermodynamics equilibrium constant at a particular temperature T  (K T 0), Gibbs free energy at a particular temperature T  (ΔG T 0), and change of enthalpy (ΔH 0) and change of entropy at temperature T  (ΔS T 0), were also determined by applying sorption value and concentrations of Cd in equilibrium solution within the temperature range. The thermodynamic parameters revealed that Cd sorption increases as the values of K T 0, ΔG T 0, ΔH 0, and ΔS T 0 were increased on reaction temperatures. The spontaneous sorption reaction can be concluded due to high values of ΔG T 0. The positive values of ΔH 0 indicated that the Cd sorption is an endothermic one. Under these present conditions, the soil and its components possibly supply a number of sites having different adsorption energies for cadmium sorption. PMID:24683322

Heavy metals binding properties of esterified lemon.

PubMed

Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

2009-05-30

Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.

Development and application of biosorption database for the control of heavy metals in waste and wastewaters

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

Min, J.H.; Hering, J.G.

1996-11-01

The rapid removal and high sorption capacity for metals as well as the cost-effectiveness of biosorption makes it a promising alternative for remediation or treatment of metals in the aquatic environment. Depending on the type of biomass, the sorption capacity may vary significantly for different metals, and thus it is important to evaluate the sorption characteristics of biomass for optimal removal of metals from the wastewaters. The objective of developing a biosorption database was to use available literature data for preliminary evaluation of potential significance of biosorption. The database was developed by collecting biosorption data sets from the published literature,more » extracting raw data from the papers, and re-analyzing the data with a consistent model. The re-analysis was crucial in developing the database because of the inconsistency in sorption models and units used by various investigators. The raw data from the literature were obtained using a digitizer and fitted with a same isotherm model with consistent units, which enabled quantitative comparison between data sets under similar conditions from different sources by comparing the isotherm constants. Metal sorption by biomass can be influenced by various environmental conditions such as pH, temperature, the characteristics or composition of the solution, and the presence of other complexing ligands in the solution. Biosorption of a specific metal by a specific species or type of biomass under different conditions can be compared to evaluate the effect of each parameter and to assess the possibility of lumping constants for a general case. The general sorption parameters for similar types of biomass under similar conditions can be used in preliminary assessment of metal/biomass combination for the optimal removal or stabilization of heavy metals.« less

Sorption and recovery of platinum from simulated spent catalyst solution and refinery wastewater using chemically modified biomass as a novel sorbent.

PubMed

Garole, Dipak J; Choudhary, Bharat C; Paul, Debajyoti; Borse, Amulrao U

2018-04-01

In this study, Lagerstroemia speciosa biomass modified by polyethylenimine (PEI-LS) was developed as a potential biosorbent for sorption and recovery of platinum(II) from platinum bearing waste solutions. Batch experiments were conducted to study the effect of various parameters on the sorption and recovery of platinum(II) using PEI-LS. The equilibrium time for platinum(II) sorption process was found to be 6 h. Both the sorption kinetics and sorption isotherm data fits pseudo second-order kinetic model and Langmuir isotherm, respectively. The maximum sorption capacity of platinum(II) onto PEI-LS at pH 2 for the studied temperature range (25-45 °C) is in the range of 122-154 mg/g. Evaluation of thermodynamic parameters suggests that the platinum(II) sorption is spontaneous and endothermic in nature. The regeneration of PEI-LS can be achieved using acidic thiourea as an eluent for recovery of platinum from the biosorbent. Fourier transform infrared (FT-IR) analysis suggests many functional groups were involved in platinum(II) sorption onto PEI-LS. Both the scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) and X-ray photoelectron spectroscopy (XPS) analysis suggest a successful modification of raw biomass with PEI. The XPS analysis further concludes that platinum(II) sorption is governed by ion-exchange and co-ordination reaction. Finally, the PEI-LS was shown to recover ≥ 90% of platinum from two simulated solutions: the acid-leached spent catalyst solution and refinery wastewater. The biosorbent developed in this study is a low-cost and eco-friendly media that can be effectively used for platinum recovery from industrial wastewater.

Revealing chemophoric sites in organophosphorus insecticides through the MIA-QSPR modeling of soil sorption data.

PubMed

Daré, Joyce K; Silva, Cristina F; Freitas, Matheus P

2017-10-01

Soil sorption of insecticides employed in agriculture is an important parameter to probe the environmental fate of organic chemicals. Therefore, methods for the prediction of soil sorption of new agrochemical candidates, as well as for the rationalization of the molecular characteristics responsible for a given sorption profile, are extremely beneficial for the environment. A quantitative structure-property relationship method based on chemical structure images as molecular descriptors provided a reliable model for the soil sorption prediction of 24 widely used organophosphorus insecticides. By means of contour maps obtained from the partial least squares regression coefficients and the variable importance in projection scores, key molecular moieties were targeted for possible structural modification, in order to obtain novel and more environmentally friendly insecticide candidates. The image-based descriptors applied encode molecular arrangement, atoms connectivity, groups size, and polarity; consequently, the findings in this work cannot be achieved by a simple relationship with hydrophobicity, usually described by the octanol-water partition coefficient. Copyright © 2017 Elsevier Inc. All rights reserved.

Investigations of Heavy Metal Ion Sorption Using Nanocomposites of Iron-Modified Biochar

NASA Astrophysics Data System (ADS)

Kołodyńska, D.; Bąk, J.; Kozioł, M.; Pylypchuk, L. V.

2017-06-01

Magnetic biochar nanocomposites were obtained by modification of biochar by zero-valent iron. The article provides information on the impact of contact time, initial Cd(II), Co(II), Zn(II), and Pb(II) ion concentrations, dose of the sorbents, solution pH and temperature on the adsorption capacity. On the basis of experiments, it was found that the optimum parameters for the sorption process are phase contact time 360 min (after this time, the equilibrium of all concentrations is reached), the dose of sorbent equal to 5 g/dm3, pH 5 and the temperature 295 K. The values of parameters calculated from the kinetic models and isotherms present the best match to the pseudo second order and Langmuir isotherm models. The calculated thermodynamic parameters ΔH 0, ΔS 0 and ΔG 0 indicate that the sorption of heavy metal ions is an exothermic and spontaneous process as well as favoured at lower temperatures, suggesting the physical character of sorption. The solution of nitric acid(V) at the concentration 0.1 mol/dm3 was the best acidic desorbing agent used for regeneration of metal-loaded magnetic sorbents. The physicochemical properties of synthesized composites were characterized by FTIR, SEM, XRD, XPS and TG analyses. The point characteristics of the double layer for biochar pHPZC and pHIEP were designated.

Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite

DOE PAGES

Tinnacher, Ruth M.; Begg, James D.; Mason, Harris; ...

2015-01-21

The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presencemore » of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu–FA–mineral complexes could enhance colloid-facilitated Pu transport. In conclusion, more representative natural conditions need to be investigated to quantify the relevance of these findings.« less

Factors influencing sorption of ciprofloxacin onto activated sludge: experimental assessment and modelling implications.

PubMed

Polesel, Fabio; Lehnberg, Kai; Dott, Wolfgang; Trapp, Stefan; Thomas, Kevin V; Plósz, Benedek Gy

2015-01-01

Many of the pharmaceuticals and personal care products occurring in municipal sewage are ionizing substances, and their partitioning behaviour is affected by ionic interactions with solid matrices. In activated sludge systems, such interactions have currently not been adequately understood and described, particularly for zwitterionic chemicals. Here we present an assessment of the effects of pH and iron salt dosing on the sorption of ciprofloxacin onto activated sludge using laboratory experiments and full-scale fate modelling. Experimental results were described with Freundlich isotherms and showed that non-linear sorption occurred under all the conditions tested. The greatest sorption potential was measured at pH=7.4, at which ciprofloxacin is speciated mostly as zwitterion. Iron salt dosing increased sorption under aerobic and, to a lesser extent, anoxic conditions, whereas no effect was registered under anaerobic conditions. The activated sludge model for xenobiotics (ASM-X) was extended with Freundlich-based sorption kinetics and used to predict the fate of ciprofloxacin in a wastewater treatment plant (WWTP). Scenario simulations, using experimental Freundlich parameters, were used to identify whether the assessed factors caused a significant increase of aqueous ciprofloxacin concentration in full-scale bioreactors. Simulation results suggest that a pH increase, rather than a reduction in iron salt dosing, could be responsible for a systematic deterioration of sorption of ciprofloxacin in the WWTP. Copyright © 2014 Elsevier Ltd. All rights reserved.

Multi-process herbicide transport in structured soil columns: Experiments and model analysis

NASA Astrophysics Data System (ADS)

Köhne, J. Maximilian; Köhne, Sigrid; Šimůnek, Jirka

2006-05-01

Model predictions of pesticide transport in structured soils are complicated by multiple processes acting concurrently. In this study, the hydraulic, physical, and chemical nonequilibrium (HNE, PNE, and CNE, respectively) processes governing herbicide transport under variably saturated flow conditions were studied. Bromide (Br -), isoproturon (IPU, 3-(4-isoprpylphenyl)-1,1-dimethylurea) and terbuthylazine (TER, N2-tert-butyl-6-chloro- N4-ethyl-1,3,5-triazine-2,4-diamine) were applied to two soil columns. An aggregated Ap soil column and a macroporous, aggregated Ah soil column were irrigated at a rate of 1 cm h - 1 for 3 h. Two more irrigations at the same rate and duration followed in weekly intervals. Nonlinear (Freundlich) equilibrium and two-site kinetic sorption parameters were determined for IPU and TER using batch experiments. The observed water flow and Br - transport were inversely simulated using mobile-immobile (MIM), dual-permeability (DPM), and combined triple-porosity (DP-MIM) numerical models implemented in HYDRUS-1D, with improving correspondence between empirical data and model results. Using the estimated HNE and PNE parameters together with batch-test derived equilibrium sorption parameters, the preferential breakthrough of the weakly adsorbed IPU in the Ah soil could be reasonably well predicted with the DPM approach, whereas leaching of the strongly adsorbed TER was predicted less well. The transport of IPU and TER through the aggregated Ap soil could be described consistently only when HNE, PNE, and CNE were simultaneously accounted for using the DPM. Inverse parameter estimation suggested that two-site kinetic sorption in inter-aggregate flow paths was reduced as compared to within aggregates, and that large values for the first-order degradation rate were an artifact caused by irreversible sorption. Overall, our results should be helpful to enhance the understanding and modeling of multi-process pesticide transport through structured soils during variably saturated water flow.

Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater.

PubMed

Gonzalez, Mário H; Araújo, Geórgia C L; Pelizaro, Claudia B; Menezes, Eveline A; Lemos, Sherlan G; de Sousa, Gilberto Batista; Nogueira, Ana Rita A

2008-11-30

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8+/-0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr(2)O(3,) with a reduction of more than 60% of the original mass.

Dynamic Simulation of a Periodic 10 K Sorption Cryocooler

NASA Technical Reports Server (NTRS)

Bhandari, P.; Rodriguez, J.; Bard, S.; Wade, L.

1994-01-01

A transient thermal simulation model has been developed to simulate the dynamic performance of a multiple-stage 10 K sorption cryocooler for spacecraft sensor cooling applications that require periodic quick-cooldown (under 2 minutes) , negligible vibration, low power consumption, and long life (5 to 10 years). The model was specifically designed to represent the Brilliant Eyes Ten-Kelvin Sorption Cryocooler Experiment (BETSCE), but it can be adapted to represent other sorption cryocooler systems as well. The model simulates the heat transfer, mass transfer, and thermodynamic processes in the cryostat and the sorbent beds for the entire refrigeration cycle, and includes the transient effects of variable hydrogen supply pressures due to expansion and overflow of hydrogen during the cooldown operation. The paper describes model limitations and simplifying assumptions, with estimates of errors induced by them, and presents comparisons of performance predictions with ground experiments. An important benefit of the model is its ability to predict performance sensitivities to variations of key design and operational parameters. The insights thus obtained are expected to lead to higher efficiencies and lower weights for future designs.

Sorption reaction mechanism of some hazardous radionuclides from mixed waste by impregnated crown ether onto polymeric resin.

PubMed

Shehata, F A; Attallah, M F; Borai, E H; Hilal, M A; Abo-Aly, M M

2010-02-01

A novel impregnated polymeric resin was practically tested as adsorbent material for removal of some hazardous radionuclides from radioactive liquid waste. The applicability for the treatment of low-level liquid radioactive waste was investigated. The material was prepared by loading 4,4'(5')di-t-butylbenzo 18 crown 6 (DtBB18C6) onto poly(acrylamide-acrylic acid-acrylonitril)-N, N'-methylenediacrylamide (P(AM-AA-AN)-DAM). The removal of (134)Cs, (60)Co, (65)Zn , and ((152+154))Eu onto P(AM-AA-AN)-DAM/DtBB18C6 was investigated using a batch equilibrium technique with respect to the pH, contact time, and temperature. Kinetic models are used to determine the rate of sorption and to investigate the mechanism of sorption process. Five kinetics models, pseudo-first-order, pseudo-second-order, intra-particle diffusion, homogeneous particle diffusion (HPDM), and Elovich models, were used to investigate the sorption process. The obtained results of kinetic models predicted that, pseudo-second-order is applicable; the sorption is controlled by particle diffusion mechanism and the process is chemisorption. The obtained values of thermodynamics parameters, DeltaH degrees , DeltaS degrees , and DeltaG degrees indicated that the endothermic nature, increased randomness at the solid/solution interface and the spontaneous nature of the sorption processes. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Cadmium removal in a biosorption column

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

Volesky, B.; Prasetyo, I.

New biosorbent material derived from a ubiquitous brown marine alga Ascophyllum nodosum has been examined in packed-bed flow-through sorption columns. It effectively removed 10 mg/L of cadmium down to 1.5 ppb levels in the effluent, representing 99.985% removal. The experimental methodology used was based on the early Bohart and Adams sorption model, resulting in quantitative determination of the characteristic process parameters which can be used for performance comparison and process design. An average metal loading of the biosorbent (N[sub 0]) determined was 30 mg Cd/g, corresponding closely to that observed for the batch equilibrium metal concentration of 10 mg Cd/L.more » The critical bed depth (D[sub min]) for the potable water effluent quality standard varied with the column feed flow rate from 20 to 50 cm. The sorption column mass transfer and dispersion coefficients were determined, which are also required for solving the sorption model equations.« less

Interpretation of aged sorption studies for pesticides and their use in European Union regulatory leaching assessments.

PubMed

Beulke, Sabine; van Beinum, Wendy; Suddaby, Laura

2015-04-01

First-tier regulatory exposure assessments for pesticides assume that pesticide sorption is instantaneous and fully reversible. In European Union (EU) regulatory guidance, an increase in sorption over time ("aged sorption") can be considered at the higher tier to refine predicted environmental concentrations in groundwater. Research commissioned by the UK Chemicals Regulation Directorate (CRD), funded by the Department for Environment Food & Rural Affairs (Defra), formed the basis of a draft regulatory guidance document proposing 1) a protocol on how to measure aged sorption of parent compounds in laboratory studies, 2) procedures to fit kinetic models to the experimental data, 3) criteria to test the reliability of the parameters, and 4) procedures for use of the parameters in the groundwater exposure assessment. The draft guidance was revised after feedback from stakeholders and testing of the guidance was performed against real data sets by an independent consultancy. The Chemicals Regulation Directorate submitted the revised document to the European Food Safety Authority (EFSA) for scrutiny. This article gives an overview of the draft guidance and explains the reasoning behind the recommendations made. 2015 Crown Copyright; Published 2015 SETAC.

Sorption and desorption studies of a reactive azo dye on effective disposal of redundant material.

PubMed

Çelekli, Abuzer; Bozkurt, Hüseyin

2013-07-01

The effective disposal of redundant elephant dung (ED) is important for environmental protection and utilization of resource. The aim of this study was to remove a toxic-azo dye, Reactive Red (RR) 120, using this relatively cheap material as a new adsorbent. The FTIR-ATR spectra of ED powders before and after the sorption of RR 120 and zero point charge (pHzpc) of ED were determined. The sorption capacity of ED for removing of RR 120 were carried out as functions of particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. Sorption isotherm, kinetic, activation energy, thermodynamic, and desorption parameters of RR 120 on ED were studied. The sorption process was found to be dependent on particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. FTIR-ATR spectroscopy indicated that amine and amide groups have significant role on the sorption of RR 120 on ED. The pHzpc of ED was found to be 7.3. Sorption kinetic of RR 120 on ED was well described by sigmoidal Logistic model. The Langmuir isotherm was well fitted to the equilibrium data. The maximum sorption capacity was 95.71 mg g(-1). The sorption of RR 120 on ED was mainly physical and exothermic according to results of D-R isotherm, Arrhenius equation, thermodynamic, and desorption studies. The thermodynamic parameters showed that this process was feasible and spontaneous. This study showed that ED as a low-cost adsorbent had a great potential for the removal of RR 120 as an alternative eco-friendly process.

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.

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

PubMed

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

2004-11-01

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

Properties comparison of biochars from corn straw with different pretreatment and sorption behaviour of atrazine.

PubMed

Zhao, Xuchen; Ouyang, Wei; Hao, Fanghua; Lin, Chunye; Wang, Fangli; Han, Sheng; Geng, Xiaojun

2013-11-01

Biochar has been recognised as an efficient pollution control material. In this study, biochars (CS450 and ADPCS450) were produced using corn straw with different pretreatment techniques (without and with ammonium dihydrogen phosphate (ADP)). The character of the two biochars was compared using elemental analysis, specific surface area (SSA) and Fourier transform infrared spectra (FTIR). ADPCS450 had a higher residue yield and a much larger specific surface area than CS450. The Freundlich, Langmuir and Redlich-Peterson models were used to interpret the sorption behaviour of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), and the results fit the Redlich-Peterson equation best. The isothermal sorption parameters indicated that the sorption capacity of atrazine on ADPCS450 was much larger than the sorption capacity of atrazine on CS450. Atrazine sorption was also favoured in acidic solution and under higher temperature conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Performance of chromatographic systems to model soil-water sorption.

PubMed

Hidalgo-Rodríguez, Marta; Fuguet, Elisabet; Ràfols, Clara; Rosés, Martí

2012-08-24

A systematic approach for evaluating the goodness of chromatographic systems to model the sorption of neutral organic compounds by soil from water is presented in this work. It is based on the examination of the three sources of error that determine the overall variance obtained when soil-water partition coefficients are correlated against chromatographic retention factors: the variance of the soil-water sorption data, the variance of the chromatographic data, and the variance attributed to the dissimilarity between the two systems. These contributions of variance are easily predicted through the characterization of the systems by the solvation parameter model. According to this method, several chromatographic systems besides the reference octanol-water partition system have been selected to test their performance in the emulation of soil-water sorption. The results from the experimental correlations agree with the predicted variances. The high-performance liquid chromatography system based on an immobilized artificial membrane and the micellar electrokinetic chromatography systems of sodium dodecylsulfate and sodium taurocholate provide the most precise correlation models. They have shown to predict well soil-water sorption coefficients of several tested herbicides. Octanol-water partitions and high-performance liquid chromatography measurements using C18 columns are less suited for the estimation of soil-water partition coefficients. Copyright © 2012 Elsevier B.V. All rights reserved.

Evaluation of theoretical and empirical water vapor sorption isotherm models for soils

NASA Astrophysics Data System (ADS)

Arthur, Emmanuel; Tuller, Markus; Moldrup, Per; de Jonge, Lis W.

2016-01-01

The mathematical characterization of water vapor sorption isotherms of soils is crucial for modeling processes such as volatilization of pesticides and diffusive and convective water vapor transport. Although numerous physically based and empirical models were previously proposed to describe sorption isotherms of building materials, food, and other industrial products, knowledge about the applicability of these functions for soils is noticeably lacking. We present an evaluation of nine models for characterizing adsorption/desorption isotherms for a water activity range from 0.03 to 0.93 based on measured data of 207 soils with widely varying textures, organic carbon contents, and clay mineralogy. In addition, the potential applicability of the models for prediction of sorption isotherms from known clay content was investigated. While in general, all investigated models described measured adsorption and desorption isotherms reasonably well, distinct differences were observed between physical and empirical models and due to the different degrees of freedom of the model equations. There were also considerable differences in model performance for adsorption and desorption data. While regression analysis relating model parameters and clay content and subsequent model application for prediction of measured isotherms showed promise for the majority of investigated soils, for soils with distinct kaolinitic and smectitic clay mineralogy predicted isotherms did not closely match the measurements.

Soil-adjusted sorption isotherms for arsenic(V) and vanadium(V)

NASA Astrophysics Data System (ADS)

Rückamp, Daniel; Utermann, Jens; Florian Stange, Claus

2017-04-01

The sorption characteristic of a soil is usually determined by fitting a sorption isotherm model to laboratory data. However, such sorption isotherms are only valid for the studied soil and cannot be transferred to other soils. For this reason, a soil-adjusted sorption isotherm can be calculated by using the data of several soils. Such soil-adjusted sorption isotherms exist for cationic heavy metals, but are lacking for heavy metal oxyanions. Hence, the aim of this study is to establish soil-adjusted sorption isotherms for the oxyanions arsenate (arsenic(V)) and vanadate (vanadium(V)). For the laboratory experiment, 119 soils (samples from top- and subsoils) typical for Germany were chosen. The batch experiments were conducted with six concentrations of arsenic(V) and vanadium(V), respectively. By using the laboratory data, sorption isotherms for each soil were derived. Then, the soil-adjusted sorption isotherms were calculated by non-linear regression of the sorption isotherms with additional soil parameters. The results indicated a correlation between the sorption strength and oxalate-extractable iron, organic carbon, clay, and electrical conductivity for both, arsenic and vanadium. However, organic carbon had a negative regression coefficient. As total organic carbon was correlated with dissolved organic carbon; we attribute this observation to an effect of higher amounts of dissolved organic substances. We conclude that these soil-adjusted sorption isotherms can be used to assess the potential of soils to adsorb arsenic(V) and vanadium(V) without performing time-consuming sorption experiments.

Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

USGS Publications Warehouse

Sharif, M.S.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.

2011-01-01

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6. m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6. m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory. ?? 2011 Elsevier Ltd.

The novel kinetics expression of Cadmium (II) removal using green adsorbent horse dung humic acid (Hd-Ha)

NASA Astrophysics Data System (ADS)

Basuki, Rahmat; Santosa, Sri Juari; Rusdiarso, Bambang

2017-03-01

Humic acid from dry horse dung powder has been prepared and this horse dung humic acid (HD-HA) was then applied as a sorbent to adsorb Cadmium(II) from a solution. Characterization of HD-HA was conducted by detection of its functional group, UV-Vis spectra, ash level, and total acidity. Result of the work showed that HD-HA had similar character compared with peat soil humic acid (PS-HA) and previous researchers. The adsorption study of this work was investigated by batch experiment in pH 5. The thermodynamics parameters in this work were determined by the Langmuir isotherm model for monolayer sorption and Freundlich isotherm model multilayer sorption. Monolayer sorption capacity (b) for HD-HA was 1.329 × 10-3 mol g-1, equilibrium constant (K) was 5.651 (mol/L)-1, and multilayer sorption capacity was 2.646 × 10-2 mol g-1. The kinetics parameters investigated in this work were determined by the novel kinetics expression resulted from the mathematical derivation the availability of binding sites of sorbent. Adsorption rate constant (ka) from this novel expression was 43.178 min-1 (mol/L)-1 and desorption rate constant (kd) was 1.250 × 10-2 min-1. Application of the kinetics model on sorption Cd(II) onto HD-HA showed the nearly all of models gave a good linearity. However, only this proposed kinetics expression has good relation with Langmuir model. The novel kinetics expression proposed in this paper seems to be more realistic and reasonable and close to the experimental real condition because the value of ka/kd (3452 (mol/L)-1) was fairly close with K from Langmuir isotherm model (5651 (mol/L)-1). Comparison of this novel kinetics expression with well-known Lagergren pseudo-first order kinetics and Ho pseudo-second order kinetics was also critically discussed in this paper.

Effects of gas sorption-induced swelling/shrinkage on the cleat compressibility of coal under different bedding directions.

PubMed

Peng, Shoujian; Fang, Zhiming; Shen, Jian; Xu, Jiang; Wang, Geoff

2017-10-30

The cleat compressibility of coal is a key parameter that is extensively used in modeling the coal reservoir permeability for Coal Bed Methane (CBM) recovery. Cleat compressibility is often determined from the permeability measurement made at different confining pressures but with a constant pore pressure. Hence, this parameter ignores the sorption strain effects on the cleat compressibility. By using the transient pulse decay (TPD) technique, this study presents the results from a laboratory characterization program using coal core drilled from different bedding directions to estimate gas permeability and coal cleat compressibility under different pore pressures while maintaining effective stress constant. Cleat compressibility was determined from permeability and sorption strain measurements that are made at different pore pressures under an effective stress constant. Results show that the cleat compressibility of coal increases slightly with the increase of pore pressure. Moreover, the cleat compressibility of Sample P (representing the face cleats in coal) is larger than that of Sample C (representing the butt cleats in coal). This result suggests that cleat compressibility should not be regarded as constant in the modeling of the CBM recovery. Furthermore, the compressibility of face cleats is considerably sensitive to the sorption-induced swelling/shrinkage and offers significant effects on the coal permeability.

Design Models for the Development of Helium-Carbon Sorption Crycoolers

NASA Technical Reports Server (NTRS)

Lindensmith, C. A.; Ahart, M.; Bhandari, P.; Wade, L. A.; Paine, C. G.

2000-01-01

We have developed models for predicting the performance of helium-based Joule-Thomson continuous-flow cryocoolers using charcoal-pumped sorption compressors. The models take as inputs the number of compressors, desired heat-lift, cold tip temperature, and available precooling temperature and provide design parameters as outputs. Future laboratory development will be used to verify and improve the models. We will present a preliminary design for a two-stage vibration-free cryocooler that is being proposed as part of a mid-infrared camera on NASA's Next Generation Space Telescope. Model predictions show that a 10 mW helium-carbon cryocooler with a base temperature of 5.5 K will reject less than 650 mW at 18 K. The total input power to the helium-carbon stage is 650 mW. These models, which run in MathCad and Microsoft Excel, can be coupled to similar models for hydrogen sorption coolers to give designs for 2-stage vibration-free cryocoolers that provide cooling from approx. 50 K to 4 K.

Design Models for the Development of Helium-Carbon Sorption Cryocoolers

NASA Technical Reports Server (NTRS)

Lindensmith, Chris A.; Ahart, M.; Bhandari, P.; Wade, L. A.; Paine, C. G.

2000-01-01

We have developed models for predicting the performance of helium-based Joule-Thomson continuous-flow cryocoolers using charcoal-pumped sorption compressors. The models take as inputs the number of compressors, desired heat-lift, cold tip temperature, and available precooling temperature and provide design parameters as outputs. Future laboratory development will be used to verify and improve the models. We will present a preliminary design for a two-stage vibration-free cryocooler that is being proposed as part of a mid-infrared camera on NASA's Next Generation Space Telescope. Model predictions show that a 10 mW helium-carbon cryocooler with a base temperature of 5.5 K will reject less than 650 mW at 18 K. The total input power to the helium-carbon stage is 650 mW. These models, which run in MathCad and Microsoft Excel, can be coupled to similar models for hydrogen sorption coolers to give designs for 2-stage vibration-free cryocoolers that provide cooling from approximately 50 K to 4 K.

Sulfamethazine Sorption to Soil: Vegetative Management, pH, and Dissolved Organic Matter Effects.

PubMed

Chu, Bei; Goyne, Keith W; Anderson, Stephen H; Lin, Chung-Ho; Lerch, Robert N

2013-01-01

Elucidating veterinary antibiotic interactions with soil is important for assessing and mitigating possible environmental hazards. The objectives of this study were to investigate the effects of vegetative management, soil properties, and >1000 Da dissolved organic matter (DOM) on sulfamethazine (SMZ) behavior in soil. Sorption experiments were performed over a range of SMZ concentrations (2.5-50 μmol L) using samples from three soils (Armstrong, Huntington, and Menfro), each planted to one of three vegetation treatments: agroforestry buffers strips (ABS), grass buffer strips (GBS), and row crops (RC). Our results show that SMZ sorption isotherms are well fitted by the Freundlich isotherm model (log = 0.44-0.93; Freundlich nonlinearity parameter = 0.59-0.79). Further investigation of solid-to-solution distribution coefficients () demonstrated that vegetative management significantly ( < 0.05) influences SMZ sorption (ABS > GBS > RC). Multiple linear regression analyses indicated that organic carbon (OC) content, pH, and initial SMZ concentration were important properties controlling SMZ sorption. Study of the two most contrasting soils in our sample set revealed that increasing solution pH (pH 6.0-7.5) reduced SMZ sorption to the Armstrong GBS soil, but little pH effect was observed for the Huntington GBS soil containing 50% kaolinite in the clay fraction. The presence of DOM (150 mg L OC) had little significant effect on the Freundlich nonlinearity parameter; however, DOM slightly reduced SMZ values overall. Our results support the use of vegetative buffers to mitigate veterinary antibiotic loss from agroecosystems, provide guidance for properly managing vegetative buffer strips to increase SMZ sorption, and enhance understanding of SMZ sorption to soil. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Waste isolation safety assessment program. Task 4. Collection and generation of transport data theoretical and experimental evaluation of waste transport in selected rocks. Annual progress report, October 1, 1978-September 30, 1979

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

Silva, R.J.; Benson, L.V.; Yee, A.W.

1979-09-30

The objective of the program is to establish a basis for the prediction of radionuclide sorption in geologic environments. In FY 79, experimental and theoretical efforts were concentrated on a study of the sorption of cesium on the solid substrates Min-u-sil (quartz) and Belle Fourche clay (montmorillonite). Cesium sorption isotherms were obtained for the two substrates at 26/sup 0/C as a function of initial Cs concentration in solution (10/sup -3/M to 10/sup -9/M), pH (5 to 10) and supporting electrolyte concentration (0.002M, 0.01M, 0.1M, and 1M) NaCl and a simulated basalt groundwater in batch-type experiments using crushed material. Characterization ofmore » the solid phases included measurements of chemical compositions, particle sizes, surface areas, and cation-exchange capacities. In addition, potentiometric acid/base titrations of the solid phases were conducted in order to determine the acid dissociation and electrolyte exchange constants of the surfaces. Preliminary analysis of the sorption data indicate that while the clay data could be explained by simple mass-action expressions, the quartz data could not. Theoretical efforts were aimed at developing and testing an electrolyte binding electrical double-layer model to predict sorption isotherms. A computerized version of the model, MINEQL, which simultaneously considers surface and solution chemical equilibria, was brought to operational status. Input parameters required by MINEQL were determined and sorption isotherms for Cs on the Belle Fourche clay were calculated over the same range of parameters as the experimental measurements. Comparisons showed that the model was able to simulate the isotherms quite well except at the lowest pH values for the 0.002M and 0.01M NaCl solutions.« less

Imidacloprid transport and sorption nonequilibrium in single and multilayered columns of Immokalee fine sand

PubMed Central

Nkedi-Kizza, Peter; Morgan, Kelly T.; Kadyampakeni, Davie M.

2017-01-01

Imidacloprid (IMD) is a neonicotinoid pesticide soil-drenched to many crops to control piercing-sucking insects such as the Asian citrus psyllid (ACP). Neonicotinoids are persistent in the environment and transport analyses are helpful estimate leaching potential from soils that could result in groundwater pollution. The objective of this study was to analyze IMD breakthrough under saturated water flow in soil columns packed with three horizons (A, E, Bh) of Immokalee Fine Sand (IFS). Also, we used the dimensionless form of the convective-dispersive model (CD-Model) to compare the optimized transport parameters from each column experiment (retardation factor, R; fraction of instantaneous-to-total retardation, β; and mass transfer coefficient, ω) with the parameters obtained from sorption batch equilibria and sorption kinetics. The tracer (Cl-) breakthrough curves (BTCs) were symmetrical and properly described by the CD-Model. IMD BTCs from A, Bh, and multilayered [A+E+Bh] soil columns showed steep fronts and tailing that were well described by the one-site nonequilibrium (OSNE) model, which was an evidence of non-ideal transport due to IMD mass transfer into the soil organic matter. In general, IMD was weakly-sorbed in the A and Bh horizons (R values of 3.72 ± 0.04 and 3.08 ± 0.07, respectively), and almost no retardation was observed in the E horizon (R = 1.20 ± 0.02) due to its low organic matter content (0.3%). Using the HYDRUS-1D package, optimized parameters (R, β, ω) from the individual columns successfully simulated IMD transport in a multilayered column mimicking an IFS soil profile. These column studies and corresponding simulations agreed with previous findings from batch sorption equilibria and kinetics experiments, where IMD showed one-site kinetic mass transfer between soil surfaces and soil solution. Ideally, sandy soils should be maintained unsaturated by crop irrigation systems and rainfall monitoring during and after soil-drench application. The unsaturated soil will increase IMD retardation factors and residence time for plant uptake, lowering leaching potential from soil layers with low sorption capacity, such as the E horizon. PMID:28837702

Transport of bisphenol-A in sandy aquifer sediment: Column experiment.

PubMed

Zakari, Sissou; Liu, Hui; Tong, Lei; Wang, Yan; Liu, Jianfeng

2016-02-01

The present paper aims to study the transport behavior of bisphenol-A (BPA) in sandy aquifer so as to provide important parameters for the prediction and control of contaminant plume in aquifer. Miscible displacement experiments were conducted and the breakthrough curves (BTCs) were simulated using HYDRUS-1D software. The effects of pore-water velocity (10-52 cm h(-1)) and initial concentration (2.5-40 mg L(-1)) on the sorption were also investigated. The BTCs of BPA fit the linear first-order non-equilibrium two-site model. The parameters such as partition coefficient (K(d)), the fraction of instantaneous adsorption on "Type-1" sites (F), the first order sorption rate coefficient for the kinetic non-equilibrium (type-2) sites (α), the retardation coefficient (R), and sorption capacity (q(column)) were computed. Results showed that BPA transported 0.11-0.83 m with various pore water velocity in sandy sediment column when water flowed 1 m. The sorption of BPA was mainly caused by the instantaneous surface adsorption as F varied from 0.596 to 0.908. The transport velocity of BPA was affected by pore water velocity (v) and followed the linear equation 1/R = 0.0600 + 0.0110v (r(2) = 0.9724). The parameter K(d) were also closely related to v and followed the equation LnK(d) = 1.0023-0.0482v (r(2) = 0.9690). The sorption capacity was more related to the initial BPA concentration (C0) and followed the linear equation q(column) = 0.265 + 0.253C0 (r(2) = 0.9727). The parameter α was affected by both v and C0 whereas F was not dramatically affected by both. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of sorption into single ODS-silica gel microparticles in acetonitrile-water.

PubMed

Nakatani, Kiyoharu; Kakizaki, Hiroshi

2003-08-01

Intraparticle mass transfer processes of Phenol Blue (PB) in single octadecylsilyl (ODS)-silica gel microparticles in acetonitrile-water were analyzed by microcapillary manipulation and microabsorption methods. An absorption maximum of PB, the sorption isotherm parameters, and the sorption rate in the microparticle system were highly dependent on the percentage of acetonitrile in solution. The results are discussed in terms of the microscopic polarity surrounding PB in the ODS phase and the relationship between the isotherm parameters and the sorption rate.

Reactive-transport simulation of phosphorus in the sewage plume at the Massachusetts Military Reservation, Cape Cod, Massachusetts

USGS Publications Warehouse

Parkhurst, David L.; Stollenwerk, Kenneth G.; Colman, John A.

2003-01-01

The subsurface transport of phosphorus introduced by the disposal of treated sewage effluent to ground-infiltration disposal beds at the Massachusetts Military Reservation on western Cape Cod was simulated with a three-dimensional reactive-transport model. The simulations were used to estimate the load of phosphorus transported to Ashumet Pond during operation of the sewage-treatment plant?from 1936 to 1995?and for 60 years following cessation of sewage disposal. The model accounted for spatial and temporal changes in water discharge from the sewage-treatment plant, ground-water flow, transport of associated chemical constituents, and a set of chemical reactions, including phosphorus sorption on aquifer materials, dissolution and precipitation of iron- and manganese-oxyhydroxide and iron phosphate minerals, organic carbon sorption and decomposition, cation sorption, and irreversible denitrification. The flow and transport in the aquifer were simulated by using parameters consistent with those used in previous flow models of this area of Cape Cod, except that numerical dispersion was much larger than the physical dispersion estimated in previous studies. Sorption parameters were fit to data derived from phosphorus sorption and desorption laboratory column experiments. Rates of organic carbon decomposition were adjusted to match the location of iron concentrations in an anoxic iron zone within the sewage plume. The sensitivity of the simulated load of phosphorus transported to Ashumet Pond was calculated for a variety of processes and input parameters. Model limitations included large uncertainties associated with the loading of the sewage beds, the flow system, and the chemistry and sorption characteristics in the aquifer. The results of current model simulations indicate a small load of phosphorus transported to Ashumet Pond during 1965?85, but this small load was particularly sensitive to model parameters that specify flow conditions and the chemical process by which non-desorbable phosphorus is incorporated in the sediments. The uncertainties were large enough to make it difficult to determine whether loads of phosphorus transported to Ashumet Pond in the 1990s were greater or less than loads during the previous two decades. The model simulations indicate substantial discharge of phosphorus to Ashumet Pond after about 1965. After the period 2000?10 the simulations indicate that the load of phosphorus transported to Ashumet Pond decreases continuously, but the load of phosphorus remains substantial for many decades. The current simulations indicate a peak in phosphorus discharge to Ashumet Pond of about 1,000 kilograms per year during the 1990s; however, comparisons of simulated phosphorus concentrations with measured concentrations in 1993 indicate that the peak in phosphorus load transported to Ashumet Pond may be larger and moving more quickly in the model simulations than in the aquifer. The results of the three-dimensional reactive-transport simulations are consistent with the loading history, experimental laboratory data, and field measurements. The results of the simulations adequately reproduce the spatial distribution of phosphorus concentrations measured in 1993, the magnitude of changes in phosphorus concentration with time in a profile near the disposal beds following cessation of sewage disposal, the observed iron zone in the sewage plume, the approximate flow of treated sewage effluent into Ashumet Valley, and laboratory-column data for phosphorus sorption and desorption.

Sorption of organic compounds by aged polystyrene microplastic particles.

PubMed

Hüffer, Thorsten; Weniger, Anne-Katrin; Hofmann, Thilo

2018-05-01

Microplastics that are released into the environment undergo aging and interact with other substances such as organic contaminants. Understanding the sorption interactions between aged microplastics and organic contaminants is therefore essential for evaluating the impact of microplastics on the environment. There is little information available on how the aging of microplastics affects their sorption behavior and other properties. We have therefore investigated the effects of an accelerated UV-aging procedure on polystyrene microplastics, which are used in products such as skin cleaners and foams. Physical and chemical particle characterizations showed that aging led to significant surface oxidation and minor localized microcrack formation. Sorption coefficients of organic compounds by polystyrene microplastics following aging were up to one order of magnitude lower than for pristine particles. Sorption isotherms were experimentally determined using a diverse set of probe sorbates covering a variety of substance classes allowing an in-depth evaluation of the poly-parameter linear free-energy relationship (ppLFER) modelling used to investigate the contribution of individual molecular interactions to overall sorption. The ppLFER modelling was validated using internal cross-validation, which confirmed its robustness. This approach therefore yields improved estimates of the interactions between aged polystyrene microplastics and organic contaminants. Copyright © 2018 Elsevier Ltd. All rights reserved.

In situ precipitation of nano-hydroxyapatite in gelatin polymatrix towards specific fluoride sorption.

PubMed

Pandi, Kalimuthu; Viswanathan, Natrayasamy

2015-03-01

This study investigates the synthesis of nano-hydroxyapatite (n-HAp) incorporated gelatin (Gel) biocomposite namely n-HAp@Gel composite for efficient removal of fluoride from aqueous solution. The results demonstrated that, the developed n-HAp@Gel biocomposite possess an enhanced defluoridation capacity (DC) of 4157 mgF-/kg. The batch experiments were optimized as a function of various influencing parameters like contact time, pH, co-ions, temperature and initial fluoride concentration. The physicochemical characteristics of n-HAp@Gel composite was examined by using different instrumental techniques like FTIR, XRD, TGA-DSC and SEM with EDAX analysis. The sorption data were fitted with various isotherm models. The acquired thermodynamic parameters showed that the sorption of fluoride onto the sorbent was endothermic and spontaneous in nature. The reaction-based and diffusion-based models were used to identify the kinetics of the reaction. At field conditions, n-HAp@Gel composite reduce the fluoride concentration below the tolerance limit. A regeneration technique was proposed in order to reuse the sorbent. Copyright © 2014 Elsevier B.V. All rights reserved.

Identification of TCE and PCE sorption and biodegradation parameters in a sandy aquifer for fate and transport modelling: batch and column studies.

PubMed

Kret, E; Kiecak, A; Malina, G; Nijenhuis, I; Postawa, A

2015-07-01

The main aim of this study was to determine the sorption and biodegradation parameters of trichloroethene (TCE) and tetrachloroethene (PCE) as input data required for their fate and transport modelling in a Quaternary sandy aquifer. Sorption was determined based on batch and column experiments, while biodegradation was investigated using the compound-specific isotope analysis (CSIA). The aquifer materials medium (soil 1) to fine (soil 2) sands and groundwater samples came from the representative profile of the contaminated site (south-east Poland). The sorption isotherms were approximately linear (TCE, soil 1, K d = 0.0016; PCE, soil 1, K d = 0.0051; PCE, soil 2, K d = 0.0069) except for one case in which the best fitting was for the Langmuir isotherm (TCE, soil 2, K f = 0.6493 and S max = 0.0145). The results indicate low retardation coefficients (R) of TCE and PCE; however, somewhat lower values were obtained in batch compared to column experiments. In the column experiments with the presence of both contaminants, TCE influenced sorption of PCE, so that the R values for both compounds were almost two times higher. Non-significant differences in isotope compositions of TCE and PCE measured in the observation points (δ(13)C values within the range of -23.6 ÷ -24.3‰ and -26.3 ÷-27.7‰, respectively) indicate that biodegradation apparently is not an important process contributing to the natural attenuation of these contaminants in the studied sandy aquifer.

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

PubMed

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

2018-03-01

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

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

PubMed

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

2014-07-01

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

Sorption, desorption, and surface oxidative fate of nicotine.

PubMed

Petrick, Lauren; Destaillats, Hugo; Zouev, Irena; Sabach, Sara; Dubowski, Yael

2010-09-21

Nicotine dynamics in an indoor environment can be greatly affected by building parameters (e.g. relative humidity (RH), air exchange rate (AER), and presence of ozone), as well as surface parameters (e.g. surface area (SA) and polarity). To better understand the indoor fate of nicotine, these parameter effects on its sorption, desorption, and oxidation rates were investigated on model indoor surfaces that included fabrics, wallboard paper, and wood materials. Nicotine sorption under dry conditions was enhanced by higher SA and higher polarity of the substrate. Interestingly, nicotine sorption to cotton and nylon was facilitated by increased RH, while sorption to polyester was hindered by it. Desorption was affected by RH, AER, and surface type. Heterogeneous nicotine-ozone reaction was investigated by Fourier transform infrared spectrometry with attenuated total reflection (FTIR-ATR), and revealed a pseudo first-order surface reaction rate of 0.035 +/- 0.015 min(-1) (at [O(3)] = 6 +/- 0.3 x 10(15) molecules cm(-3)) that was partially inhibited at high RH. Extrapolation to a lower ozone level ([O(3)] = 42 ppb) showed oxidation on the order of 10(-5) min(-1) corresponding to a half-life of 1 week. In addition, similar surface products were identified in dry and high RH using gas chromatography-mass spectrometry (GC-MS). However, FTIR analysis revealed different product spectra for these conditions, suggesting additional unidentified products and association with surface water. Knowing the indoor fate of condensed and gas phase nicotine and its oxidation products will provide a better understanding of nicotine's impact on personal exposures as well as overall indoor air quality.

Theoretical and experimental evaluation of effective stress-induced sorption capacity change and its influence on coal permeability

NASA Astrophysics Data System (ADS)

Li, Chengwu; Dong, Lihui; Xu, Xiaomeng; Hu, Po; Tian, Jianwei; Zhang, Yihuai; Yang, Leilei

2017-06-01

The gas sorption effect is an important factor affecting the gas permeability of a coal seam, which has been proved in many previous experimental measurements and analytical permeability studies. However, the sorption capacity of coal is usually not static due to the complexity of external stress variation and internal gas media features. The stress-induced sorption capacity variation and its effect on the coal permeability change have not been fully identified yet. Thus, in this paper we present a preliminary evaluation of the stress-induced sorption capacity change by introducing the adsorption capacity modified term, and an experiment is carried out to verify the influence of the altered effective stress on coal permeability. Langmuir-like adsorption deformation constant parameters were combined into the modified coal permeability model and were given values to fully estimate the influence on permeability caused by the modification term. We found that different change modes of effective stress would yield different change effects on the permeability, that is, with the same effective stress change amount, the altered external stress-induced change had less influence than the altered-pore pressure-induced change; however, both modes demonstrated that the model taking sorption capacity change into consideration is more consistent with the experimental data. The effect of sorption capacity change on coal permeability variation was also found to be tightly connected with the physical and mechanical properties of the coal itself. It is proved that considering stress-induced sorption ability change has a critical role in characterizing the permeability variation of coal.

Upgrade to Ion Exchange Modeling for Removal of Technetium from Hanford Waste Using SuperLig® 639 Resin

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

Hamm, L.; Smith, F.; Aleman, S.

2013-05-16

This report documents the development and application of computer models to describe the sorption of pertechnetate [TcO₄⁻], and its surrogate perrhenate [ReO₄⁻], on SuperLig® 639 resin. Two models have been developed: 1) A thermodynamic isotherm model, based on experimental data, that predicts [TcO₄⁻] and [ReO₄⁻] sorption as a function of solution composition and temperature and 2) A column model that uses the isotherm calculated by the first model to simulate the performance of a full-scale sorption process. The isotherm model provides a synthesis of experimental data collected from many different sources to give a best estimate prediction of the behaviormore » of the pertechnetate-SuperLig® 639 system and an estimate of the uncertainty in this prediction. The column model provides a prediction of the expected performance of the plant process by determining the volume of waste solution that can be processed based on process design parameters such as column size, flow rate and resin physical properties.« less

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

USGS Publications Warehouse

Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

1999-01-01

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Thermodynamic parameters of U (VI) sorption onto soils in aquatic systems.

PubMed

Kumar, Ajay; Rout, Sabyasachi; Ghosh, Malay; Singhal, Rakesh Kumar; Ravi, Pazhayath Mana

2013-01-01

The thermodynamic parameters viz. the standard free energy (∆Gº), Standard enthalpy change (∆Hº) and standard entropy change (∆Sº) were determined using the obtained values of distribution coefficient (kd) of U (VI) in two different types of soils (agricultural and undisturbed) by conducting a batch equilibrium experiment with aqueous media (groundwater and deionised water) at two different temperatures 25°C and 50°C. The obtained distribution coefficients (kd) values of U for undisturbed soil in groundwater showed about 75% higher than in agricultural soil at 25°C while in deionised water, these values were highly insignificant for both soils indicating that groundwater was observed to be more favorable for high surface sorption. At 50°C, the increased kd values in both soils revealed that solubility of U decreased with increasing temperature. Batch adsorption results indicated that U sorption onto soils was promoted at higher temperature and an endothermic and spontaneous interfacial process. The high positive values of ∆Sº for agricultural soil suggested a decrease in sorption capacity of U in that soil due to increased randomness at solid-solution interface. The low sorption onto agricultural soil may be due to presence of high amount of coarse particles in the form of sand (56%). Geochemical modeling predicted that mixed hydroxo-carbonato complexes of uranium were the most stable and abundant complexes in equilibrium solution during experimental.

Sorption interactions of heavy metals with biochar in soil remediation studies

NASA Astrophysics Data System (ADS)

Fristak, Vladimir; Friesl-Hanl, Wolfgang; Wawra, Anna; Soja, Gerhard

2015-04-01

The search for new materials in soil remediation applications has led to new conversion technologies such as carbonization and pyrolysis. Biochar represents the pyrolytic product of different biomass input materials processed at 350-1000°C and anoxic conditions. The pyrolysis temperature and feedstock have a considerable influence on the quality of the charred product and also its main physico-chemical properties. Biochar as porous material with large specific surface and C-stability is utilized in various environmental and agricultural technologies. Carbon sequestration, increase of soil water-holding capacity and pH as well as sorption of different xenobiotics present only a fraction of the multitude of biochar application possibilities. Heavy metals as potential sources of ecotoxicological risks are characterized by their non-degradability and the potential transfer into the food chain. Carbonaceous materials have been used for a long time as sorbents for heavy metals and organic contaminants in soil and water technologies. The similarity of biochar with activated carbon predetermines this material as remediation tool which plays an important role in heavy metal immobilization and retention with a parallel reduction in the risk of ground water and food crop contamination. In all this processes the element-specific sorption behaviour of biochar creates new conditions for pollutant binding. Sorption interaction and separation of contaminants from soil solution or waste effluent can be affected by wide-ranging parameters. In detail, our study was based on batch-sorption comparisons of two biochars produced from wood chips and green waste residues. We observed that sorption efficiency of biochar for model bivalent heavy metals (Cd, Zn, Cu) can be influenced by equilibrium parameters such as pH, contact time, initial concentration of metal in reaction solutions, presence of surfactants and chemical modification by acid hydrolysis, esterification and methylation. The study of sorption mechanisms showed differences in the sorption of the targeted heavy metals in relation to the contribution of ion-exchange and precipitation processes. We confirmed the effectivity of physico-chemical artificial aging on sorption capacity of biochar in terms of changes in surface structure. Based on these results, the application potential of biochar as sorption material for stabilizing heavy metals in soils is discussed.

Environmental Interactions of Hydrazine Fuels in Soil/Water Systems

DTIC Science & Technology

1988-10-01

model requires that two equations be solved numerically, one for convective-dispersive transport ac/at = D a2 C/az 2 - uaC/az + [p/Glk S I - kfC [7...the menu and get the users choice; if [CHoice.LE.0) THEN If (.Not.AskOus’Do you wish to terminate?’,.true.,12)) (confirm termination before...Return to General Simulation Parameters Menu ’,’ & ’<l> Ion-Exchange (Hydrazium vs Calcium)’, & ’ɚ> Reversible Sorption’, & ’ɛ> Irreversible Sorption

Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder: Kinetics, isotherms, and thermodynamic studies.

PubMed

Subbaiah, Munagapati Venkata; Kim, Dong-Su

2016-06-01

Present research discussed the utilization of aminated pumpkin seed powder (APSP) as an adsorbent for methyl orange (MO) removal from aqueous solution. Batch sorption experiments were carried to evaluate the influence of pH, initial dye concentration, contact time, and temperature. The APSP was characterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The experimental equilibrium adsorption data were fitted using two two-parameter models (Langmuir and Freundlich) and two three-parameter models (Sips and Toth). Langmuir and Sips isotherms provided the best model for MO adsorption data. The maximum monolayer sorption capacity was found to be 200.3mg/g based on the Langmuir isotherm model. The pseudo-first-order and pseudo-second-order model equations were used to analyze the kinetic data of the adsorption process and the data was fitted well with the pseudo-second-order kinetic model (R(2)>0.97). The calculated thermodynamic parameters such as ΔG(0), ΔH(0) and ΔS(0) from experimental data showed that the sorption of MO onto APSP was feasible, spontaneous and endothermic in the temperature range 298-318 K. The FTIR results revealed that amine and carboxyl functional groups present on the surface of APSP. The SEM results show that APSP has an irregular and porous surface which is adequate morphology for dye adsorption. Desorption experiments were carried to explore the feasibility of adsorbent regeneration and the adsorbed MO from APSP was desorbed using 0.1M NaOH with an efficiency of 93.5%. Findings of the present study indicated that APSP can be successfully used for removal of MO from aqueous solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Sorption, degradation and transport phenomena of alcohol ethoxysulfates in agricultural soils. Laboratory studies.

PubMed

Fernández-Ramos, C; Rodríguez-Gómez, R; Reis, M S; Zafra-Gómez, A; Verge, C; de Ferrer, J A; Pérez-Pascual, M; Vílchez, J L

2017-03-01

In the present work, laboratory studies were conducted in order to determine and model the sorption, degradation and transport processes of alcohol ethoxysulfates (AES), one of the most important groups of anionic surfactants. Adsorption/desorption isotherms were obtained for several structurally related AES ethoxymers (homologue AES-C 12 E n with n = 0-10 ethoxymer units and homologue AES-C 14 E n with n = 0-7 ethoxymer units) using a batch equilibrium method. Data were fitted to a linear and a Freundlich isotherm models. Additionally, experiments in continuous-flow soil columns were also carried out and the breakthrough curves observed for each compound were studied. Breakthrough curves were used to determine the fundamental parameters of the transport model (hydrodynamic dispersion coefficient, degradation rate constant and adsorption/desorption isotherm slope), that is the main phenomena that take place simultaneously when AES move through agricultural soil. When the results obtained for the AES ethoxymers are combined, they reveal a clear and consistent trend towards a sorption increase with the number of ethoxylated units and with the length of the alkyl chain that opens the possibility to estimate the values of the transport parameters for other structurally related ethoxymers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Moisture sorption characteristics of extrusion-cooked starch protective loose-fill cushioning foams

NASA Astrophysics Data System (ADS)

Combrzyński, Maciej; Mościcki, Leszek; Kwaśniewska, Anita; Oniszczuk, Tomasz; Wójtowicz, Agnieszka; Sołowiej, Bartosz; Gładyszewska, Bożena; Muszyński, Siemowit

2017-10-01

The aim of this work was to determine the water vapour sorption properties of thermoplastic starch filling foams processed by extrusion-cooking technique from various combinations of potato starch and two foaming agents: poly(vinyl) alcohol and Plastronfoam, in amount of 1, 2 and 3% each. Foams were processed with the single screw extruder-cooker at two different screw rotational speeds 100 and 130 r.p.m. The sorption isotherms of samples were determined and described using the Guggenheim-Anderson-de Boer model. Also, the kinetics of water vapour adsorption by foams, as a function of time, was measured and fitted with Peleg model. On the basis of the analysis the influence of the applied foaming agents, as well as the technological parameters of extrusion-cooking process in relation to water vapour adsorption by thermoplastic starch foams was demonstrated. There was no difference between the shapes of the isotherms for poly(vinyl) alcohol foams while for Plastronfoam foams a notable difference among foams extruded at 100 r.p.m. was observed in the regions of low and high humidity content. The analysis of the Guggenheim-Anderson-de Boer model parameters showed that the water molecules were less strongly bound with the foam surface when extruded at a lower screw speed.

Adsorptive removal of Cu(II) from aqueous solution and industrial effluent using natural/agricultural wastes.

PubMed

Singha, Biswajit; Das, Sudip Kumar

2013-07-01

The potentiality of low cost natural/agricultural waste biomasses for the removal of Cu(II) ion from aqueous solution has been investigated in batch experiments. The effect of various physico-chemical parameters such as initial pH, initial Cu(II) concentration, adsorbent dosage, contact time and temperature has been studied. The optimum pH for adsorption was found to be 6 for all adsorbents used. Kinetics data were best described by the pseudo-2nd-order model. The experimental data were fitted well with Freundlich and Halsey isotherm models. The diffusion coefficient and sorption energy indicated that the adsorption process was chemical in nature. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated, and it was observed that the adsorption process was spontaneous and endothermic. The mean sorption energy was calculated using Dubinin-Radushkevich isotherm model and it confirmed that the sorption process was chemical in nature. Different active functional groups were identified by FTIR studies which were responsible for Cu(II) ion adsorption process. Application study using electroplating industrial waste water and regeneration experiment of the adsorbent were also investigated. Design procedure for the batch process was also reported. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Impact of alkaline alterations to a Brazilian soil on cesium retention under low temperature conditions.

PubMed

Calábria, Jaqueline Alves de Almeida; Cota, Stela Dalva Santos; de Morais, Gustavo Ferrari; Ladeira, Ana Cláudia Queiroz

2017-11-01

To be used as backfilling materials in radioactive waste disposal facilities, a natural material must have a suitable permeability, mechanical properties and a high sorption capacity for radionuclides. Also important when considering a material as a backfill is the effect of its interaction with the alkaline solution generated from concrete degradation. This solution promotes mineralogical alterations that result in significant changes in the material key properties influencing its performance as a safety component of the repository. This paper presents results of an investigation on the effect of alkaline interaction under a low temperature on cesium retention properties of a local soil being considered suitable as a backfill for the Brazilian near surface disposal facility. A sample of the Brazilian soil was mixed with an alkaline solution, simulating the pore water leached in the first stage of cement degradation, during 1, 7, 14 and 28 days. The experiments were conducted under low temperature (25 °C) aiming to evaluate similar conditions found on a low and intermediate level radioactive waste disposal installation. A non-classical isotherm sorption model was fitted to sorption data obtained from batch experiments, for unaltered and altered samples, providing parameters that allowed us to assess the effect of the interaction on material quality as Cs sorbent. The sorption parameters obtained from the data-fitted isotherm were used then to estimate the corresponding retardation factor (R). Alkaline interaction significantly modified the soil sorption properties for Cs. The parameter Q, related to the maximum sorption capacity, as well as the affinity parameter (K) and the retardation coefficients became significantly smaller (about 1000 times for the R coefficient) after pretreatment with the simulated alkaline solutions. Moreover, the increase in n-values, which is related with the energy distribution width and heterogeneity of surface site energies, demonstrated that the adsorbent surface became more homogenous as a consequence of the alkaline alteration. Together these results suggest that cementitious leachate has a profound effect on Cs retention and should be accounted for estimating radionuclide retention in radioactive waste disposal systems containing cementitious materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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

Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

PubMed

Amosa, Mutiu K

2016-08-01

Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process.

Air drying modelling of Mastocarpus stellatus seaweed a source of hybrid carrageenan

NASA Astrophysics Data System (ADS)

Arufe, Santiago; Torres, Maria D.; Chenlo, Francisco; Moreira, Ramon

2018-01-01

Water sorption isotherms from 5 up to 65 °C and air drying kinetics at 35, 45 and 55 °C of Mastocarpus stellatus seaweed were determined. Experimental sorption data were modelled using BET and Oswin models. A four-parameter model, based on Oswin model, was proposed to estimate equilibrium moisture content as function of water activity and temperature simultaneously. Drying experiments showed that water removal rate increased significantly with temperature from 35 to 45 °C, but at higher temperatures drying rate remained constant. Some chemical modifications of the hybrid carrageenans present in the seaweed can be responsible of this unexpected thermal trend. Experimental drying data were modelled using two-parameter Page model (n, k). Page parameter n was constant (1.31 ± 0.10) at tested temperatures, but k varied significantly with drying temperature (from 18.5 ± 0.2 10-3 min-n at 35 °C up to 28.4 ± 0.8 10-3 min-n at 45 and 55 °C). Drying experiments allowed the determination of the critical moisture content of seaweed (0.87 ± 0.06 kg water (kg d.b.)-1). A diffusional model considering slab geometry was employed to determine the effective diffusion coefficient of water during the falling rate period at different temperatures.

Water sorption equilibria and kinetics of henna leaves

NASA Astrophysics Data System (ADS)

Sghaier, Khamsa; Peczalski, Roman; Bagane, Mohamed

2018-05-01

In this work, firstly the sorption isotherms of henna leaves were determined using a dynamic vapor sorption ( DVS) device at 3 temperatures (30, 40, 50 °C). The equilibrium data were well fitted by the GAB model. Secondly, drying kinetics were measured using a pilot convective dryer for 3 air temperatures (same as above), 3 velocities (0.5, 1, 1.42 m/s) and 4 relative humidities (20, 30, 35, 40%). The drying kinetic coefficients were identified by fitting the DVS and pilot dryer data by Lewis semi-empirical model. In order to compare the obtained kinetic parameters with literature, the water diffusivities were also identified by fitting the data by the simplified solution of fickian diffusion equation. The identified kinetic coefficient was mainly dependent on air temperature and velocity what proved that it represented rather the external transfer and not the internal one.

Modelling of hydrogen permeability of membranes for high-purity hydrogen production

NASA Astrophysics Data System (ADS)

Zaika, Yury V.; Rodchenkova, Natalia I.

2017-11-01

High-purity hydrogen is required for clean energy and a variety of chemical technology processes. Different alloys, which may be well-suited for use in gas-separation plants, were investigated by measuring specific hydrogen permeability. One had to estimate the parameters of diffusion and sorption to numerically model the different scenarios and experimental conditions of the material usage (including extreme ones), and identify the limiting factors. This paper presents a nonlinear mathematical model taking into account the dynamics of sorption-desorption processes and reversible capture of diffusing hydrogen by inhomogeneity of the material’s structure, and also modification of the model when the transport rate is high. The results of numerical modelling allow to obtain information about output data sensitivity with respect to variations of the material’s hydrogen permeability parameters. Furthermore, it is possible to analyze the dynamics of concentrations and fluxes that cannot be measured directly. Experimental data for Ta77Nb23 and V85Ni15 alloys were used to test the model. This work is supported by the Russian Foundation for Basic Research (Project No. 15-01-00744).

Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 1. Transport of triton X-100

USGS Publications Warehouse

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

1997-01-01

Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer at Picatinny Arsenal, NJ, has been studied through a series of laboratory and field experiments. In the laboratory, batch and column experiments were conducted to quantify the rate and amount of Triton X-100 sorption to the aquifer sediments. In the field, a 400 mg/L aqueous Triton X-100 solution was injected into the aquifer at a rate of 26.5 L/min for a 35-d period. The transport of Triton X-100 was monitored by sampling and analysis of groundwater at six locations surrounding the injection well. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two- dimensional (respectively) transient solute transport models with either equilibrium or rate-limited sorption. These analyses reveal that Triton X- 100 sorption to the aquifer solids is slow relative to advective and dispersive transport and that an equilibrium sorption model cannot simulate accurately the observed soil column and field data. Comparison of kinetic sorption parameters from batch, column, and field transport data indicate that both physical heterogeneities and Triton X-100 mass transfer between water and soil contribute to the kinetic transport effects.Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer was studied. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two-dimensional transient solute transport models with either equilibrium or rate-limited sorption. These analyses revealed that Triton X-100 sorption to the aquifer solids was slow relative to advective and dispersive transport.

Synthesis, characterization and study of sorption parameters of multi-walled carbon nanotubes/chitosan nanocomposite for the removal of picric acid from aqueous solutions.

PubMed

Khakpour, Roghayeh; Tahermansouri, Hasan

2018-04-01

The modification of carboxylated multi-wall carbon nanotubes (MWCNT-COOH) with chitosan (Chi) has been investigated to prepare a nanocomposite material (MWCNT-Chi) for the removal of picric acid from aqueous solutions. Materials were characterized by FT-IR, TGA, DTG, FESEM, EDX, BET and zeta potential. Batch experiments such as solution pH, dosage of adsorbents, contact time, concentration of the picric acid and temperature were achieved to study sorption process. Kinetic studies were well described by pseudo-second-order kinetic model for both adsorbents. The six isotherm models: Langmuir (four linear forms), Freundlich, Tempkin, Halsey, Harkins-Jura and Dubinin-Radushkevich models were applied to determine the characteristic parameters of the adsorption process. Isotherm studies showed that the Langmuir isotherm for MWCNT-Chi and Freundlich and Halsey models for both adsorbents were found to best represent the measured sorption data. In addition, the results of Dubinin-Radushkevich model confirmed the physical adsorption. Negative ΔG° values for MWCNT-Chi and positive ones for MWCNT-COOH indicated the nature of spontaneous and unspontaneous, respectively for adsorption process in the range of the studied concentrations. In addition, picric acid molecules can be desorbed from MWCNT-Chi up to 90% at pH = 9 and that the consumed MWCNT-Chi could be reutilized up to 5th cycle of regeneration. Copyright © 2017 Elsevier B.V. All rights reserved.

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 was in between that of Ultisols and Mollisols. HPLC results revealed significantly higher sorption of D-glucose and L-alanine than did TOC results, and duplicate experiments with sterilized soils confirmed that glucose and alanine were mineralized leading to higher apparent sorption values via HPLC. This study demonstrated that three common temperate soil orders experienced differential sorption of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC.« less

The Effects of Polymer Carrier, Hot Melt Extrusion Process and Downstream Processing Parameters on the Moisture Sorption Properties of Amorphous Solid Dispersions

PubMed Central

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V.; Alshetaili, Abdullah S.; Pimparade, Manjeet B.; Repka, Michael A.

2017-01-01

Objective The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion (HME) and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Methods Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing HME technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the Dynamic Vapor Sorption system, and the effect of polymer hydrophobicity, hygroscopicity, molecular weight and the HME process were investigated. FTIR imaging was performed to understand the phase separation driven by the moisture. Key findings Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity, and higher molecular weight could sorb less moisture under the high RH conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared to the physical mixture after HME, which might be due to the decreased surface area and porosity. The FTIR imaging indicated the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Conclusion Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. PMID:26589107

Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

USGS Publications Warehouse

Glynn, P.D.

2003-01-01

One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the simulation conditions. Functional behaviors that cannot be fit include concentration trend reversals and radionuclide desorption spikes. Other simulation results are fit successfully but the fitted parameters (Kd and dispersivity) vary significantly depending on simulation conditions (e.g. "infiltration" vs. "cleanup" conditions). Notably, an increase in the variance of the specified sorption capacities results in a marked increase in the dispersion of the radionuclides. The results presented have implications for the simulation of radionuclide migration in performance assessments of nuclear waste-disposal sites, for the future monitoring of those sites, and more generally for modeling contaminant transport in ground-water environments. ?? 2003 Published by Elsevier Science Ltd.

The Importance of Parameter Variances, Correlations Lengths, and Cross-Correlations in Reactive Transport Models: Key Considerations for Assessing the Need for Microscale Information (Invited)

NASA Astrophysics Data System (ADS)

Reimus, P. W.

2010-12-01

A process-oriented modeling approach is implemented to examine the importance of parameter variances, correlation lengths, and especially cross-correlations in contaminant transport predictions over large scales. It is shown that the most important consideration is the correlation between flow rates and retardation processes (e.g., sorption, matrix diffusion) in the system. If flow rates are negatively correlated with retardation factors in systems containing multiple flow pathways, then characterizing these negative correlation(s) may have more impact on reactive transport modeling than microscale information. Such negative correlations are expected in porous-media systems where permeability is negatively correlated with clay content and rock alteration (which are usually associated with increased sorption). Likewise, negative correlations are expected in fractured rocks where permeability is positively correlated with fracture apertures, which in turn are negatively correlated with sorption and matrix diffusion. Parameter variances and correlation lengths are also shown to have important effects on reactive transport predictions, but they are less important than parameter cross-correlations. Microscale information pertaining to contaminant transport has become more readily available as characterization methods and spectroscopic instrumentation have achieved lower detection limits, greater resolution, and better precision. Obtaining detailed mechanistic insights into contaminant-rock-water interactions is becoming a routine practice in characterizing reactive transport processes in groundwater systems (almost necessary for high-profile publications). Unfortunately, a quantitative link between microscale information and flow and transport parameter distributions or cross-correlations has not yet been established. One reason for this is that quantitative microscale information is difficult to obtain in complex, heterogeneous systems, so simple systems that lack the complexity and heterogeneity of real aquifer materials are often studied. Another is that instrumentation used to obtain microscale information often probes only one variable or family of variables at a time, so linkages to other variables must be inferred by indirect means from other lines of evidence. Despite these limitations, microscale information can be useful in the development and validation of reactive transport models. For example, knowledge of mineral phases that have strong affinities for contaminants can help in the development of cross-correlations between flow and sorption parameters via characterization of permeability and mineral distributions in aquifers. Likewise, microscale information on pore structures in low-permeability zones and contaminant penetration distances into these zones from higher-permeability zones (e.g., fractures) can provide valuable constraints on the representation of diffusive mass transfer processes between flowing porosity and secondary porosity. The prioritization of obtaining microscale information in any groundwater system can be informed by modeling exercises such as those conducted for this study.

H/C atomic ratio as a smart linkage between pyrolytic temperatures, aromatic clusters and sorption properties of biochars derived from diverse precursory materials

PubMed Central

Xiao, Xin; Chen, Zaiming; Chen, Baoliang

2016-01-01

Biochar is increasingly gaining attention due to multifunctional roles in soil amelioration, pollution mitigation and carbon sequestration. It is a significant challenge to compare the reported results from world-wide labs regarding the structure and sorption of biochars derived from various precursors under different pyrolytic conditions due to a lack of a simple linkage. By combining the published works on various biochars, we established a quantitative relationship between H/C atomic ratio and pyrolytic temperature (T), aromatic structure, and sorption properties for naphthalene and phenanthrene. A reverse sigmoid shape between T and the H/C ratio was observed, which was independent of the precursors of biochars, including the ash contents. Linear correlations of Freundlich parameters (N, log Kf) and sorption amount (log Qe, log QA) with H/C ratios were found. A rectangle-like model was proposed to predict the aromatic cluster sizes of biochars from their H/C ratios, and then a good structure-sorption relationship was derived. These quantitative relationships indicate that the H/C atomic ratio is a universal linkage to predict pyrolytic temperatures, aromatic cluster sizes, and sorption characteristics. This study would guide the global study of biochars toward being comparable, and then the development of the structure-sorption relationships will benefit the structural design and environmental application of biochars. PMID:26940984

Cadmium removal by bioclastic granules (Lithothamnium calcareum): batch and fixed-bed column systems sorption studies.

PubMed

Veneu, Diego Macedo; Schneider, Claudio Luiz; de Mello Monte, Marisa Bezerra; Cunha, Osvaldo Galvão Caldas; Yokoyama, Lídia

2018-07-01

The potential of Bioclastic Granules - BG (calcium-carbonate-based material) using the algae Lithothamnium calcareum as sorbent for the removal of Cd(II) from aqueous solutions by sorption was evaluated through batch and continuous systems tests using a fixed-bed column. Sorption process variables, in particular pH (2-7), particle size (<38-300 μm), initial BG concentration (0.1-1.0 g L -1 ), initial Cd(II) concentrations (5-400 mg L -1 ) and contact time (5-240 min), were evaluated. Adsorption isotherm profiles of Cd(II) per BG were similar to an L-type, or Langmuir type, with the adsorption forming a monolayer of approximately 0.61 μm, with a q max of 188.74 mg g -1 and k L of 0.710 L mg -1 . Thomas's model considers that sorption is not limited to a chemical reaction but is controlled by mass transfer at the interface. In the present study, the obtained value of k Th was 0.895 mL h -1  mg -1 , reaching a sorption capacity q o of 124.4 mg g -1 . For the Yoon-Nelson model, it was possible to obtain two important parameters to describe the behavior of the column, the rate constant (k YN ), obtaining a value of 0.09 h -1 and an τ of 82.12 h corresponding to the time required for sorption to occur of 50% of the solute in the rupture curve. X-ray diffraction and scanning electron microscopy analyses coupled to the X-ray dispersive energy system (SEM/EDS) of the BG after the Cd(II) ion sorption tests evidenced the formation of crystals with the prevalence of a new mineral phase (otavite).

Quantitative structure property relationships for the adsorption of pharmaceuticals onto activated carbon.

PubMed

Dickenson, E R V; Drewes, J E

2010-01-01

Isotherms were determined for the adsorption of five pharmaceutical residues, primidone, carbamazepine, ibuprofen, naproxen and diclofenac, to Calgon Filtrasorb 300 powdered activated carbon (PAC). The sorption behavior was examined in ultra-pure and wastewater effluent organic matter (EfOM) matrices, where more sorption was observed in the ultra-pure water for PAC doses greater than 10 mg/L suggesting the presence of EfOM hinders the sorption of the pharmaceuticals to the PAC. Adsorption behaviors were described by the Freundlich isotherm model. Quantitative structure property relationships (QSPRs) in the form of polyparameter linear solvation energy relationships were developed for simulating the Freundlich adsorption capacity in both ultra-pure and EfOM matrices. The significant 3D-based descriptors for the QSPRs were the molar volume, polarizability and hydrogen-bond donor parameters.

Effect of plasticizer on moisture sorption isotherm of sugar palm (Arenga Pinnata) starch film

NASA Astrophysics Data System (ADS)

Jatmiko, Tri Hadi; Poeloengasih, Crescentiana D.; Prasetyo, Dwi Joko; Rosyida, Vita Taufika

2016-02-01

The effect of plasticizer type (glycerol, sorbitol) and plasticizer concentrations (30, 35, 40, 45% w/w polymer) on the moisture sorption isotherm characteristics of sugar palm (Arenga pinnata) starch films were investigated. Moisture affinity of sugar palm starch films was influenced by the plasticizer type and plasticizer concentration. The affinity of the glycerol plasticized film is stronger than that of sorbitol plasticized film. Sugar palm starch film with a higher concentration of glycerol absorbs more moisture with higher initial absorption rate than that of with sorbitol. Films with higher plasticizer concentration of glycerol and sorbitol show higher equilibrium moisture contents at the given relative humidity. The moisture sorption isotherm characteristic of sugar palm starch films can be described very well with the semi empirical 4 parameter Peleg's model.

Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

PubMed

Maksin, Danijela D; Nastasović, Aleksandra B; Milutinović-Nikolić, Aleksandra D; Suručić, Ljiljana T; Sandić, Zvjezdana P; Hercigonja, Radmila V; Onjia, Antonije E

2012-03-30

Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta. Copyright © 2012 Elsevier B.V. All rights reserved.

Derived and thiourea-functionalized silica for cadmium removal: isotherm, kinetic and thermodynamic studies

NASA Astrophysics Data System (ADS)

Omotunde, Iyanu; Okoronkwo, Afamefuna; Oluwashina, Olugbenga

2018-03-01

The present study explored the feasibility of using derived and thiourea-functionalized silica as adsorbent for the removal of cadmium under different experimental conditions. Effects of various parameters such as function of point of zero charge (pHPZC), solution pH, sorbent-sorbate resident time and ratio, concentration and temperature were investigated. The sorption of cadmium followed the pseudo-second-order rate kinetics. Thermodynamic studies revealed that the sorption of cadmium was endothermic and spontaneous, with good affinity toward the sorbent. Various isotherm models, viz. Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Harkins-Jura, and Halsey isotherms were used to analyze the equilibrium data at different temperatures. The Freundlich, Halsey, Langmuir, and Temkin models were found to be in good agreement with the experimental data with high R 2, low RMSE, and low χ 2 values. The results show that the sorption capacity increases with an increase in solution temperature from 28 to 65 °C. The maximum sorption capacity calculated from Langmuir isotherm was 27.55 and 28.41 mg g-1 for derived and thiourea-functionalized silica, respectively, at optimum condition of pH 5 and contact time of 120 min.

Solubility properties of siloxane polymers for chemical sensors

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

Grate, J.W.; Abraham, M.H.

1995-05-01

This paper discusses the factors governing the sorption of vapors by organic polymers. The principles have been applied in the past for designing and selecting polymers for acoustic wave sensors; however they apply equally well to sorption of vapors by polymers used on optical chemical sensors. A set of solvation parameters (a table is presented for various organic vapors) have been developed that describe the particular solubility properties of individual solute molecules; they are used in linear solvation energy relationships (LSER) that model the sorption process. LSER coefficients are tabulated for five polysiloxanes; so are individual interaction terms for eachmore » of the 5 polymers. Dispersion interactions play a major role in determining overall partition coefficients; the log L{sup 16} (gas-liquid partition coefficient of solute on hexadecane) value of vapors are important in determining overall sorption. For the detection of basic vapors such as organophosphates, a hydrogen-bond acidic polymers will be most effective at sorbing them. Currently, fiber optic sensors are being developed where the cladding serves as a sorbent layer to collect and concentrate analyte vapors, which will be detected and identified spectroscopically. These solubility models will be used to design the polymers for the cladding for particular vapors.« less

Effect of α-stable sorptive waiting times on microbial transport in microflow cells

NASA Astrophysics Data System (ADS)

Bonilla, F. Alejandro; Cushman, John H.

2002-09-01

The interaction of bacteria in the fluid phase with pore walls of a porous material involves a wide range of effective reaction times which obey a diversity of substrate-bacteria adhesion conditions, and adhesive mechanisms. For a transported species, this heterogeneity in sorption conditions occurs both in time and space. Modern experimental methods allow one to measure adhesive reaction times of individual bacteria. This detailed information may be incorporated into nonequilibrium transport-sorption models that capture the heterogeneity in reaction times caused by varying chemical conditions. We have carried out particle (Brownian dynamic) simulations of adhesive, self-motile bacteria convected between two infinite plates as a model for a microflow cell. The adhesive heterogeneity is included by introducing adhesive reaction time (understood as time spent at a solid boundary once the particle collides against it) as a random variable that can be infinite (irreversible sorption) or vary over a wide range of values. This is made possible by treating this reaction time random variable as having an α-stable probability distribution whose properties (e.g., infinite moments and long tails) are distinctive from the standard exponential distribution commonly used to model reversible sorption. In addition, the α-stable distribution is renormalizable and hence upscalable to complex porous media. Simulations are performed in a pressure-driven microflow cell. Bacteria motility (driven by an effective Brownian force) acts as a dispersive component in the convective field. Upon collision with the pore wall, bacteria attachment or detachment occurs. The time bacteria spend at the wall varies over a wide range of time scales. This model has the advantage of being parsimonious, that is, involving very few parameters to model complex irreversible or reversible adhesion in heterogeneous environments. It is shown that, as in Taylor dispersion, the ratio of the channel half width b to the Brownian bacteria motility coefficient (D0 or dispersion coefficient) tb=b2/D0 controls the different adhesion regimes along with the value of α. Universal scalings (with respect to dimensionless time t*=t/tb) for the mean position, =V*efftθ*, and mean-square displacement, <ΔX2>=D*efftγ* exist for long-time dispersion and the coefficients were obtained. The model can account for a great many sorptive processes including reversible and irreversible sorption, and sub- and superdispersive regimes with just a few parameters.

An investigation of the moisture sorption and permeability properties of mill-fabricated oriented strandboard

NASA Astrophysics Data System (ADS)

Timusk, Paul Christopher

This thesis brings the disciplines of Building Science and Wood Science together in the study of the moisture-related properties of oriented strand board (OSB). Using controlled mill-manufactured panels specifically made for this project, this research reveals how the sorption and permeance properties of OSB are affected by several variables including production parameters and physical panel properties, moisture-history, and relative humidity exposure. Since OSB varies in composition through its thickness, this study isolated and tested various core and surface components. Permeability and sorption properties of individual OSB layers, intact panel sections, and panel sections that had undergone cyclic wetting and drying or relative humidity cycling prior to testing, were evaluated. After laboratory testing and analysis, a set of OSB permeance and sorption values were entered into the material database of a finite-element hygrothermal computer modeling program. Relying on this data, a series of hygrothermal wall simulations were carried out using standard wall sections exposed to various climate conditions found throughout North America. These simulations revealed that the results vary widely depending upon the permeance and sorption values used. Thus the common practice of characterizing a range of OSB products with various moisture histories by using a single permeance or sorption value may not be wise.

Effects of Mineral Compositions on Matrix Diffusion and Sorption of 75Se(IV) in Granite.

PubMed

Yang, Xiaoyu; Ge, Xiangkun; He, Jiangang; Wang, Chunli; Qi, Liye; Wang, Xiangyun; Liu, Chunli

2018-02-06

Exploring the migration behaviors of selenium in granite is critical for the safe disposal of radioactive waste. The matrix diffusion and sorption of 75 Se(IV) (analogue for 79 Se) in granite were systematically studied to set reliable parameters in this work. Through-diffusion and batch sorption experiments were conduct with four types of Beishan granite. The magnitudes of the obtained apparent diffusion coefficient (D a ) values are of the following order: monzogranite > granodiorite-2 > granodiorite-1, which is opposite to the sequence of the K d values obtained from both the diffusion model and batch sorption experiments. The EPMA results of the granitic flakes showed that there was no obvious enrichment of Se(IV) on quartz, microcline and albite. Only biotite showed a weak affinity for Se(IV). Macroscopic sorption behaviors of Se(IV) on the four types of granite were identical with the sequence of the granitic biotite contents. Quantitative fitting results were also provided. XPS and XANES spectroscopy data revealed that bidentate inner-sphere complexes were formed between Se(IV) and Fe(III). Our results indicate that biotite can be representative of the Se(IV) sorption in complex mineral assemblages such as granite, and the biotite contents are critically important to evaluate Se(IV) transport in granite.

Advances in modeling sorption and diffusion of moisture in porous reactive materials.

PubMed

Harley, Stephen J; Glascoe, Elizabeth A; Lewicki, James P; Maxwell, Robert S

2014-06-23

Water-vapor-uptake experiments were performed on a silica-filled poly(dimethylsiloxane) (PDMS) network and modeled by using two different approaches. The data was modeled by using established methods and the model parameters were used to predict moisture uptake in a sample. The predictions are reasonably good, but not outstanding; many of the shortcomings of the modeling are discussed. A high-fidelity modeling approach is derived and used to improve the modeling of moisture uptake and diffusion. Our modeling approach captures the physics and kinetics of diffusion and adsorption/desorption, simultaneously. It predicts uptake better than the established method; more importantly, it is also able to predict outgassing. The material used for these studies is a filled-PDMS network; physical interpretations concerning the sorption and diffusion of moisture in this network are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

Dittrich, Timothy M.; Reimus, Paul William

2015-10-29

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

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil.

PubMed

Milfont, Mônica Lúcia; Martins, Jean Manuel Fonseca; Antonino, Antonio Celso Dantas; Gouveia, Ester Ribeiro; Netto, André Maciel; Guiné, Véronique; Mas, Hélène; dos Santos Freire, Maria Betânia Galvão

2008-01-01

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

NASA Astrophysics Data System (ADS)

Serrano, Susana; O'Day, Peggy A.; Vlassopoulos, Dimitri; García-González, Maria Teresa; Garrido, Fernando

2009-02-01

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X - and Y -), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions. Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.

In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

PubMed

Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

2015-02-17

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

A study of equilibrium and FTIR, SEM/EDS analysis of trimethoprim adsorption onto K10

NASA Astrophysics Data System (ADS)

Bekçi, Zehra; Seki, Yoldaş; Kadir Yurdakoç, M.

2007-02-01

The sorption behavior of K10, a type of montmorillonite for trimethoprim (TMP) drug, was studied by using batch technique under different pH and temperature. The interaction between K10 and TMP was investigated using SEM, and FTIR. It was observed that adsorption was increased between pH 2.5 and 6.3. By performing kinetic experiments, the pseudo-second-order kinetic model provides the best fit for TMP adsorption onto K10 montmorillonite. The sorption of TMP reached the equilibrium state after 6 h sorption time and has been described by using Langmuir, Freundlich and Dubinin-Radushkevich equations to obtain adsorption capacity values. The results indicate that the relative adsorption capacity values ( Kf) are decreasing with the increase of temperature in the range of 298-318 K. The sorption energy values obtained from DR isotherm show that sorption of TMP onto K10 can be explained by ion exchange mechanism at 298, 308 and 318 K. The thermodynamic studies were conducted to find the thermodynamic parameters Δ H°, Δ S° and Δ G°. It was determined that adsorption process is spontaneous and exothermic in nature.

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.

Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

PubMed

Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

2017-04-01

Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (T g ), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔT g (≡T g  - T g0 ; where T g0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

Non-Fickian dispersive transport of strontium in laboratory-scale columns: Modelling and evaluation

NASA Astrophysics Data System (ADS)

Liu, Dongxu; Jivkov, Andrey P.; Wang, Lichun; Si, Gaohua; Yu, Jing

2017-06-01

In the context of environmental remediation of contaminated sites and safety assessment of nuclear waste disposal in the near-surface zone, we investigate the leaching and non-Fickian dispersive migration with sorption of strontium (mocking strontium-90) through columns packed with sand and clay. Analysis is based on breakthrough curves (BTCs) from column experiments, which simulated rainfall infiltration and source term release scenario, rather than applying constant tracer solution at the inlet as commonly used. BTCs are re-evaluated and transport parameters are estimated by inverse modelling using two approaches: (1) equilibrium advection-dispersion equation (ADE); and (2) continuous time random walk (CTRW). Firstly, based on a method for calculating leach concentration, the inlet condition with an exponential decay input is identified. Secondly, the results show that approximately 39%-58% of Br- and 16%-49% of Sr2+ are eluted from the columns at the end of the breakthrough experiments. This suggests that trapping mechanisms, including diffusion into immobile zones and attachment of tracer on mineral surfaces, are more pronounced for Sr2+ than for Br-. Thirdly, we demonstrate robustness of CTRW-based truncated power-law (TPL) model in capturing non-Fickian reactive transport with 0 < β < 2, and Fickian transport with β > 2. The non-Fickian dispersion observed experimentally is explained by variations of local flow field from preferential flow paths due to physical heterogeneities. Particularly, the additional sorption process of strontium on clay minerals contributes to the delay of the peak concentration and the tailing features, which leads to an enhanced non-Fickian transport for strontium. Finally, the ADE and CTRW approaches to environmental modelling are evaluated. It is shown that CTRW with a sorption term can describe non-Fickian dispersive transport of strontium at laboratory scale by identifying appropriate parameters, while the traditional ADE with a retardation factor fails to reproduce the complex non-Fickian transport of strontium with strong sorption on clay surface.

The effects of polymer carrier, hot melt extrusion process and downstream processing parameters on the moisture sorption properties of amorphous solid dispersions.

PubMed

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V; Alshetaili, Abdullah S; Pimparade, Manjeet B; Repka, Michael A

2016-05-01

The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing the hot melt extrusion technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the dynamic vapour sorption system, and the effects of polymer hydrophobicity, hygroscopicity, molecular weight and the hot melt extrusion process were investigated. Fourier transform infrared (FTIR) imaging was performed to understand the phase separation driven by the moisture. Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity and higher molecular weight could sorb less moisture under the high relative humidity (RH) conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared with the physical mixture after hot melt extrusion, which might be due to the decreased surface area and porosity. The FTIR imaging indicated that the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. © 2015 Royal Pharmaceutical Society.

Vanadium sorption by mineral soils: Development of a predictive model.

PubMed

Larsson, Maja A; Hadialhejazi, Golshid; Gustafsson, Jon Petter

2017-02-01

The toxicity of vanadium in soils depends on its sorption to soil components. Here we studied the vanadate(V) sorption properties of 26 mineral soils. The data were used to optimise parameters for a Freundlich equation with a pH term. Vanadium K-edge XANES spectroscopy for three selected soils confirmed that the added vanadate(V) had accumulated mostly as adsorbed vanadate(V) on Fe and Al hydrous oxides, with only minor contributions from organically complexed vanadium(IV). Data on pH-dependent V solubility for seven soils showed that on average 0.36 H + accompanied each V during adsorption and desorption. The resulting model provided reasonable fits to the V sorption data, with r 2  > 0.99 for 20 of 26 soils. The observed K dS value, i.e. the ratio of total to dissolved V, was strongly dependent on V addition and soil; it varied between 3 and 4 orders of magnitude. The model was used to calculate the Freundlich sorption strength (FSS), i.e. the amount of V sorbed at [V] = 2.5 mg L -1 , in the concentration range of observed plant toxicities. A close relationship between FSS and oxalate-extractable Fe and Al was found (r 2  = 0.85) when one acidic soil was removed from the regression. The FSS varied between 27 and 8718 mg V kg -1 , showing that the current environmental guidelines can be both under- and overprotective for vanadium. Copyright © 2016 Elsevier Ltd. All rights reserved.

“Multi-temperature” method for high-pressure sorption measurements on moist shales

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

Gasparik, Matus; Ghanizadeh, Amin; Gensterblum, Yves

2013-08-15

A simple and effective experimental approach has been developed and tested to study the temperature dependence of high-pressure methane sorption in moist organic-rich shales. This method, denoted as “multi-temperature” (short “multi-T”) method, enables measuring multiple isotherms at varying temperatures in a single run. The measurement of individual sorption isotherms at different temperatures takes place in a closed system ensuring that the moisture content remains constant. The multi-T method was successfully tested for methane sorption on an organic-rich shale sample. Excess sorption isotherms for methane were measured at pressures of up to 25 MPa and at temperatures of 318.1 K, 338.1more » K, and 348.1 K on dry and moisture-equilibrated samples. The measured isotherms were parameterized with a 3-parameter Langmuir-based excess sorption function, from which thermodynamic sorption parameters (enthalpy and entropy of adsorption) were obtained. Using these, we show that by taking explicitly into account water vapor as molecular species in the gas phase with temperature-dependent water vapor pressure during the experiment, more meaningful results are obtained with respect to thermodynamical considerations. The proposed method can be applied to any adsorbent system (coals, shales, industrial adsorbents) and any supercritical gas (e.g., CH{sub 4}, CO{sub 2}) and is particularly suitable for sorption measurements using the manometric (volumetric) method.« less

BEARKIMPE-2: A VBA Excel program for characterizing granular iron in treatability studies

NASA Astrophysics Data System (ADS)

Firdous, R.; Devlin, J. F.

2014-02-01

The selection of a suitable kinetic model to investigate the reaction rate of a contaminant with granular iron (GI) is essential to optimize the permeable reactive barrier (PRB) performance in terms of its reactivity. The newly developed Kinetic Iron Model (KIM) determines the surface rate constant (k) and sorption parameters (Cmax &J) which were not possible to uniquely identify previously. The code was written in Visual Basic (VBA), within Microsoft Excel, was adapted from earlier command line FORTRAN codes, BEARPE and KIMPE. The program is organized with several user interface screens (UserForms) that guide the user step by step through the analysis. BEARKIMPE-2 uses a non-linear optimization algorithm to calculate transport and chemical kinetic parameters. Both reactive and non-reactive sites are considered. A demonstration of the functionality of BEARKIMPE-2, with three nitroaromatic compounds showed that the differences in reaction rates for these compounds could be attributed to differences in their sorption behavior rather than their propensities to accept electrons in the reduction process.

Parameterizing sorption isotherms using a hybrid global-local fitting procedure.

PubMed

Matott, L Shawn; Singh, Anshuman; Rabideau, Alan J

2017-05-01

Predictive modeling of the transport and remediation of groundwater contaminants requires an accurate description of the sorption process, which is usually provided by fitting an isotherm model to site-specific laboratory data. Commonly used calibration procedures, listed in order of increasing sophistication, include: trial-and-error, linearization, non-linear regression, global search, and hybrid global-local search. Given the considerable variability in fitting procedures applied in published isotherm studies, we investigated the importance of algorithm selection through a series of numerical experiments involving 13 previously published sorption datasets. These datasets, considered representative of state-of-the-art for isotherm experiments, had been previously analyzed using trial-and-error, linearization, or non-linear regression methods. The isotherm expressions were re-fit using a 3-stage hybrid global-local search procedure (i.e. global search using particle swarm optimization followed by Powell's derivative free local search method and Gauss-Marquardt-Levenberg non-linear regression). The re-fitted expressions were then compared to previously published fits in terms of the optimized weighted sum of squared residuals (WSSR) fitness function, the final estimated parameters, and the influence on contaminant transport predictions - where easily computed concentration-dependent contaminant retardation factors served as a surrogate measure of likely transport behavior. Results suggest that many of the previously published calibrated isotherm parameter sets were local minima. In some cases, the updated hybrid global-local search yielded order-of-magnitude reductions in the fitness function. In particular, of the candidate isotherms, the Polanyi-type models were most likely to benefit from the use of the hybrid fitting procedure. In some cases, improvements in fitness function were associated with slight (<10%) changes in parameter values, but in other cases significant (>50%) changes in parameter values were noted. Despite these differences, the influence of isotherm misspecification on contaminant transport predictions was quite variable and difficult to predict from inspection of the isotherms. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation and mechanism of ammonia nitrogen removal using sediments from a malodorous river

NASA Astrophysics Data System (ADS)

Chen, Xing; Jiang, Xia; Huang, Wei

2018-03-01

Malodorous rivers are among the major environmental problems of cities in developing countries. In addition to the unpleasant smell, the sediments of such rivers can act as a sink for pollutants. The excessive amount of ammonia nitrogen (NH3-N) in rivers is the main factor that causes the malodour. Therefore, a suitable method is necessary for sediment disposition and NH3-N removal in malodorous rivers. The sediment in a malodorous river (PS) in Beijing, China was selected and modified via calcination (PS-D), Na+ doping (PS-Na) and calcination-Na+ doping (PS-DNa). The NH3-N removal efficiency using the four sediment materials was evaluated, and results indicated that the NH3-N removal efficiency using the modified sediment materials could reach over 60%. PS-DNa achieved the highest NH3-N removal efficiency (90.04%). The kinetics study showed that the pseudo-second-order model could effectively describe the sorption kinetics and that the exterior activated site had the main function of P sorption. The results of the sorption isotherms indicated that the maximum sorption capacities of PS-Na, PS-D and PS-DNa were 0.343, 0.831 and 1.113 mg g-1, respectively, and a high temperature was favourable to sorption. The calculated thermodynamic parameters suggested that sorption was a feasible or spontaneous (ΔG < 0), entropy-driven (ΔS > 0), and endothermic (ΔH > 0) reaction.

Parameters estimation for reactive transport: A way to test the validity of a reactive model

NASA Astrophysics Data System (ADS)

Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

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.

Moisture diffusion and permeability characteristics of hydroxypropylmethylcellulose and hard gelatin capsules.

PubMed

Barham, Ahmad S; Tewes, Frederic; Healy, Anne Marie

2015-01-30

The primary objective of this paper is to compare the sorption characteristics of hydroxypropylmethylcellulose (HPMC) and hard gelatin (HG) capsules and their ability to protect capsule contents. Moisture sorption and desorption isotherms for empty HPMC and HG capsules have been investigated using dynamic vapour sorption (DVS) at 25°C. All sorption studies were analysed using the Young-Nelson model equations which distinguishes three moisture sorption types: monolayer adsorption moisture, condensation and absorption. Water vapour diffusion coefficients (D), solubility (S) and permeability (P) parameters of the capsule shells were calculated. ANOVA was performed with the Tukey comparison test to analyse the effect of %RH and capsule type on S, P, and D parameters. The moisture uptake of HG capsules were higher than HPMC capsules at all %RH conditions studied. It was found that values of D and P across HPMC capsules were greater than for HG capsules at 0-40 %RH; whereas over the same %RH range S values were higher for HG than for HPMC capsules. S values decreased gradually as the %RH was increased up to 60% RH. To probe the effect of moisture ingress, spray dried lactose was loaded into capsules. Phase evolution was characterised by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and differential scanning calorimetry (DSC). The capsules under investigation are not capable of protecting spray dried lactose from induced solid state changes as a result of moisture uptake. For somewhat less moisture sensitive formulations, HPMC would appear to be a better choice than HG in terms of protection of moisture induced deterioration. Copyright © 2014 Elsevier B.V. All rights reserved.

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils.

PubMed

Müller, K; Duwig, C; Prado, B; Siebe, C; Hidalgo, C; Etchevers, J

2012-01-01

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers' breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils' hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.

Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.

PubMed

Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana

2016-12-01

Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

Batch experiments versus soil pore water extraction--what makes the difference in isoproturon (bio-)availability?

PubMed

Folberth, Christian; Suhadolc, Metka; Scherb, Hagen; Munch, Jean Charles; Schroll, Reiner

2009-10-01

Two approaches to determine pesticide (bio-)availability in soils (i) batch experiments with "extraction with an excess of water" (EEW) and (ii) the recently introduced "soil pore water (PW) extraction" of pesticide incubated soil samples have been compared with regard to the sorption behavior of the model compound isoproturon in soils. A significant correlation between TOC and adsorbed pesticide amount was found when using the EEW approach. In contrast, there was no correlation between TOC and adsorbed isoproturon when using the in situ PW extraction method. Furthermore, sorption was higher at all concentrations in the EEW method when comparing the distribution coefficients (K(d)) for both methods. Over all, sorption in incubated soil samples at an identical water tension (-15 kPa) and soil density (1.3 g cm(-3)) appears to be controlled by a complex combination of sorption driving soil parameters. Isoproturon bioavailability was found to be governed in different soils by binding strength and availability of sorption sites as well as water content, whereas the dominance of either one of these factors seems to depend on the individual composition and characteristics of the respective soil sample. Using multiple linear regression analysis we obtained furthermore indications that the soil pore structure is affected by the EEW method due to disaggregation, resulting in a higher availability of pesticide sorption sites than in undisturbed soil samples. Therefore, it can be concluded that isoproturon sorption is overestimated when using the EEW method, which should be taken into account when using data from this approach or similar batch techniques for risk assessment analysis.

Development of a graphene oxide/chitosan nanocomposite for the removal of picric acid from aqueous solutions: Study of sorption parameters.

PubMed

Mohseni Kafshgari, Mona; Tahermansouri, Hasan

2017-12-01

The functionalization of graphene oxide (GO) with chitosan (Chi) has been investigated to prepare a nanocomposite material (GO-Chi) for the removal of picric acid from aqueous solutions. Materials were characterized by FT-IR, TGA, DTG, FESEM, EDX, XRD and BET. Batch experiments such as solution pH, amount of adsorbents, contact time, concentration of the picric acid and temperature were achieved to study sorption process. Kinetic studies were well described by pseudo-second-order kinetic model for both adsorbents. Isotherm studies showed that the Langmuir isotherm for GO and Freundlich and Halsey models for GO-Chi were found to best represent the measured sorption data. Negative ΔG° values for GO-Chi and positive ones for GO indicated the nature of spontaneous and unspontaneous, respectively for adsorption process. In addition, picric acid molecules can be desorbed from GO-Chi up to 80% at pH=9 and that the consumed GO-Chi could be reutilized up to 5th cycle of regeneration. Copyright © 2017 Elsevier B.V. All rights reserved.

Estimation of soil sorption coefficients of veterinary pharmaceuticals from soil properties.

PubMed

ter Laak, Thomas L; Gebbink, Wouter A; Tolls, Johannes

2006-04-01

Environmental exposure assessment of veterinary pharmaceuticals requires estimating the sorption to soil. Soil sorption coefficients of three common, ionizable, antimicrobial agents (oxytetracycline [OTC], tylosin [TYL], and sulfachloropyridazine [SCP]) were studied in relation to the soil properties of 11 different soils. The soil sorption coefficient at natural pH varied from 950 to 7,200, 10 to 370, and 0.4 to 35 L/kg for OTC, TYL, and SCP, respectively. The variation increased by almost two orders of magnitude for OTC and TYL when pH was artificially adjusted. Separate soil properties (pH, organic carbon content, clay content, cation-exchange capacity, aluminum oxyhydroxide content, and iron oxyhydroxide content) were not able to explain more than half the variation observed in soil sorption coefficients. This reflects the complexity of the sorbent-sorbate interactions. Partial-least-squares (PLS) models, integrating all the soil properties listed above, were able to explain as much as 78% of the variation in sorption coefficients. The PLS model was able to predict the sorption coefficient with an accuracy of a factor of six. Considering the pH-dependent speciation, species-specific PLS models were developed. These models were able to predict species-specific sorption coefficients with an accuracy of a factor of three to four. However, the species-specific sorption models did not improve the estimation of sorption coefficients of species mixtures, because these models were developed with a reduced data set at standardized aqueous concentrations. In conclusion, pragmatic approaches like PLS modeling might be suitable to estimate soil sorption for risk assessment purposes.

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 may serve as a base to estimate the environmental fate of organic acids in the presence of carbonized sorbents such as biochar, and help assess (i) the potential application of biochar for remediation purposes and (ii) the potential effect of biochar addition to soil.

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

Influence of relative humidity and gaseous ammonia on the nicotine sorption to indoor materials.

PubMed

Ongwandee, M; Sawanyapanich, P

2012-02-01

Sorption of nitrogen-containing organic constituents of environmental tobacco smoke may be influenced by ammonia, a common indoor gas, and relative humidity (RH). We quantified sorption kinetics and equilibria of nicotine with stainless steel, cotton-polyester curtain, and polypropylene carpet at 0%, 50%, and 90% RH and in the presence of ammonia using a 10-l stainless steel chamber. Nicotine was introduced into the chamber by flash evaporating 50 μl of pure liquid. Kinetic sorption parameters were determined by fitting a mass balance model to experimental results using a nonlinear regression. Results show that an equilibrium partition coefficient, k(e) , of nicotine tended to increase as the RH increased for the curtain and carpet. Adsorbed water may contribute to an increase in available sites for nicotine sorption on the surface. In the presence of 20- and 40-ppm NH(3) , the values of k(e) for carpet were decreased by 14-40% at 50% and 90% RH, but the effect of NH(3) was not observed at 0% RH. The values of k(e) ranged from 54 to 152 m. Our findings indicate the relative importance of nicotine sorption to surfaces is dependent on the relative humidity and the presence of ammonia. This research demonstrates that relative humidity and gaseous ammonia can influence nicotine sorption to common indoor surfaces, i.e., curtains and carpets. Increasing the relative humidity from dry to modest appears to enhance the sorptive capacity. Presence of the typical range of gaseous ammonia concentrations can reduce the nicotine sorption in a humid environment but does not affect the sorptive capacity in the absence of added water. Thus, studies on the dynamic sorption of other alkaloids or amine constituents of environmental tobacco smoke to indoor surfaces should consider the impact of water vapor concentration because of the interaction of water with the surface and sorbates. Furthermore, the mixture of gaseous amines may participate in adsorption site competition. © 2011 John Wiley & Sons A/S.

Evaluation and mechanism of ammonia nitrogen removal using sediments from a malodorous river

PubMed Central

Chen, Xing; Jiang, Xia

2018-01-01

Malodorous rivers are among the major environmental problems of cities in developing countries. In addition to the unpleasant smell, the sediments of such rivers can act as a sink for pollutants. The excessive amount of ammonia nitrogen (NH3−N) in rivers is the main factor that causes the malodour. Therefore, a suitable method is necessary for sediment disposition and NH3−N removal in malodorous rivers. The sediment in a malodorous river (PS) in Beijing, China was selected and modified via calcination (PS-D), Na+ doping (PS-Na) and calcination–Na+ doping (PS-DNa). The NH3−N removal efficiency using the four sediment materials was evaluated, and results indicated that the NH3−N removal efficiency using the modified sediment materials could reach over 60%. PS-DNa achieved the highest NH3−N removal efficiency (90.04%). The kinetics study showed that the pseudo-second-order model could effectively describe the sorption kinetics and that the exterior activated site had the main function of P sorption. The results of the sorption isotherms indicated that the maximum sorption capacities of PS-Na, PS-D and PS-DNa were 0.343, 0.831 and 1.113 mg g−1, respectively, and a high temperature was favourable to sorption. The calculated thermodynamic parameters suggested that sorption was a feasible or spontaneous (ΔG < 0), entropy-driven (ΔS > 0), and endothermic (ΔH > 0) reaction. PMID:29657816

Enhancing oil removal from water by immobilizing multi-wall carbon nanotubes on the surface of polyurethane foam.

PubMed

Keshavarz, Alireza; Zilouei, Hamid; Abdolmaleki, Amir; Asadinezhad, Ahmad

2015-07-01

A surface modification method was carried out to enhance the light crude oil sorption capacity of polyurethane foam (PUF) through immobilization of multi-walled carbon nanotube (MWCNT) on the foam surface at various concentrations. The developed sorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and tensile elongation test. The results obtained from thermogravimetric and tensile elongation tests showed the improvement of thermal and mechanical resistance of surface-modified foam. The experimental data also revealed that the immobilization of MWCNT on PUF surface enhanced the sorption capacity of light crude oil and reduced water sorption. The highest oil removal capacity was obtained for 1 wt% MWCNT on PUF surface which was 21.44% enhancement in light crude oil sorption compared to the blank PUF. The reusability of surface modified PUF was determined through four cycles of chemical regeneration using petroleum ether. The adsorption of light crude oil with 30 g initial mass showed that 85.45% of the initial oil sorption capacity of this modified sorbent was remained after four regeneration cycles. Equilibrium isotherms for adsorption of oil were analyzed by the Freundlich, Langmuir, Temkin, and Redlich-Peterson models through linear and non-linear regression methods. Results of equilibrium revealed that Langmuir isotherm is the best fitting model and non-linear method is a more accurate way to predict the parameters involved in the isotherms. The overall findings suggested the promising potentials of the developed sorbent in order to be efficiently used in large-scale oil spill cleanup. Copyright © 2015 Elsevier Ltd. All rights reserved.

The sorption of lead, cadmium, copper and zinc ions from aqueous solutions on a raw diatomite from Algeria.

PubMed

Safa, Messaouda; Larouci, Mohammed; Meddah, Boumediene; Valemens, Pierre

2012-01-01

The adsorption of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) ions from aqueous solution by Algerian raw diatomite was studied. The influences of different sorption parameters such as contact pH solution, contact time and initial metal ions concentration were studied to optimize the reaction conditions. The metals ions adsorption was strictly pH dependent. The maximum adsorption capacities towards Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were 0.319, 0.311, 0.18 and 0.096 mmol g(-1), respectively. The kinetic data were modelled using the pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analysed using the Langmuir and the Freundlich isotherms; the results showed that the adsorption equilibrium was well described by both model isotherms. The negative value of free energy change ΔG indicates feasible and spontaneous adsorption of four metal ions on raw diatomite. According to these results, the high exchange capacities of different metal ions at high and low concentration levels, and given the low cost of the investigated adsorbent in this work, Algerian diatomite was considered to be an excellent adsorbent.

Dysprosium sorption by polymeric composite bead: robust parametric optimization using Taguchi method.

PubMed

Yadav, Kartikey K; Dasgupta, Kinshuk; Singh, Dhruva K; Varshney, Lalit; Singh, Harvinderpal

2015-03-06

Polyethersulfone-based beads encapsulating di-2-ethylhexyl phosphoric acid have been synthesized and evaluated for the recovery of rare earth values from the aqueous media. Percentage recovery and the sorption behavior of Dy(III) have been investigated under wide range of experimental parameters using these beads. Taguchi method utilizing L-18 orthogonal array has been adopted to identify the most influential process parameters responsible for higher degree of recovery with enhanced sorption of Dy(III) from chloride medium. Analysis of variance indicated that the feed concentration of Dy(III) is the most influential factor for equilibrium sorption capacity, whereas aqueous phase acidity influences the percentage recovery most. The presence of polyvinyl alcohol and multiwalled carbon nanotube modified the internal structure of the composite beads and resulted in uniform distribution of organic extractant inside polymeric matrix. The experiment performed under optimum process conditions as predicted by Taguchi method resulted in enhanced Dy(III) recovery and sorption capacity by polymeric beads with minimum standard deviation. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-06-01

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

Laboratory Experiments on Bentonite Samples: FY16 Progress

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

Ruth M. Tinnacher; Tournassat, Christophe; James A. Davis

2016-08-22

The primary goal of this study is to improve the understanding of U(VI) sorption and diffusion behavior in sodium-montmorillonite in order to support the development of realistic conceptual models describing these processes in performance assessment models while (1) accounting for potential changes in system conditions over time and space, (2) avoiding overly conservative transport predictions, and (3) using a minimum number of fitting parameters.

Three-parameter modeling of the soil sorption of acetanilide and triazine herbicide derivatives.

PubMed

Freitas, Mirlaine R; Matias, Stella V B G; Macedo, Renato L G; Freitas, Matheus P; Venturin, Nelson

2014-02-01

Herbicides have widely variable toxicity and many of them are persistent soil contaminants. Acetanilide and triazine family of herbicides have widespread use, but increasing interest for the development of new herbicides has been rising to increase their effectiveness and to diminish environmental hazard. The environmental risk of new herbicides can be accessed by estimating their soil sorption (logKoc), which is usually correlated to the octanol/water partition coefficient (logKow). However, earlier findings have shown that this correlation is not valid for some acetanilide and triazine herbicides. Thus, easily accessible quantitative structure-property relationship models are required to predict logKoc of analogues of the these compounds. Octanol/water partition coefficient, molecular weight and volume were calculated and then regressed against logKoc for two series of acetanilide and triazine herbicides using multiple linear regression, resulting in predictive and validated models.

Dynamic behavior of semivolatile organic compounds in indoor air. 2. Nicotine and phenanthrene with carpet and wallboard.

PubMed

Van Loy, M D; Riley, W J; Daisey, J M; Nazaroff, W W

2001-02-01

The surface interactions of nicotine and phenanthrene with carpet, painted wallboard, and stainless steel were investigated in a room-sized environmental test chamber. Adsorption kinetics were tested by flash evaporating a known mass of each compound into a sealed 20 m3 chamber containing one or more of the tested sorbents. In each experiment, one or more emissions were performed after the gas-phase concentration had reached an apparent plateau. At the end of each experiment, the chamber was ventilated and resealed to monitor reemission of the compound from the sorbents. Kinetic sorption parameters were determined by fitting a mass-balance model to the experimental results. The sorption capacity of stainless steel was of similar magnitude for nicotine and phenanthrene. Sorption of nicotine on carpet and wallboard was much stronger, with equilibrium partitioning values 2-3 orders of magnitude higher. The sorption capacities of phenanthrene on carpet and wallboard were smaller, approximately 10-20% of the stainless steel values. The rates of uptake are of similar magnitude for all sorbate--sorbent pairs and are consistent with the limit imposed by gas-phase boundary-layer mass transport. The rates of desorption are much faster for phenanthrene than for nicotine. Model simulations predict average nicotine levels in a typical smoking residence that are consistent with published data.

Nicotine as a Marker for Environmental Tobacco Smoke: Implications of Sorption on Indoor Surface Materials.

PubMed

Van Loy, Michael D; Nazaroff, William W; Daisey, Joan M

1998-10-01

Recently developed models and data describing the interactions of gas-phase semi-volatile organic compounds with indoor surfaces are employed to examine the effects of sorption on nicotine's suitability as an environmental tobacco smoke (ETS) marker. Using parameters from our studies of nicotine sorption on carpet, painted wallboard, and stainless steel and previously published data on ETS particle deposition, the dynamic behavior of nicotine was modeled in two different indoor environments: a house and a stainless steel chamber. The results show that apparently contradictory observations of nicotine's behavior in indoor air can be understood by considering the effects of sorption under different experimental conditions. In indoor environments in which smoking has occurred regularly for an extended period, the sorbed mass of nicotine is very large relative to the mass emitted by a single cigarette. The importance of nicotine adsorption relative to ventilation as a gas-phase removal mechanism is reduced. Where smoking occurs less regularly or the indoor surfaces are cleaned prior to smoking (as in a laboratory chamber), nicotine deposition is more significant. Nicotine concentrations closely track the levels of other ETS constituents in environments with habitual smoking if the data are averaged over a period significantly longer than the period between cigarette combustion episodes. However, nicotine is not a suitable tracer for predicting ETS exposures at fine time scales or in settings where smoking occurs infrequently and irregularly.

Probing the Interaction of Ionic Liquids with CO2: A Raman Spectroscopy and Ab Initio Study

DTIC Science & Technology

2008-05-05

called physisorption. Regardless of the sorption mechanism, a few quantitative parameters can be used to describe a gas-liquid interaction at a...Controllers (I and II) I II 22 and tube fittings, 0.062 inch perfluoroalkoxy ( PFA ) tubing, Tylan General Model FC-128 Flow Controllers

Experimental and Numerical Investigations on Colloid-facilitated Plutonium Reactive Transport in Fractured Tuffaceous Rocks

NASA Astrophysics Data System (ADS)

Dai, Z.; Wolfsberg, A. V.; Zhu, L.; Reimus, P. W.

2017-12-01

Colloids have the potential to enhance mobility of strongly sorbing radionuclide contaminants in fractured rocks at underground nuclear test sites. This study presents an experimental and numerical investigation of colloid-facilitated plutonium reactive transport in fractured porous media for identifying plutonium sorption/filtration processes. The transport parameters for dispersion, diffusion, sorption, and filtration are estimated with inverse modeling for minimizing the least squares objective function of multicomponent concentration data from multiple transport experiments with the Shuffled Complex Evolution Metropolis (SCEM). Capitalizing on an unplanned experimental artifact that led to colloid formation and migration, we adopt a stepwise strategy to first interpret the data from each experiment separately and then to incorporate multiple experiments simultaneously to identify a suite of plutonium-colloid transport processes. Nonequilibrium or kinetic attachment and detachment of plutonium-colloid in fractures was clearly demonstrated and captured in the inverted modeling parameters along with estimates of the source plutonium fraction that formed plutonium-colloids. The results from this study provide valuable insights for understanding the transport mechanisms and environmental impacts of plutonium in fractured formations and groundwater aquifers.

Impacts of compound properties and sediment characteristics on the sorption behaviour of pharmaceuticals in aquatic systems.

PubMed

Al-Khazrajy, Omar S A; Boxall, Alistair B A

2016-11-05

Sorption is a key factor in determining the persistence, attenuation and bioavailability of sediment-associated contaminants. However, our understanding of the sorption behaviour of pharmaceuticals in sediments is poor. In this study, we investigated the sorption behaviour of a diverse set of pharmaceuticals in a range sediment types. Sorption affinity of pharmaceuticals for all sediments was found to increase in the order mefenamic acid

Comparison of adsorption equilibrium models for the study of CL-, NO3- and SO4(2-) removal from aqueous solutions by an anion exchange resin.

PubMed

Dron, Julien; Dodi, Alain

2011-06-15

The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)

Effects of sorption kinetics on the fate and transport of pharmaceuticals in estuaries.

PubMed

Liu, Dong; Lung, Wu-Seng; Colosi, Lisa M

2013-08-01

Many current fate and transport models based on the assumption of instantaneous sorption equilibrium of contaminants in the water column may not be valid for certain pharmaceuticals with long times to reach sorption equilibrium. In this study, a sorption kinetics model was developed and incorporated into a water quality model for the Patuxent River Estuary to evaluate the effect of sorption kinetics. Model results indicate that the assumption of instantaneous sorption equilibrium results in significant under-prediction of water column concentrations for some pharmaceuticals. The relative difference between predicted concentrations for the instantaneous versus kinetic approach is as large as 150% at upstream locations in the Patuxent Estuary. At downstream locations, where sorption processes have had sufficient time to reach equilibrium, the relative difference decreases to roughly 25%. This indicates that sorption kinetics affect a model's ability to capture accumulation of pharmaceuticals into riverbeds and the transport of pharmaceuticals in estuaries. These results offer strong evidence that chemicals are not removed from the water column as rapidly as has been assumed on the basis of equilibrium-based analyses. The findings are applicable not only for pharmaceutical compounds, but also for diverse contaminants that reach sorption equilibrium slowly. Copyright © 2013 Elsevier Ltd. All rights reserved.

Experimental study and modelling of selenite sorption onto illite and smectite clays.

PubMed

Missana, T; Alonso, U; García-Gutiérrez, M

2009-06-15

This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated (from 1x10(-10) to 1x10(-3) M); and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions, as follows: (a) 30% illite-70% smectite and (b) 43% illite-57% smectite. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data, separately obtained in the single mineral systems, were modeled using both a one- and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. Although the use of a two-site model slightly improved the fit of data at a pH below 4, the simpler one-site model reproduced satisfactorily all the sorption data from pH 3 to 8. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/smectite mixtures; the model's predictions were consistent with the experimental adsorption data.

Enhanced Removal of Lead by Chemically and Biologically Treated Carbonaceous Materials

PubMed Central

Mahmoud, Mohamed E.; Osman, Maher M.; Ahmed, Somia B.; Abdel-Fattah, Tarek M.

2012-01-01

Hybrid sorbents and biosorbents were synthesized via chemical and biological treatment of active carbon by simple and direct redox reaction followed by surface loading of baker's yeast. Surface functionality and morphology of chemically and biologically modified sorbents and biosorbents were studied by Fourier Transform Infrared analysis and scanning electron microscope imaging. Hybrid carbonaceous sorbents and biosorbents were characterized by excellent efficiency and superiority toward lead(II) sorption compared to blank active carbon providing a maximum sorption capacity of lead(II) ion as 500 μmol g−1. Sorption processes of lead(II) by these hybrid materials were investigated under the influence of several controlling parameters such as pH, contact time, mass of sorbent and biosorbent, lead(II) concentration, and foreign ions. Lead(II) sorption mechanisms were found to obey the Langmuir and BET isotherm models. The potential applications of chemically and biologically modified-active carbonaceous materials for removal and extraction of lead from real water matrices were also studied via a double-stage microcolumn technique. The results of this study were found to denote to superior recovery values of lead (95.0–99.0 ± 3.0–5.0%) by various carbonaceous-modified-bakers yeast biosorbents. PMID:22629157

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

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.

Nickel(II) biosorption by Rhodotorula glutinis.

PubMed

Suazo-Madrid, Alicia; Morales-Barrera, Liliana; Aranda-García, Erick; Cristiani-Urbina, Eliseo

2011-01-01

The present study reports the feasibility of using Rhodotorula glutinis biomass as an alternative low-cost biosorbent to remove Ni(II) ions from aqueous solutions. Acetone-pretreated R. glutinis cells showed higher Ni(II) biosorption capacity than untreated cells at pH values ranging from 3 to 7.5, with an optimum pH of 7.5. The effects of other relevant environmental parameters, such as initial Ni(II) concentration, shaking contact time and temperature, on Ni(II) biosorption onto acetone-pretreated R. glutinis were evaluated. Significant enhancement of Ni(II) biosorption capacity was observed by increasing initial metal concentration and temperature. Kinetic studies showed that the kinetic data were best described by a pseudo-second-order kinetic model. Among the two-, three-, and four-parameter isotherm models tested, the Fritz-Schluender model exhibited the best fit to experimental data. Thermodynamic parameters (activation energy, and changes in activation enthalpy, activation entropy, and free energy of activation) revealed that the biosorption of Ni(II) ions onto acetone-pretreated R. glutinis biomass is an endothermic and non-spontaneous process, involving chemical sorption with weak interactions between the biosorbent and Ni(II) ions. The high sorption capacity (44.45 mg g(-1) at 25°C, and 63.53 mg g(-1) at 70°C) exhibited by acetone-pretreated R. glutinis biomass places this biosorbent among the best adsorbents currently available for removal of Ni(II) ions from aqueous effluents.

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

PubMed

Fernandes, M Marques; Scheinost, A C; Baeyens, B

2016-08-01

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks. Copyright © 2016 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 positive correlation of Kr for Pb and the soil pH, effective cation exchange capacity (CECe), the different forms of C (inorganic, humin, fulvic and humic acids), the percentage of clay fraction and the percentage of crystalline minerals in that fraction (P < 0.01). Therefore, the best treatment to increase the sorption capacity of Pb by mine soils is the amendment with organic wastes. References Giles, C.H.; Smith, D.; Huitson, A. 1974. J. Colloid. Interface Sci. 47: 755-756. Vega, F.A.; Covelo, E.F.; Andrade, M.L. 2009. J. Hazard. Mater. 169: 36-45. Vega, F.A.; Covelo, E.F.; Andrade, M.L. 2008. J. Colloid. Interface Sci. 327: 275-286.

Adsorption of copper (II) by using derived-farmyard and poultry manure biochars: Efficiency and mechanism

NASA Astrophysics Data System (ADS)

Batool, Saima; Idrees, Muhammad; Hussain, Qaiser; Kong, Jie

2017-12-01

Biochar (BC) has recently become an attractive adsorbent for the removal of toxic metals from aqueous media. In this study, the adsorption efficiency of BCs derived through farmyard and poultry manure (DBC-FYM, DBC-PM) for the removal of copper (Cu2+) from water was evaluated. The porosity, surface structure, internal morphology, thermal stability and functional groups of the DBCs were analyzed using different analytical techniques such as scanning electron microscopy (SEM), X-ray photon spectroscopy (XPS), thermogravimetric analyses (TGA) and fourier transmission infrared spectroscopy (FTIR). Kinetics and isothermal data were acquired by batch adsorption mode. The isothermal sorption data was well correlated (R2 > 0.98) with the Freundlich model describing multilayer sorption of Cu2+ on heterogeneous DBCs surface. The maximum Cu2+ sorption was estimated as 44.50 mg/g for DBC-FYM and 43.68 mg/g for DBC-PM. The sorption data followed the pseudo-second order kinetics, indicating the chemical interaction between Cu2+ and the negative charged surface of DBCs. The thermodynamic parameters indicated that the reaction was exothermic and spontaneous. Post-sorption analysis of the DBCs by XPS suggested the formation of CuO and carbonate dihydroxide. The outcomes of the present study indicated that DBCs could be valuable green sorbents for removing Cu2+ from contaminated aqueous media.

Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer.

PubMed

Appell, Michael; Jackson, Michael A

2012-02-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1-10 μg·L(-1). These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples.

Properties of Silurian shales from the Barrandian Basin, Czech Republic

NASA Astrophysics Data System (ADS)

Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

2017-04-01

Although shale gas-bearing deposits have a markedly lower gas content than coal deposits, great attention has recently been paid to shale gas as a new potential source of fossil energy. Shale gas extraction is considered to be quite economical, despite the lower sorption capacity of shales, which is only about 10% of coal sorption capacities The selection of a suitable locality for extracting shale gas requires the sorption capacity of the shale to be determined. The sorption capacity is determined in the laboratory by measuring the amount of methane absorbed in a shale specimen at a pressure and a temperature corresponding to in situ conditions, using high pressure sorption. According to the principles of reversibility of adsorption/desorption, this amount should be roughly related to the amount of gas released by forced degassing. High pressure methane sorption isotherms were measured on seven representative samples of Silurian shales from the Barrandian Basin, Czech Republic. Excess sorption measurements were performed at a temperature of 45oC and at pressures up to 15 MPa on dry samples, using a manometric method. Experimental methane high-pressure isotherms were fitted to a modified Langmuir equation. The maximum measured excess sorption parameter and the Langmuir sorption capacity parameter were used to study the effect of TOC content, organic maturity, inorganic components and porosity on the methane sorption capacity. The studied shale samples with random reflectance of graptolite 0.56 to 1.76% had a very low TOC content and dominant mineral fractions. Illite was the prevailing clay mineral. The sample porosity ranged from 4.6 to 18.8%. In most samples, the micropore volumes were markedly lower than the meso- and macropore volumes. In the Silurian black shales, the occurrence of fractures parallel with the original sedimentary bending was highly significant. A greater proportion of fragments of carbonaceous particles of graptolites and bitumens in the Barrandian Silurian shales had a smooth surface without pores. No relation has been proven between TOC-normalized excess sorption capacities or the TOC-normalized Langmuir sorption capacities and thermal maturation of the shales. The methane sorption capacities of shale samples show a positive correlation with TOC and a positive correlation with the clay content. The highest sorption capacity was observed in shale samples with the highest percentage of micropores, indicating that the micropore volume in the organic matter and clay minerals is a principal factor affecting the sorption capacity of the shale samples.

[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.

Insight from simulations of single-well injection-withdrawal tracer tests on simple and complex fractures

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

Tsang, C.-F.; Doughty, C.

2009-08-06

The single-well injection withdrawal (SWIW) test, a tracer test utilizing only one well, is proposed as a useful contribution to site characterization of fractured rock, as well as providing parameters relevant to tracer diffusion and sorption. The usual conceptual model of flow and solute transport through fractured rock with low matrix permeability involves solute advection and dispersion through a fracture network coupled with diffusion and sorption into the surrounding rock matrix. Unlike two-well tracer tests, results of SWIW tests are ideally independent of advective heterogeneity, channeling and flow dimension, and, instead, focus on diffusive and sorptive characteristics of tracer (solute)more » transport. Thus, they can be used specifically to study such characteristics and evaluate the diffusive parameters associated with tracer transport through fractured media. We conduct simulations of SWIW tests on simple and complex fracture models, the latter being defined as having two subfractures with altered rock blocks in between and gouge material in their apertures. Using parameters from the Aspo site in Sweden, we calculate and study SWIW tracer breakthrough curves (BTCs) from a test involving four days of injection and then withdrawal. By examining the peak concentration C{sub pk} of the SWIW BTCs for a variety of parameters, we confirm that C{sub pk} is largely insensitive to the fracture advective flow properties, in particular to permeability heterogeneity over the fracture plane or to subdividing the flow into two subfractures in the third dimension orthogonal to the fracture plane. The peak arrival time t{sub pk} is not a function of fracture or rock properties, but is controlled by the time schedule of the SWIW test. The study shows that the SWIW test is useful for the study of tracer diffusion-sorption processes, including the effect of the so-called flow-wetted surface (FWS) of the fracture. Calculations with schematic models with different FWS values are conducted and the possibility of direct in situ measurement of FWS with SWIW tests is demonstrated.« less

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

PubMed

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

2018-02-15

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

Cs sorption to potential host rock of low-level radioactive waste repository in Taiwan: experiments and numerical fitting study.

PubMed

Wang, Tsing-Hai; Chen, Chin-Lung; Ou, Lu-Yen; Wei, Yuan-Yaw; Chang, Fu-Lin; Teng, Shi-Ping

2011-09-15

A reliable performance assessment of radioactive waste repository depends on better knowledge of interactions between nuclides and geological substances. Numerical fitting of acquired experimental results by the surface complexation model enables us to interpret sorption behavior at molecular scale and thus to build a solid basis for simulation study. A lack of consensus on a standard set of assessment criteria (such as determination of sorption site concentration, reaction formula) during numerical fitting, on the other hand, makes lower case comparison between various studies difficult. In this study we explored the sorption of cesium to argillite by conducting experiments under different pH and solid/liquid ratio (s/l) with two specific initial Cs concentrations (100mg/L, 7.5 × 10(-4)mol/L and 0.01 mg/L, 7.5 × 10(-8)mol/L). After this, numerical fitting was performed, focusing on assessment criteria and their consequences. It was found that both ion exchange and electrostatic interactions governed Cs sorption on argillite. At higher initial Cs concentration the Cs sorption showed an increasing dependence on pH as the solid/liquid ratio was lowered. In contrast at trace Cs levels, the Cs sorption was neither s/l dependent nor pH sensitive. It is therefore proposed that ion exchange mechanism dominates Cs sorption when the concentration of surface sorption site exceeds that of Cs, whereas surface complexation is attributed to Cs uptake under alkaline environments. Numerical fitting was conducted using two different strategies to determine concentration of surface sorption sites: the clay model (based on the cation exchange capacity plus surface titration results) and the iron oxide model (where the concentration of sorption sites is proportional to the surface area of argillite). It was found that the clay model led to better fitting than the iron oxide model, which is attributed to more amenable sorption sites (two specific sorption sites along with larger site density) when using clay model. Moreover, increasing s/l ratio would produce more sorption sites, which helps to suppress the impact of heterogeneous surface on Cs sorption behavior under high pH environments. Copyright © 2011 Elsevier B.V. All rights reserved.

Glyphosate sorption to soils of Argentina. Estimation of affinity coeficient by pedotransfer function

NASA Astrophysics Data System (ADS)

De Geronimo, Eduardo; Aparicio, Virginia; Costa, José Luis

2017-04-01

Argentine agricultural production is fundamentally based on a technological package that combines direct seeding and glyphosate with transgenic crops (soybean, maize and cotton). Therefore, glyphosate is the most employed herbicide in the country, where 180 to 200 million liters are applied every year. Glyphosate is strongly sorbed to soil by binding to clay minerals, layer silicates, metal oxides, non-crystalline materials or organic matter. Sorption of glyphosate is a reversible process that regulates the half-life and mobility of the herbicide and it is therefore related to the risk of contaminating courses of surface and groundwater. However, this behavior may vary depending on the characteristics of the soil on which it is applied. In addition, pH is a determining factor since it modifies the net charge in the molecule and, with it, the force of the electrostatic interaction between the glyphosate and the components of the soil. For a reliable risk assessment of groundwater contamination from pesticides precise predictions of sorption coefficients are needed. The aim of this work is to study the affinity of glyphosate to different soils of Argentina and create a model to estimate the glyphosate Freundlich sorption coefficient (Kf) from easily measurable soil properties. Adsorption of glyphosate was investigated on 12 different agricultural soils of Argentina using batch equilibration technique and fit to Freundlich sorption model. The correlation coefficients and the effects of soil characteristic factors on glyphosate adsorption parameter were analyzed through principal component and multiple lineal regression analysis. Results indicate that pH and clay contents were found to be the most significant soil factors which affect the glyphosate adsorption process. The Freundlich (Kf) pedotransfer function obtained by stepwise regression analysis was Kf = 735.2*Clay - 104.2*pH + 0.7*Polsen - 3.8*Alin. A 97.9% of the variation of glyphosate sorption coefficient could be attributed to the variation of the soil clay contents, pH, Polsen and Alin.

Estimation of biotransformation and sorption of emerging organic compounds (EOCs) during artificial recharge through a reactive barrier.

NASA Astrophysics Data System (ADS)

Valhondo, C.; Martinez-Landa, L.; Carrera, J.; Hidalgo, J. J.; Ayora, C.

2016-12-01

The reuse of lesser quality water such as effluents from wastewater treatment plants or effluent-receiving water bodies has been promoted due to the water shortages affecting many regions of the world. Artificial recharge through infiltration basins is known to improve several water quality parameters including the attenuation of emerging organic compounds (EOCs). Many of these contaminants exhibit redox dependent biotransformation because the redox state is one of the factors controlling microbial community development. Together with biotransformation, sorption also affects the behavior of EOCs in their passage through the soil. We studied EOCs attenuation in an infiltration system is located in Sant Vicenç dells Horts on the Llobregat delta (Barcelona, Spain), where the local water agency has an artificial recharge pilot project . The Llobregat river water used for the artificial recharge is affected by treatment plant effluents which contain EOCs. A reactive barrier consisting of vegetable compost, clay, and iron oxide was installed in the bottom of the infiltration basin to enhance biotransformation and sorption of EOCs. The barrier releases dissolved organic carbon, which favors the development of a broad range of redox environments, and supplies neutral, cationic, and anionic surfaces to favor sorption of different types of contaminants. Results were excellent, but quantitative evaluation of the EOCs attenuation requires knowledge of the residence time distribution of infiltrated water. A tracer test was performed by adding tracers to the infiltration water and interpreting the breakthrough curves at diverse monitoring points with a 2D multilayer numerical model. The calibrated model quantify degradation, as a first order law, and sorption through a linear distribution coefficient for ten selected EOCs. Results indicate higher degradation rates and sorption coefficients in the reactive barrier than in the rest of the aquifer for nine and eight of the ten studied EOCs, respectively, which demonstrates the efficiency of the reactive barrier to enhance the removal of EOCs.

Conservative and reactive solute transport in constructed wetlands

USGS Publications Warehouse

Keefe, Steffanie H.; Barber, Larry B.; Runkel, Robert L.; Ryan, Joseph N.; McKnight, Diane M.; Wass, Roland D.

2004-01-01

The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater‐dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first‐order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%).

Water Dynamics in Egg White Peptide, Asp-His-Thr-Lys-Glu, Powder Monitored by Dynamic Vapor Sorption and LF-NMR.

PubMed

Yang, Shuailing; Liu, Xuye; Jin, Yan; Li, Xingfang; Chen, Feng; Zhang, Mingdi; Lin, Songyi

2016-03-16

Water absorbed into the bulk amorphous structure of peptides can have profound effects on their properties. Here, we elucidated water dynamics in Asp-His-Thr-Lys-Glu (DHTKE), an antioxidant peptide derived from egg white ovalbumin, using water dynamic vapor sorption (DVS) and low-field nuclear magnetic resonance (LF-NMR). The DVS results indicated that parallel exponential kinetics model fitted well to the data of sorption kinetics behavior of DHTKE. Four different proton fractions with different mobilities were identified based on the degree of interaction between peptide and water. The water could significantly change the proton distribution and structure of the sample. The different phases of moisture absorption were reflected in the T2 parameters. In addition, the combined water content was dominant in the hygroscopicity of DHTKE. This study provides an effective real-time monitoring method for water mobility and distribution in synthetic peptides, and this method may have applications in promoting peptide quality assurance.

SORPTION OF TOXIC ORGANIC COMPOUNDS ON WATERWATER SOLIDS: MECHANISMS AND MODELING

EPA Science Inventory

It is proposed that sorption is a combination of two fundamentally different processes: adsorption and partitioning. A sorption model was developed for both single-component and multicomponent systems. The model was tested using single-component experimental isotherm data of eig...

Modeling and risk assessment of a 30-Year-old subsurface radioactive-liquid drain field

NASA Astrophysics Data System (ADS)

Dawson, Lon A.; Pohl, Phillip I.

1997-11-01

The contamination from a 30-year-old radioactive liquid drain field was assessed for movement in the subsurface and potential risks to humans. This assessment included determining field concentrations of cesium 137 (137Cs) and other inorganic contaminants and modeling of the flow and transport of the liquid waste that was sent to the drain field. The field investigation detected no contamination deeper than 15 feet (4.6 m) from the bottom of the drain field. Prediction of the water content of the vadose zone showed no saturated conditions for times greater than 10 years after the known infiltration. Sensitivity analysis of the modeling parameters showed the equilibrium sorption coefficient to be the most important factor in predicting the contaminant plumes. Calibration of modeling results with field data gave a 137Cs sorption coefficient that is within the range of values found in the literature. The risk assessment for the site showed that the contamination poses no significant risk to human health.

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

PubMed

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

2014-01-30

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

Surface complexation modeling of americium sorption onto volcanic tuff.

PubMed

Ding, M; Kelkar, S; Meijer, A

2014-10-01

Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways. Published by Elsevier Ltd.

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Photocatalytic TMO-NMs adsorbent: Temperature-Time dependent Safranine degradation, sorption study validated under optimized effective equilibrium models parameter with standardized statistical analysis

PubMed Central

Wahab, Rizwan; Khan, Farheen; Kaushik, Nagendra Kumar; Musarrat, Javed; Al-Khedhairy, Abdulaziz A.

2017-01-01

In this paper, chemically synthesized copper oxide nanoparticles (CuO-NPs), were employed for two processes: one is photocatalytic degradation and second one adsorption for the sorption of safranine (SA) dye in an aqueous medium at pH = 12.01. The optimized analytes amount (nano-adsorbent = 0.10 g, conc. range of SA dye 56.13 ppm to 154.37 ppm, pH = 12.01, temperature 303 K) reached to equilibrium point in 80 min, which acquired for chemical adsorption-degradation reactions. The degredated SA dye data’s recorded by UV-visible spectroscopy for the occurrence of TMO-NMs of CuO-NPs at anticipated period of interval. The feasible performance of CuO-NPs was admirable, shows good adsorption capacity qm = 53.676 mg g−1 and most convenient to best fitted results establish by linear regression equation, corresponded for selected kinetic model (pseudo second order (R2 = 0.9981), equilibrium isotherm models (Freundlich, Langmuir, Dubnin-Radushkevich (D-R), Temkin, H-J and Halsey), and thermodynamic parameters (∆H° = 75461.909 J mol−1, ∆S° = 253.761 J mol−1, ∆G° = −1427.93 J mol−1, Ea = 185.142 J mol−1) with error analysis. The statistical study revealed that CuO-NPs was an effective adsorbent certified photocatalytic efficiency (η = 84.88%) for degradation of SA dye, exhibited more feasibility and good affinity toward adsorbate, the sorption capacity increases with increased temperature at equilibrium point. PMID:28195174

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.

Influence of Manufacturing Parameters on Microstructure and Hydrogen Sorption Behavior of Electron Beam Melted Titanium Ti-6Al-4V Alloy

PubMed Central

Pushilina, Natalia; Syrtanov, Maxim; Murashkina, Tatyana; Kudiiarov, Viktor; Lider, Andrey; Koptyug, Andrey

2018-01-01

Influence of manufacturing parameters (beam current from 13 to 17 mA, speed function 98 and 85) on microstructure and hydrogen sorption behavior of electron beam melted (EBM) Ti-6Al-4V parts was investigated. Optical and scanning electron microscopies as well as X-ray diffraction were used to investigate the microstructure and phase composition of EBM Ti-6Al-4V parts. The average α lath width decreases with the increase of the speed function at the fixed beam current (17 mA). Finer microstructure was formed at the beam current 17 mA and speed function 98. The hydrogenation of EBM Ti-6Al-4V parts was performed at the temperatures 500 and 650 °С at the constant pressure of 1 atm up to 0.3 wt %. The correlation between the microstructure and hydrogen sorption kinetics by EBM Ti-6Al-4V parts was demonstrated. Lower average hydrogen sorption rate at 500 °C was in the sample with coarser microstructure manufactured at the beam current 17 mA and speed function 85. The difference of hydrogen sorption kinetics between the manufactured samples at 650 °C was insignificant. The shape of the kinetics curves of hydrogen sorption indicates the phase transition αH + βH→βH. PMID:29747471

Influence of Manufacturing Parameters on Microstructure and Hydrogen Sorption Behavior of Electron Beam Melted Titanium Ti-6Al-4V Alloy.

PubMed

Pushilina, Natalia; Syrtanov, Maxim; Kashkarov, Egor; Murashkina, Tatyana; Kudiiarov, Viktor; Laptev, Roman; Lider, Andrey; Koptyug, Andrey

2018-05-10

Influence of manufacturing parameters (beam current from 13 to 17 mA, speed function 98 and 85) on microstructure and hydrogen sorption behavior of electron beam melted (EBM) Ti-6Al-4V parts was investigated. Optical and scanning electron microscopies as well as X-ray diffraction were used to investigate the microstructure and phase composition of EBM Ti-6Al-4V parts. The average α lath width decreases with the increase of the speed function at the fixed beam current (17 mA). Finer microstructure was formed at the beam current 17 mA and speed function 98. The hydrogenation of EBM Ti-6Al-4V parts was performed at the temperatures 500 and 650 °С at the constant pressure of 1 atm up to 0.3 wt %. The correlation between the microstructure and hydrogen sorption kinetics by EBM Ti-6Al-4V parts was demonstrated. Lower average hydrogen sorption rate at 500 °C was in the sample with coarser microstructure manufactured at the beam current 17 mA and speed function 85. The difference of hydrogen sorption kinetics between the manufactured samples at 650 °C was insignificant. The shape of the kinetics curves of hydrogen sorption indicates the phase transition α H + β H →β H .

Nonideal transport of reactive solutes in heterogeneous porous media: 4. Analysis of the Cape Cod Natural‐Gradient Field Experiment

USGS Publications Warehouse

Brusseau, Mark L.; Srivastava, Rajesh

1999-01-01

One of the largest field studies of reactive‐solute transport is the natural‐gradient experiment conducted at Cape Cod from 1985 to 1988. Major findings regarding the transport behavior of the reactive solute (lithium) were that the rate of plume displacement decreased with time (temporal increase in effective retardation), the degree of longitudinal spreading was much greater than that observed for bromide for an equivalent travel distance, and the plume was asymmetric, with maximum concentrations located near the leading edges. The objective of our work was to quantitatively analyze the transport of lithium and to attempt to identify the factor or factors that contributed significantly to its observed nonideal transport. We used a mathematical model that accounted for several transport factors, including spatially variable hydraulic conductivity and spatially variable, nonlinear, rate‐limited sorption, with all parameter values obtained independently. The transport behavior observed during the first 250 days, corresponding to a transport distance of 60 m, was predicted reasonably well by the simulation that incorporated spatially variable hydraulic conductivity; nonlinear, rate‐limited, spatially variable sorption; and uniform water chemistry. However, the larger degree of deceleration observed during the latter stage of the experiment (the filial 20 m) was not. The larger deceleration was successfully simulated by increasing 3‐fold the mean sorption capacity of the latter portion of the transport domain. Such a change in sorption capacity is consistent with the potential impact on lithium sorption of measured changes in water chemistry (e.g.,pH increase, reduction in resident Zn)at occur in the zone through which the lithium plume traversed. The results of the analyses suggest that nonlinear sorption and variable water chemistry may have btors responsible for the nonuniform displacement of the lithium plume, with rate‐limited sorption/desorption having minimal impact. In addition, the asymmetry of the plume appears to have been caused primarily by nonlinear sorption, whereas the enhanced longitudinal spreading appears to have been caused by the combined influences of spatially variable hydraulic conductivity and sorption, nonlinear sorption, and rate‐limited sorption/desorption. A comparison of the results of this analysis to those we obtained from an analysis of the Borden natural‐gradient study reveals several similarities regarding the transport of reactive contaminants at the field scale.

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature.

PubMed

Vereecken, H; Vanderborght, J; Kasteel, R; Spiteller, M; Schäffer, A; Close, M

2011-01-01

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

Transport processes and mutual interactions of three bacterial strains in saturated porous media

NASA Astrophysics Data System (ADS)

Stumpp, Christine; Lawrence, John R.; Hendry, M. Jim; Maloszewski, Pitor

2010-05-01

Transport processes of the bacterial strains Klebsiella oxytoca, Burkholderia cepacia G4PR-1 and Pseudomonas sp #5 were investigated in saturated column experiments to study the differences in transport characteristics and the mutual interactions of these strains during transport. Soil column experiments (114 mm long x 33 mm in diameter) were conducted with constant water velocities (3.9-5.7 cm/h) through a medium to coarse grained silica sand. All experiments were performed in freshly packed columns in quadruplicate. Chloride was used as tracer to determine the mean transit time, dispersivity and flow rate. It was injected as a pulse into the columns together with the bacterial strains suspended in artificial groundwater medium. In the first setup, each strain was investigated alone. In the second setup, transport processes were performed injecting two strains simultaneously. Finally, the transport characteristics were studied in successive experiments when one bacterium was resident on the sand grains prior to the introduction of the second strain. In all experiments the peak C/Co bacterial concentrations were attenuated with respect to the conservative tracer chloride and a well defined tailing was observed. A one dimensional mathematical model for advective-dispersive transport that accounts for irreversible and reversible sorption was used to analyze the bacterial breakthrough curves and tailing patterns. It was shown that the sorption parameters were different for the three strains that can be explained by the properties of the bacteria. For the species Klebsiella oxytoca and Burkholderia cepacia G4PR-the transport parameters were mostly in the same range independent of the experimental setup. However, Pseudomonas sp #5, which is a motile bacterium, showed differences in the breakthrough curves and sorption parameters during the experiments. The simultaneous and successive experiments indicated an influence on the reversible sorption processes when another strain was present during the transport processes.

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.

Understanding the sorption and biotransformation of organic micropollutants in innovative biological wastewater treatment technologies.

PubMed

Alvarino, T; Suarez, S; Lema, J; Omil, F

2018-02-15

New technologies for wastewater treatment have been developed in the last years based on the combination of biological reactors operating under different redox conditions. Their efficiency in the removal of organic micropollutants (OMPs) has not been clearly assessed yet. This review paper is focussed on understanding the sorption and biotransformation of a selected group of 17 OMPs, including pharmaceuticals, hormones and personal care products, during biological wastewater treatment processes. Apart from considering the role of "classical" operational parameters, new factors such as biomass conformation and particle size, upward velocity applied or the addition of adsorbents have been considered. It has been found that the OMP removal by sorption not only depends on their physico-chemical characteristics and other parameters, such as the biomass conformation and particle size, or some operational conditions also relevant. Membrane biological reactors (MBR), have shown to enhance sorption and biotransformation of some OMPs. The same applies to technologies bases on direct addition of activated carbon in bioreactors. The OMP biotransformation degree and pathway is mainly driven by the redox potential and the primary substrate activity. The combination of different redox potentials in hybrid reactor systems can significantly enhance the overall OMP removal efficiency. Sorption and biotransformation can be synergistically promoted in biological reactors by the addition of activated carbon. The deeper knowledge of the main parameters influencing OMP removal provided by this review will allow optimizing the biological processes in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site

NASA Astrophysics Data System (ADS)

Dangelmayr, Martin A.; Reimus, Paul W.; Johnson, Raymond H.; Clay, James T.; Stone, James J.

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO3 and 360 mg/l CaCO3) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO3 over columns fed with 160 mg/l CaCO3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site.

PubMed

Dangelmayr, Martin A; Reimus, Paul W; Johnson, Raymond H; Clay, James T; Stone, James J

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO 3 and 360 mg/l CaCO 3 ) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO 3 over columns fed with 160 mg/l CaCO 3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments. Copyright © 2018 Elsevier B.V. All rights reserved.

Modeling of copper sorption onto GFH and design of full-scale GFH adsorbers.

PubMed

Steiner, Michele; Pronk, Wouter; Boller, Markus A

2006-03-01

During rain events, copper wash-off occurring from copper roofs results in environmental hazards. In this study, columns filled with granulated ferric hydroxide (GFH) were used to treat copper-containing roof runoff. It was shown that copper could be removed to a high extent. A model was developed to describe this removal process. The model was based on the Two Region Model (TRM), extended with an additional diffusion zone. The extended model was able to describe the copper removal in long-term experiments (up to 125 days) with variable flow rates reflecting realistic runoff events. The four parameters of the model were estimated based on data gained with specific column experiments according to maximum sensitivity for each parameter. After model validation, the parameter set was used for the design of full-scale adsorbers. These full-scale adsorbers show high removal rates during extended periods of time.

Sorption of benzotriazoles under the conditions of RP HPLC

NASA Astrophysics Data System (ADS)

Dzhabieva, S. A.; Kurbatova, S. V.; Belousova, Z. P.

2016-02-01

The results of a chromatographic study of sorption of several benzotriazole derivatives on octadecyl silica gel were reported. The physicochemical and electronic parameters of benzotriazoles were calculated. The effect of the structure of analyte molecules and eluent composition on chromatographic retention of these substances was analyzed.

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 from 6.5 to 8.0. Sorption capacity was reduced with aging time. From kinetic results, two-compartment first order model was more suitable than one-compartment first order model. Fast sorption site of biochar-amended soils dominated total sorption process (i.e., Fraction of fast sorption site ranged from 0.55 to 0.96). Reduced sorption capacity with aging time could be attributed to changes in physico-chemical properties of biochar-amended soils (e.g., reduced pores and increased hydrophilic carboxyl and carbonyl functional groups). Verification is FI-IR and SSA. It is assumed that biochar is a suitable material for PHE contaminated soil in order to reduce the lability of PHE. However, aging effects would lessen biochar benefit for reducing the sorption capacity of PHE by forming hydrophilic functional group and reducing pores.

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments. Copyright 2003 Elsevier B.V.

Numerical modeling of sorption kinetics of organic compounds to soil and sediment particles

NASA Astrophysics Data System (ADS)

Wu, Shian-chee; Gschwend, Phillip M.

1988-08-01

A numerical model is developed to simulate hydrophobic organic compound sorption kinetics, based on a retarded intraaggregate diffusion conceptualization of this solid-water exchange process. This model was used to ascertain the sensitivity of the sorption process for various sorbates to nonsteady solution concentrations and to polydisperse soil or sediment aggregate particle size distributions. Common approaches to modeling sorption kinetics amount to simplifications of our model and appear justified only when (1) the concentration fluctuations occur on a time scale which matches the sorption timescale of interest and (2) the particle size distribution is relatively narrow. Finally, a means is provided to estimate the extent of approach of a sorbing system to equilibrium as a function of aggregate size, chemical diffusivity and hydrophobicity, and system solids concentration.

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

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

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

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

2014-01-01

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

Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field.

PubMed

Rakowska, Magdalena I; Kupryianchyk, Darya; Koelmans, Albert A; Grotenhuis, Tim; Rijnaarts, Huub H M

2014-12-15

Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of PAHs and PCBs to powdered and granular activated carbons (AC) after three different sediment treatments: sediment mixed with powdered AC (PAC), sediment mixed with granular AC (GAC), and addition of GAC followed by 2 d mixing and subsequent removal ('sediment stripping'). Remediation efficiency was assessed by quantifying fluxes of PAHs towards SPME passive samplers inserted in the sediment top layer, which showed that the efficiency decreased in the order of PAC > GAC stripping > GAC addition. Sorption was very strong to PAC, with Log KAC (L/kg) values up to 10.5. Log KAC values for GAC ranged from 6.3-7.1 and 4.8-6.2 for PAHs and PCBs, respectively. Log KAC values for GAC in the stripped sediment were 7.4-8.6 and 5.8-7.7 for PAH and PCB. Apparent first order adsorption rate constants for GAC (kGAC) in the stripping scenario were calculated with a first-order kinetic model and ranged from 1.6 × 10(-2) (PHE) to 1.7 × 10(-5) d(-1) (InP). Sorption affinity parameters did not change within 9 months post treatment, confirming the longer term effectiveness of AC in field applications for PAC and GAC. Copyright © 2014. Published by Elsevier Ltd.

Sorption of Ochratoxin A from Aqueous Solutions Using β-Cyclodextrin-Polyurethane Polymer

PubMed Central

Appell, Michael; Jackson, Michael A.

2012-01-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1–10 μg·L−1. These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples. PMID:22474569

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

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.

Sorption of 3,3',4,4'-tetrachlorobiphenyl by microplastics: A case study of polypropylene.

PubMed

Zhan, Zhiwei; Wang, Jundong; Peng, Jinping; Xie, Qilai; Huang, Ying; Gao, Yifan

2016-09-15

Though plastics show good chemical inertness, they could sorb polychlorinated biphenyls (PCBs) and other toxic pollutants from the surrounding environment. Thus, ingestion of microplastics by marine organisms potentially enhances the transport and bioavailability of toxic chemicals. However, there is lack of studies on the sorption capacity, mechanism and factors affecting the sorption behavior. Here, sorption of PCBs by microplastics in the simulated seawater was studied using the batch oscillation equilibration technique, in which polypropylene (PP) and 3,3',4,4'-tetrachlorobiphenyl (PCB77) acted as model plastic and PCB, respectively. Factors including particle size, temperature and solution environment were investigated. Results showed that, equilibrium sorption time is about 8h and sorption capacity increase with decreasing particle size and temperature. Different sorption capacity in three solution environments was observed. Equilibrium data in three solution environments fitted very well to the Langmuir sorption model, indicating chemical sorption is the predominant mechanism. Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2011-04-01

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively. Copyright © 2010 Elsevier Inc. All rights reserved.

Pedotransfer functions for isoproturon sorption on soils and vadose zone materials.

PubMed

Moeys, Julien; Bergheaud, Valérie; Coquet, Yves

2011-10-01

Sorption coefficients (the linear K(D) or the non-linear K(F) and N(F)) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K(D) and 55 K(F)) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K(D) . The pedotransfer function is K(D) = 1.7822 + 0.0162 OC(1.5) - 0.1958 pH (K(D) in L kg(-1) and OC in g kg(-1)). For low-OC soils (OC < 6.15 g kg(-1)), clay and pH are most influential. The pedotransfer function is then K(D) = 0.9980 + 0.0002 clay - 0.0990 pH (clay in g kg(-1)). Benchmarking K(D) estimations showed that functions calibrated on more specific subsets of the data perform better on these subsets than functions calibrated on larger subsets. Predicting isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site- or soil-specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K(OC) values calculated on a large dataset or (d) K(OC) values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry.

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.

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.

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...

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, L.B.; Thurman, E.M.; Runnells, D.R.; ,

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on solution of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is < 0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Assessment of bioavailability of soil-sorbed atrazine.

PubMed

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

2003-06-01

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

Assessment of Bioavailability of Soil-Sorbed Atrazine

PubMed Central

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

2003-01-01

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

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.

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 diffuse to lower concentration regions according to their individual concentration gradients. Since locally the cation concentration for potassium, (sodium and calcium) is increased, sorption of these cations is also locally enhanced, affecting in return the sorption behaviour of migrating caesium. Consequently, the sorption process of caesium in such diffusion experiments cannot be addressed by a non-linear isotherm formalism any longer. (3) A reasonable analysis of such single tracer diffusion experiments therefore requires the combined description of transport (diffusion) and sorption of many cations and the whole complex water chemistry of the system. Thus, single-species models can only be applied with care in the considered concentration ranges.

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride.

PubMed

Boudrahem, F; Aissani-Benissad, F; Aït-Amar, H

2009-07-01

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions. The influence of impregnation ratio (ZnCl2/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m2/g) and micropore volume (0.772 cm3/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio. Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 degrees C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others. Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl2 is a suitable activating agent for the preparation of high-porosity carbons.

Biosorption of neodymium on Chlorella vulgaris in aqueous solution obtained from hard disk drive magnets

PubMed Central

Kucuker, Mehmet Ali; Wieczorek, Nils; Kuchta, Kerstin; Copty, Nadim K.

2017-01-01

In recent years, biosorption is being considered as an environmental friendly technology for the recovery of rare earth metals (REE). This study investigates the optimal conditions for the biosorption of neodymium (Nd) from an aqueous solution derived from hard drive disk magnets using green microalgae (Chlorella vulgaris). The parameters considered include solution pH, temperature and biosorbent dosage. Best-fit equilibrium as well as kinetic biosorption models were also developed. At the optimal pH of 5, the maximum experimental Nd uptakes at 21, 35 and 50°C and an initial Nd concentration of 250 mg/L were 126.13, 157.40 and 77.10 mg/g, respectively. Analysis of the optimal equilibrium sorption data showed that the data fitted well (R2 = 0.98) to the Langmuir isotherm model, with maximum monolayer coverage capacity (qmax) of 188.68 mg/g, and Langmuir isotherm constant (KL) of 0.029 L/mg. The corresponding separation factor (RL) is 0.12 indicating that the equilibrium sorption was favorable. The sorption kinetics of Nd ion follows well a pseudo-second order model (R2>0.99), even at low initial concentrations. These results show that Chlorella vulgaris has greater biosorption affinity for Nd than activated carbon and other algae types such as: A. Gracilis, Sargassum sp. and A. Densus. PMID:28388641

Equilibrium and kinetic modelling of chromium(III) sorption by animal bones.

PubMed

Chojnacka, Katarzyna

2005-04-01

The paper discusses sorption of Cr(III) ions from aqueous solutions by animal bones. Animal bones were found to be an efficient sorbent with the maximum experimentally determined sorption capacity in the range 29-194 mg g(-1) that depended on pH and temperature. The maximum experimentally determined sorption capacity was obtained at 50 degrees C, pH 5. Batch kinetics and equilibrium experiments were performed in order to investigate the influence of contact time, initial concentration of sorbate and sorbent, temperature and pH. It was found that sorption capacity increased with increase of Cr(III) concentration, temperature and initial pH of metal solution. Mathematical models describing kinetics and statics of sorption were proposed. It was found that process kinetics followed the pseudo-second-order pattern. The influence of sorbent concentration was described with Langmuir-type equation and the influence of sorbate concentration was described with empirical dependence. The models were positively verified.

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.

Interaction of copper and fulvic acid at the hematite-water interface

NASA Astrophysics Data System (ADS)

Christl, Iso; Kretzschmar, Ruben

2001-10-01

The influence of surface-bound fulvic acid on the sorption of Cu(II) to colloidal hematite particles was studied experimentally and the results were compared with model calculations based on the linear additivity assumption. In the first step, proton and Cu binding to colloidal hematite particles and to purified fulvic acid was studied by batch equilibration and ion-selective electrode titration experiments, respectively. The sorption data for these binary systems were modeled with a basic Stern surface complexation model for hematite and the NICA-Donnan model for fulvic acid. In the second step, pH-dependent sorption of Cu and fulvic acid in ternary systems containing Cu, hematite, and fulvic acid in NaNO3 electrolyte solutions was investigated in batch sorption experiments. Sorption of fulvic acid to the hematite decreased with increasing pH (pH 3-10) and decreasing ionic strength (0.01-0.1 M NaNO3), while the presence of 22 μM Cu had a small effect on fulvic acid sorption, only detectable at low ionic strength (0.01 M). Sorption of Cu to the solid phase separated by centrifugation was strongly affected by the presence of fulvic acid. Below pH 6, sorption of Cu to the solid phase increased by up to 40% compared with the pure hematite. Above pH 6, the presence of fulvic acid resulted in a decrease in Cu sorption due to increasing concentrations of dissolved metal-organic complexes. At low ionic strength (0.01 M), the effects of fulvic acid on Cu sorption to the solid phase were more pronounced than at higher ionic strength (0.1 M). Comparison of the experimental data with model calculations shows that Cu sorption in ternary hematite-fulvic acid systems is systematically underestimated by up to 30% using the linear additivity assumption. Therefore, specific interactions between organic matter and trace metal cations at mineral surfaces must be taken into account when applying surface complexation models to soils or sediments which contain oxides and natural organic matter.

Techniques to measure sorption and migration between small molecules and packaging. A critical review.

PubMed

Kadam, Ashish A; Karbowiak, Thomas; Voilley, Andrée; Debeaufort, Frédéric

2015-05-01

The mass transfer parameters diffusion and sorption in food and packaging or between them are the key parameters for assessing a food product's shelf-life in reference to consumer safety. This has become of paramount importance owing to the legislations set by the regulated markets. The technical capabilities that can be exploited for analyzing product-package interactions have been growing rapidly. Different techniques categorized according to the state of the diffusant (gas or liquid) in contact with the packaging material are emphasized in this review. Depending on the diffusant and on the analytical question under review, the different ways to study sorption and/or migration are presented and compared. Some examples have been suggested to reach the best possible choice, consisting of a single technique or a combination of different approaches. © 2014 Society of Chemical Industry.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Yves; Merkel, Alexej; Busch, Andreas; Krooß, Bernhard

2013-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Colloquium on High Resolution Molecular Spectroscopy (16th) Held in Universite de Bourgogne, Dijon, France on 6-10 September 1999

DTIC Science & Technology

1999-09-28

part of the talk will be devoted to the high resolution ab- sorption spectroscopy of the vi = 2-6 acetylenic overtone bands of propyned (CH 3-C=C-H...period CATGAS (Calibration Apparatus for Trace GAs Spectra), a transportable laboratory set-up for ab- sorption spectroscopy, was connected to the...the NIR around 1.95- 2.04 nm and 2.26- 2.39 nm, where accurate line parameters of ozone ab- sorption are available by high-resolution Fourier transform

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.

Part V--Sorption of pharmaceuticals and personal care products.

PubMed

Pan, Bo; Ning, Ping; Xing, Baoshan

2009-01-01

Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP-soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)-mineral-water). The complexity of three-phase systems was also discussed. Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical-physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.

Moisture sorption isotherms and glass transition temperature of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) roots at 25°C.

PubMed

Cervenka, L; Kubínová, J; Juszczak, L; Witczak, M

2012-02-01

Sorption isotherms of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) root samples were obtained at 25 °C. Elecampe exhibited hysteresis loop in the range of 0.35-0.90 a(w) , whereas burdock roots showed significant differences between adsorption and desorption isotherms from 0.65 to 0.80 a(w) . Blahovec-Yanniotis was considered to give the best fit over the whole range of a(w) tested. Various parameters describing the properties of sorbed water derived from GAB, Henderson and Blahovec-Yanniotis models have been discussed. Differential scanning calorimetric method was used to measure the glass transition temperature (T (g)) of root samples in relation to water activity. The safe moisture content was determined in 12.01 and 14.96 g/100 g d. b. for burdock and elecampe root samples at 25 °C, respectively. Combining the T (g) line with sorption isotherm in one plot, it was found that the glass transition temperature concept overestimated the temperature stability for both root samples.

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.

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.

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.

Competitive sorption of persistent organic pollutants onto microplastics in the marine environment.

PubMed

Bakir, Adil; Rowland, Steven J; Thompson, Richard C

2012-12-01

Plastics are known to sorb persistent organic pollutants from seawater. However, studies to quantify sorption rates have only considered the affinity of chemicals in isolation, unlike the conditions in the environment where contaminants are present as complex mixtures. Here we examine whether phenanthrene and 4,4'-DDT, in a mixture, compete for sorption sites onto PVC with no added additives (unplasticised PVC or uPVC) and Ultra-High Molecular Weight polyethylene. Interactions were investigated by exposing particles of uPVC and UHMW PE to mixtures of 3H and 14C radiolabelled Phe and DDT. Changes in sorption capacity were modelled by applying a Freundlich binding sorption isotherms. An Extended Langmuir Model and an Interaction Factor Model were also applied to predict equilibrium concentrations of pollutants onto plastic. This study showed that in a bi-solute system, DDT exhibited no significantly different sorption behaviour than in single solute systems. However, DDT did appear to interfere with the sorption of Phe onto plastic, indicating an antagonistic effect. Copyright © 2012 Elsevier Ltd. All rights reserved.

Material Selection Guide Derived from Material - Chemical Compatibility Database: Feasibility Based on Database and Predictive Model Evaluation

DTIC Science & Technology

1992-09-01

PI) 297 S S S S 15 Polyamideimide (PAI) 297 S S S S 14 Polyamide 6:6 (PA 6:6) 297 S S S S 35 Perfluoroakloxyethylene ( PFA ) 297 S S S S 42 Phenol...Procedures for the Measurement of Vapor Sorption Followed by Desorption and Comparisons with Polymer Cohesion Parameter and Polymer Coil Expansion Values

Water binding in legume seeds

NASA Technical Reports Server (NTRS)

Vertucci, C. W.; Leopold, A. C.

1987-01-01

The physical status of water in seeds has a pivotal role in determining the physiological reactions that can take place in the dry state. Using water sorption isotherms from cotyledon and axis tissue of five leguminous seeds, the strength of water binding and the numbers of binding sites have been estimated using van't Hoff analyses and the D'Arcy/Watt equation. These parameters of water sorption are calculated for each of the three regions of water binding and for a range of temperatures. Water sorption characteristics are reflective of the chemical composition of the biological materials as well as the temperature at which hydration takes place. Changes in the sorption characteristics with temperature and hydration level may suggest hydration-induced structural changes in cellular components.

Regularities of the sorption of 1,2,3,4-tetrahydroquinoline derivatives under conditions of reversed phase HPLC

NASA Astrophysics Data System (ADS)

Nekrasova, N. A.; Kurbatova, S. V.; Zemtsova, M. N.

2016-12-01

Regularities of the sorption of 1,2,3,4-tetrahydroquinoline derivatives on octadecylsilyl silica gel and porous graphitic carbon from aqueous acetonitrile solutions were investigated. The effect the molecular structure and physicochemical parameters of the sorbates have on their retention characteristics under conditions of reversed phase HPLC are analyzed.

IN SITU BIOREMEDIATION OF TRICHLOROETHYLENE USING BURKHOLDERIA CEPACIA G4 PR1: ANALYSIS OF TRANSPORT PARAMETERS FOR RISK ASSESSMENT (RESEARCH BRIEF)

EPA Science Inventory

Transport of bacteria through geologic media may be viewed as being governed by sorption-desorption reactions. In this investigation, four facets of the process were examined: (I) the impact of sorption on bacterial transport under typical ground water flow velocities and a diffe...

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.

Usefulness of Mehlich-3 test in the monitoring of phosphorus dispersion from Polish arable soils.

PubMed

Szara, Ewa; Sosulski, Tomasz; Szymańska, Magdalena; Szyszkowska, Katarzyna

2018-04-19

A considerable area of soils with low abundance of plant-available phosphorus and relatively low consumption of phosphorus fertilisers recorded in Poland over the last 20-25 years suggests that the dispersion of phosphates from arable soils in Poland can be low. The literature, however, provides reports on a considerable share of Polish agriculture in phosphorus pollution of Baltic Sea waters. The literature provides no data concerning phosphorus sorption parameters of arable soils in Poland. Due to this, the study involved the analysis of sorption properties: 1-point phosphorus sorption index (PSI) and degree of phosphorus saturation, based on molar ratio P, Al, and Fe determined by the Mehlich-3 method (DPS-1 M3  = P / (Al + Fe) and DPS-2 M3  = P / Al), 59 soils representing the main types of texture of soils in Poland, characterised by variable content of plant-available phosphorus by Egner-Riehm DL, organic carbon, and soil pH. The obtained results suggest that the soil texture has a lower effect on sorption properties (PSI) than the degree of acidification. Sorption parameters of soils increased with soil acidification as a result of an increase in the content of Al and Fe extracted by the Mehlich-3 extract in strongly acidified soils. An important finding of our study was evidencing that within the same class of abundance in plant-available phosphorus, the soils varied in the degree of phosphorus saturation and content of active phosphorus. This suggests the possibility of losses of phosphorus even from soils with low abundance of the component provided they are characterised by a high value of parameters DPS-1 M3 and DPS-2 M3 .

Experimental assessment of the spatial variability of porosity, permeability and sorption isotherms in an ordinary building concrete

NASA Astrophysics Data System (ADS)

Issaadi, N.; Hamami, A. A.; Belarbi, R.; Aït-Mokhtar, A.

2017-10-01

In this paper, spatial variabilities of some transfer and storage properties of a concrete wall were assessed. The studied parameters deal with water porosity, water vapor permeability, intrinsic permeability and water vapor sorption isotherms. For this purpose, a concrete wall was built in the laboratory and specimens were periodically taken and tested. The obtained results allow highlighting a statistical estimation of the mean value, the standard deviation and the spatial correlation length of the studied fields for each parameter. These results were discussed and a statistical analysis was performed in order to assess for each of these parameters the appropriate probability density function.

[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.

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.

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

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 estimation of K d values for more structurally complex organic cations to homoionic montmorillonites and to heteroionic soils (mean absolute error of 0.27 log unit). Accordingly, we concluded that the use of phenyltrimethylammonium as a probe compound was a promising means to account for the identity, affinity, and abundance of natural exchange ions in the prediction of organic cation sorption coefficients for environmental solids.

Enhancement of soil retention for phenanthrene in binary cationic gemini and nonionic surfactant mixtures: characterizing two-step adsorption and partition processes through experimental and modeling approaches.

PubMed

Zhao, Shan; Huang, Gordon; An, Chunjiang; Wei, Jia; Yao, Yao

2015-04-09

The enhancement of soil retention for phenanthrene (PHE) through the addition of a binary mixture of cationic gemini (12-2-12) and nonionic surfactants (C12E10) was investigated. The maximum apparent sorption coefficient Kd(*) reached 4247.8 mL/g through the addition of mixed 12-2-12 gemini and C12E10 surfactants, which was markedly higher than the summed individual results in the presence of individual 12-2-12 gemini (1148.6 mL/g) or C12E10 (210.0 mL/g) surfactant. However, the sorption of 12-2-12 gemini was inhibited by the increasing C12E10 dose; and a higher initial 12-2-12 gemini dose showed a higher "desorption" rate. The present study also addressed the sorption behavior of the single 12-2-12 gemini surfactant at the soil/aqueous interface. The sorption isotherm was divided into two steps to elucidate the sorption process; and the sorption schematics were proposed to elaborate the growth of surfactant aggregates corresponding to the various steps of the sorption isotherm. Finally, a two-step adsorption and partition model (TAPM) was developed to simulate the sorption process. Analysis of the equilibrium data indicated that the sorption isotherms of 12-2-12 gemini fitted the TAPM model better. Thermodynamic calculations confirmed that the 12-2-12 gemini sorption at the soil/aqueous interface was spontaneous and exothermic from 288 to 308K. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Acoustic emission and sorptive deformation induced in coals of various rank by the sorption-desorption of gas

NASA Astrophysics Data System (ADS)

Majewska, Zofia; Ziętek, Jerzy

2007-09-01

Simultaneous measurements of acoustic emission (AE) and expansion/contraction of coal samples subjected to gas sorption-desorption processes were conducted on high-and medium-rank coal. The aim of this study was to examine the influence of the coal rank and type of sorbate on measured AE and strain characteristics. The experimental equipment employed in this study consisted of a pressure vessel and associated pressurisation and monitoring units. The arrangement of pressure-vacuum valves permitted the coal sample to be pressurised and depressurised. Carbon-dioxide and methane were used as sorbats. Acoustic emission and strains were recorded continuously for a period of 50 hours during sorption and for at least 12 hours during the desorption process. Tests were conducted on cylindrical coal samples at 298 K. The experimental data were presented as plots of AE basic parameters versus time and in strain diagrams. These studies lead to the following conclusions: 1. There are significant differences in AE and strain characteristics for the two systems (coal-CO2 and coal-CH4); 2. There is a direct influence of rank and type of coal on its behaviour during the sorption-desorption of gas. An attempt has been made to interpret the results obtained on the grounds of the copolymer model of coal structure. More research is needed into this topic in order to get a quantitative description of the observed facts.

Desorption isotherms and isosteric heat of desorption of previously frozen raw pork meat.

PubMed

Clemente, G; Bon, J; Benedito, J; Mulet, A

2009-08-01

Some meat products involve drying previously frozen pork meat, which makes the knowledge of sorption characteristics very important for the design and management of meat dehydration processes. The sorption isotherms of raw pork meat from the Biceps femoris and Semimembranosus muscles were determined at four temperatures: 25, 30, 35 and 40°C. The experimental results were modelled using the GAB (Guggenheim, Anderson and De Boer) model. The effect of temperature was also taken into account to model the experimental sorption isotherms using four models (GAB, Oswin, Halsey and Henderson). The best results were provided by the GAB model. From the experimental sorption isotherms the isosteric heats of sorption were determined. For a moisture content higher than 0.15kgwater/kgdm, the isosteric heat of meat was similar to the latent heat of vaporization for pure water. For a lower moisture content, an increase in the isosteric heat was observed when the moisture content decreased.

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.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, Larry B.; Thurman, E. Michael; Runnells, Donald D.

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

On the biosorption, by brown seaweed, Lobophora variegata, of Ni(II) from aqueous solutions: equilibrium and thermodynamic studies.

PubMed

Basha, Shaik; Jaiswar, Santlal; Jha, Bhavanath

2010-09-01

The biosorption equilibrium isotherms of Ni(II) onto marine brown algae Lobophora variegata, which was chemically-modified by CaCl(2) were studied and modeled. To predict the biosorption isotherms and to determine the characteristic parameters for process design, twenty-three one-, two-, three-, four- and five-parameter isotherm models were applied to experimental data. The interaction among biosorbed molecules is attractive and biosorption is carried out on energetically different sites and is an endothermic process. The five-parameter Fritz-Schluender model gives the most accurate fit with high regression coefficient, R (2) (0.9911-0.9975) and F-ratio (118.03-179.96), and low standard error, SE (0.0902-0.0.1556) and the residual or sum of square error, SSE (0.0012-0.1789) values to all experimental data in comparison to other models. The biosorption isotherm models fitted the experimental data in the order: Fritz-Schluender (five-parameter) > Freundlich (two-parameter) > Langmuir (two-parameter) > Khan (three-parameter) > Fritz-Schluender (four-parameter). The thermodynamic parameters such as DeltaG (0), DeltaH (0) and DeltaS (0) have been determined, which indicates the sorption of Ni(II) onto L. variegata was spontaneous and endothermic in nature.

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

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

Khan, M.A.; Khan, S.A.

Sorption studies of cesium, strontium, and cobalt (Cs, Sr, and Co) on bentonite under various experimental conditions, such as contact time, pH, sorbent and sorbate concentration, and temperature, have been performed. The sorption data for all these metals have been interpreted in terms of Freundlich, Langmuir, and Dubinin-Radushkevich equations. Thermodynamics parameters, such as heat of sorption {Delta}H{degrees}, free energy change {Delta}G{degrees}, and entropy change {Delta}S{degrees}, for the sorption of these metals on bentonite have been calculated. The value of {Delta}H{degrees} shows that the sorption of Cs was exothermic, while the sorption of Sr and Co on bentonite were endothermic inmore » nature. The value of {Delta}G{degrees} for their sorption was negative, showing the spontaneity of the process. The maximum loading capacity of Cs, Sr, and Co were 75.5, 22, and 27.5 meq, respectively, for 100 g of bentonite. The mean free energy E of Cs, Sr, and Co sorption on bentonite was 14.5, 9, and 7.7 kJ/mol, respectively. The value of E indicates that ion exchange may be the predominant mode of sorption for these radionuclides. The desorption studies with 0.01 M CaCl{sub 2} and groundwater at low-metal loading on bentonite showed that about 95% of Cs, 85-90% of Sr, and 97% of Co were irreversibly sorbed. Bentonite could be effectively used for the decontamination of wastewater effluent containing low concentrations of radioactive nuclides of Cs, Sr, and Co. 16 refs., 7 figs., 3 tabs.« less

Modeling the Effect of Nonlinear and Rate-Limited Sorption on the Natural Attenuation of Chlorinated Ethenes

DTIC Science & Technology

2000-03-01

toxicity. Determine what parameters lead to minimized risk to human health. 64 6.0 Bibliography Atlas , R.M. and R. Bartha . Microbial Ecology ...single-celled organisms ( Atlas and Bartha , 1993). Biodegradation - Process where bacteria mineralize or transform contaminants using organic...NRC, 1994) Methanogenesis - The process of creating methane from H2 and CO2 during the respiration of methanogens ( Atlas and Bartha , 1993

Sorption of carbamazepine from water by magnetic molecularly imprinted polymers based on chitosan-Fe₃O₄.

PubMed

Zhang, Ya-Lei; Zhang, Juan; Dai, Chao-Meng; Zhou, Xue-Fei; Liu, Shu-Guang

2013-09-12

A novel magnetic-molecularly imprinted polymer (MMIP) based on chitosan-Fe₃O₄ has been synthesized for fast separation of carbamazepine (CBZ) from water. During polymerization, the modified chitosan-Fe₃O₄ was used not only as supporter but also as functional monomer. The properties of obtained MMIP were characterized by scanning electron and transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectra, thermo-gravimetric analysis and so on. The sorption equilibrium data was well described by Freundlich isotherm model and the increase in the temperature generated an increase in the sorption amount, indicating endothermic nature of adsorption process. Sorption kinetics followed the pseudo-second-order model. The feasibility of selective sorption of CBZ from real water by the MMIP was analyzed by using spiked real water samples. The result showed that the sorption capacity of MMIP has no obvious decrease in different water samples whereas there was obvious decline in the sorption amount of the MNIP. Copyright © 2013 Elsevier Ltd. All rights reserved.

A nonequilibrium model for reactive contaminant transport through fractured porous media: Model development and semianalytical solution

NASA Astrophysics Data System (ADS)

Joshi, Nitin; Ojha, C. S. P.; Sharma, P. K.

2012-10-01

In this study a conceptual model that accounts for the effects of nonequilibrium contaminant transport in a fractured porous media is developed. Present model accounts for both physical and sorption nonequilibrium. Analytical solution was developed using the Laplace transform technique, which was then numerically inverted to obtain solute concentration in the fracture matrix system. The semianalytical solution developed here can incorporate both semi-infinite and finite fracture matrix extent. In addition, the model can account for flexible boundary conditions and nonzero initial condition in the fracture matrix system. The present semianalytical solution was validated against the existing analytical solutions for the fracture matrix system. In order to differentiate between various sorption/transport mechanism different cases of sorption and mass transfer were analyzed by comparing the breakthrough curves and temporal moments. It was found that significant differences in the signature of sorption and mass transfer exists. Applicability of the developed model was evaluated by simulating the published experimental data of Calcium and Strontium transport in a single fracture. The present model simulated the experimental data reasonably well in comparison to the model based on equilibrium sorption assumption in fracture matrix system, and multi rate mass transfer model.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Y.; Merkel, A.; Busch, A.; Krooss, B. M.

2012-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • N2, CH4, CO2 displacement experiments and the volumetric response of the coal on the present gas type (sorbing or inert) in the pore system • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Equilibrium and Kinetic Studies of Cd2+ Biosorption by the Brown Algae Sargassum fusiforme

PubMed Central

Zou, Hui-Xi; Li, Nan; Wang, Li-Hua; Yu, Ping; Yan, Xiu-Feng

2014-01-01

A fundamental investigation of the biosorption of Cd2+ from aqueous solution by the edible seaweed Sargassum fusiforme was performed under batch conditions. The influences of experimental parameters, such as the initial pH, sorption time, temperature, and initial Cd2+ concentration, on Cd2+ uptake by S. fusiforme were evaluated. The results indicated that the biosorption of Cd2+ depended on the initial Cd2+ concentration, as well as the pH. The uptake of Cd2+ could be described by the Langmuir isotherm model, and both the Langmuir biosorption equilibrium constant and the maximum biosorption capacity of the monolayer decreased with increasing temperature, thereby confirming the exothermic character of the sorption process. The biosorption kinetics follows the pseudo-second-order kinetic model, and intraparticle diffusion is the sole rate-limiting step for the entire biosorption period. These fundamental equilibrium and kinetic results can support further studies to the removal of cadmium from S. fusiforme harvested from cadmium-polluted waters. PMID:24736449

Effect of biochar particle size on hydrophobic organic compound sorption kinetics: Applicability of using representative size.

PubMed

Kang, Seju; Jung, Jihyeun; Choe, Jong Kwon; Ok, Yong Sik; Choi, Yongju

2018-04-01

Particle size of biochar may strongly affect the kinetics of hydrophobic organic compound (HOC) sorption. However, challenges exist in characterizing the effect of biochar particle size on the sorption kinetics because of the wide size range of biochar. The present study suggests a novel method to determine a representative value that can be used to show the dependence of HOC sorption kinetics to biochar particle size on the basis of an intra-particle diffusion model. Biochars derived from three different feedstocks are ground and sieved to obtain three daughter products each having different size distributions. Phenanthrene sorption kinetics to the biochars are well described by the intra-particle diffusion model with significantly greater sorption rates observed for finer grained biochars. The time to reach 95% of equilibrium for phenanthrene sorption to biochar is reduced from 4.6-17.9days for the original biochars to <1-4.6days for the powdered biochars with <125μm in size. A moderate linear correlation is found between the inverse square of the representative biochar particle radius obtained using particle size distribution analysis and the apparent phenanthrene sorption rates determined by the sorption kinetics experiments and normalized to account for the variation of the sorption rate-determining factors other than the biochar particle radius. The results suggest that the representative biochar particle radius reasonably describes the dependence of HOC sorption rates on biochar particle size. Copyright © 2017 Elsevier B.V. All rights reserved.

Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites.

PubMed

Jain, Shailesh K; Shakil, Najam A; Dutta, Anirban; Kumar, Jitendra; Saini, Mukesh K

2017-05-04

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31-22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94-83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K f .1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g -1 ) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).

Microbial Reduction of Fe(III) and U(VI) in Aquifers: Simulations Exploring Coupled Effects of Heterogeneity and Fe(II) Sorption

NASA Astrophysics Data System (ADS)

Scheibe, T. D.; Fang, Y.; Roden, E. E.; Brooks, S. C.; Chien, Y.; Murray, C. J.

2004-05-01

Uranium is a significant groundwater contaminant at many former mining and processing sites. In its oxidized state, U(VI) is soluble and mobile, although strongly retarded by sorption to natural iron oxide surfaces. It has been demonstrated that commonly occurring subsurface microorganisms can reduce uranium and other metals when provided sufficient carbon as an electron donor. Reduced U(IV) precipitates as a solid phase; therefore biostimulation provides a potential strategy for in situ removal from contaminated groundwater. However, these biogeochemical reactions occur in the context of a complex heterogeneous environment in which flow and transport dynamics and abiotic reactions can have significant impacts. We have constructed a high-resolution numerical model of groundwater flow and multicomponent reactive transport that incorporates heterogeneity in hydraulic conductivity and initial Fe(III) distribution, microbial growth and transport dynamics, and effects of sorption or precipitation of biogenic Fe(II) on availability of Fe(III) as an electron acceptor. The biogeochemical reaction models and their parameters are based on laboratory experiments; the heterogeneous field-scale property distributions are based on interpretations of geophysical and other observations at a highly characterized field site. The model is being run in Monte Carlo mode to examine the controls that these factors exert on 1) the initial distribution of sorbed uranium in an oxic environment and 2) the reduction and immobilization of uranium upon introduction of a soluble electron donor.

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study.

PubMed

Yu, Qiang; Zhang, Ruiqi; Deng, Shubo; Huang, Jun; Yu, Gang

2009-03-01

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168h to achieve the equilibrium, much longer than 4h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04mmolg(-1) for PFOS and 2.92mmolg(-1) for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.

Removal of Organophosphorus Pesticides from Aqueous Solution by Magnetic Fe3O4/Red Mud-Nanoparticles.

PubMed

Aydin, Senar

2016-12-01

  The aim of this study was to investigate the usability of magnetic Fe3O4/red mud nanoparticles (NPs) for the removal of organophosphorus pesticides from water samples. The effect of various experimental parameters such as red mud amount in Fe3O4/red mud-NPs, pH, contact time, initial pesticide concentrations and adsorbent dose was studied in order to find the optimum conditions for their removal in a batch process. The Fe3O4/red mud-NPs were characterized by using TGA, SEM, XRD, VSM, and determination of the BET surface area. After the regenerated Fe3O4/red mud-NPs were used three times, the sorption capacity and the magnetic separability were observed to be unaffected. Freundlich model described the sorption process better than Langmuir isotherm and the pseudo second-order kinetic model was determined as the best-fit model. The film diffusion mechanism was found to be a main rate control mechanism. The Fe3O4/red mud-NPs satisfactorily removed the OPPS from real water samples.

Novel kinetic model of the removal of divalent heavy metal ions from aqueous solutions by natural clinoptilolite.

PubMed

Jovanovic, Mina; Rajic, Nevenka; Obradovic, Bojana

2012-09-30

Removal of heavy metal ions from aqueous solutions using zeolites is widely described by pseudo-second order kinetics although this model may not be valid under all conditions. In this work, we have extended approaches used for derivation of this model in order to develop a novel kinetic model that is related to the ion exchange mechanism underlying sorption of metal ions in zeolites. The novel model assumed two reversible steps, i.e. release of sodium ions from the zeolite lattice followed by bonding of the metal ion. The model was applied to experimental results of Cu(II) sorption by natural clinoptilolite-rich zeolitic tuff at different initial concentrations and temperatures and then validated by predictions of ion exchange kinetics of other divalent heavy metal ions (i.e. Mn(II), Zn(II) and Pb(II)). Model predictions were in excellent agreements with experimental data for all investigated systems. In regard to the proposed mechanism, modeling results implied that the sodium ion release rate was constant for all investigated metals while the overall rate was mainly determined by the rate of heavy metal ion bonding to the lattice. In addition, prediction capabilities of the novel model were demonstrated requiring one experimentally determined parameter, only. Copyright © 2012 Elsevier B.V. All rights reserved.

Sorption of Cu and Pb to kaolinite-fulvic acid colloids: Assessment of sorbent interactions

NASA Astrophysics Data System (ADS)

Heidmann, Ilona; Christl, Iso; Kretzschmar, Ruben

2005-04-01

The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L -1 kaolinite and 0.03 g L -1 fulvic acid in 0.01 M NaNO 3 were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu 2+ and Pb 2+ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu 2+ ion activity (10 -12 to 10 -5). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms.

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...

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.

Mesoporous silicas with covalently immobilized β-cyclodextrin moieties: synthesis, structure, and sorption properties

NASA Astrophysics Data System (ADS)

Roik, Nadiia V.; Belyakova, Lyudmila A.; Trofymchuk, Iryna M.; Dziazko, Marina O.; Oranska, Olena I.

2017-09-01

Mesoporous silicas with chemically attached macrocyclic moieties were successfully prepared by sol-gel condensation of tetraethyl orthosilicate and β-cyclodextrin-silane in the presence of a structure-directing agent. Introduction of β-cyclodextrin groups into the silica framework was confirmed by the results of IR spectral, thermogravimetric, and quantitative chemical analysis of surface compounds. The porous structure of the obtained materials was characterized by nitrogen adsorption-desorption measurements, powder X-ray diffraction, transmission electron microscopy, and dynamic light scattering. It was found that the composition of the reaction mixture used in β-cyclodextrin-silane synthesis significantly affects the structural parameters of the resulting silicas. The increase in (3-aminopropyl)triethoxysilane as well as the coupling agent content in relation to β-cyclodextrin leads ultimately to the lowering or complete loss of hexagonal arrangement of pore channels in the synthesized materials. Formation of hexagonally ordered mesoporous structure was observed at molar composition of the mixture 0.049 TEOS:0.001 β-CD-silane:0.007 CTMAB:0.27 NH4OH:7.2 H2O and equimolar ratio of components in β-CD-silane synthesis. The sorption of alizarin yellow on starting silica and synthesized materials with chemically attached β-cyclodextrin moieties was studied in phosphate buffer solutions with pH 7.0. Experimental results of the dye equilibrium sorption were analyzed using Langmuir, Freundlich, and Redlich-Peterson isotherm models. It was proved that the Redlich-Peterson isotherm model is the most appropriate for fitting the equilibrium sorption of alizarin yellow on parent silica with hexagonally arranged mesoporous structure as well as on modified one with chemically immobilized β-cyclodextrin groups. [Figure not available: see fulltext.

Assessment of the banana pseudostem as a low-cost biosorbent for the removal of reactive blue 5G dye.

PubMed

Módenes, Aparecido N; Espinoza-Quiñones, Fernando R; Geraldi, Claudinéia A Q; Manenti, Diego R; Trigueros, Daniela E G; Oliveira, Ana Paula de; Borba, Carlos E; Kroumov, Alexander D

2015-01-01

In this work, the removal of reactive blue 5G (RB5G) dye using the drying biomass of banana pseudostem (BPS) was investigated. The characterization of BPS particles was performed. Improvement in the RB5G dye removal performance at the following sorption conditions was evidenced: pH 1, 30°C sorption temperature and 40 rpm shaking, regardless of the particle size range. Kinetic RB5G dye sorption data obtained at better conditions fit well in an Elovich model. A combined Langmuir-BET isotherm model provides a good representation of the RB5G dye equilibrium sorption data, which shows the evidence of a physical sorption process on the BPS surface. Based on the results, the removal of RB5G dye molecules by BPS is based on a physical sorption process.

Role of Brine Chemistry and Sorption in Potential Long-Term Storage of Radioactive Waste in Geologic Salt Formations: Experimental Evaluation of Sorption Parameters

NASA Astrophysics Data System (ADS)

Dittrich, T. M.; Emerson, H. P.; Michael, D. P.; Reed, D. T.

2016-12-01

Bedded geologic salt formations have been shown to have many favorable properties for the disposal of radioactive waste (i.e., reducing conditions, fracture healing). Performance assessment (PA) modeling for a 10,000 year period for the Waste Isolation Pilot Plant (WIPP) near Carlsbad, NM have predicted an extremely low risk of radioactive material reaching the surrounding environment after the 100 year period required for creep to seal the waste panels and access shafts. Human intrusion caused by drilling operations for oil and gas exploration is the main pathway of concern for environmental release of radioactive material due to pressurized brine pockets located within the salt formation below the repository. Our work focuses on the long-term capability of salt repositories and the associated geologic media to safely isolate stored radioactive waste from the surrounding environment, even in the event of a human intrusion scenario such as a direct brine release (DBR) due to a drilling operation intersecting a brine pocket. In particular, we are revisiting the degree of conservatism in the estimated sorption partition coefficients (Kds) used in the PA model based on complementary batch and column experimental methods (Dittrich and Reimus, 2016). The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected in the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV). We will present (1) a conceptual overview of Kd use in the PA model, (2) background and evolution of the Kd ranges used, and (3) results from batch and column experiments and model predictions for Kds with WIPP-relevant geologic media. We will also briefly discuss the challenges of upscaling from lab experiments to field scale predictions, the presence of ligands (e.g., acetate, citrate, EDTA), the role of colloids and microbes, and the effect of engineered barrier materials (e.g., MgO) on sorption and transport conditions. References: Dittrich, T.M., Reimus, P.W. 2016. Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance. J Environ Manage 165, 124-132.

Fixed bed sorption of phosphorus from wastewater using iron oxide-based media derived from acid mine drainage

USGS Publications Warehouse

Sibrell, Philip L.; Tucker, T.W.

2012-01-01

Phosphorus (P) releases to the environment have been implicated in the eutrophication of important water bodies worldwide. Current technology for the removal of P from wastewaters consists of treatment with aluminum (Al) or iron (Fe) salts, but is expensive. The neutralization of acid mine drainage (AMD) generates sludge rich in Fe and Al oxides that has hitherto been considered a waste product, but these sludges could serve as an economical adsorption media for the removal of P from wastewaters. Therefore, we have evaluated an AMD-derived media as a sorbent for P in fixed bed sorption systems. The homogenous surface diffusion model (HSDM) was used to analyze fixed bed test data and to determine the value of related sorption parameters. The surface diffusion modulus Ed was found to be a useful predictor of sorption kinetics. Values of Ed < 0.2 were associated with early breakthrough of P, while more desirable S-shaped breakthrough curves resulted when 0.2 < Ed < 0.5. Computer simulations of the fixed bed process with the HSDM confirmed that if Ed was known, the shape of the breakthrough curve could be calculated. The surface diffusion coefficient D s was a critical factor in the calculation of Ed and could be estimated based on the sorption test conditions such as media characteristics, and influent flow rate and concentration. Optimal test results were obtained with a relatively small media particle size (average particle radius 0.028 cm) and resulted in 96 % removal of P from the influent over 46 days of continuous operation. These results indicate that fixed bed sorption of P would be a feasible option for the utilization of AMD residues, thus helping to decrease AMD treatment costs while at the same time ameliorating the impacts of P contamination.

Black carbon inclusive multichemical modeling of PBDE and PCB biomagnification and -transformation in estuarine food webs.

PubMed

Di Paolo, Carolina; Gandhi, Nilima; Bhavsar, Satyendra P; Van den Heuvel-Greve, Martine; Koelmans, Albert A

2010-10-01

Bioavailability and bioaccumulation of polybrominated diphenylethers (PBDEs) are affected by adsorption on black carbon (BC) and metabolism in biota, respectively. Recent studies have addressed these two processes separately, illustrating their importance in assessing contaminant dynamics. In order to properly examine biomagnification of polychlorinated biphenyls (PCBs) and PBDEs in an estuarine food-web, here we set up a black carbon inclusive multichemical model. A dual domain sorption model, which accounted for sorption to organic matter (OM) and black carbon (BC), was used to estimate aqueous phase concentrations from the measured chemical concentrations in suspended solids. We adapted a previously published multichemical model that tracks the movement of a parent compound and its metabolites in each organism and within its food web. First, the model was calibrated for seven PCB congeners assuming negligible metabolism. Subsequently, PBDE biomagnification was modeled, including biotransformation and bioformation of PBDE congeners, keeping the other model parameters the same. The integrated model was capable of predicting trophic magnification factors (TMF) within error limits. PBDE metabolic half-lives ranged 21-415 days and agreed to literature data. The results showed importance of including BC as an adsorbing phase, and biotransformation and bioformation of PBDEs for a proper assessment of their dynamics in aquatic systems.

Sorption of perfluorooctanoic acid, perfluorooctane sulfonate and perfluoroheptanoic acid on granular activated carbon.

PubMed

Zhang, Di; Luo, Qi; Gao, Bin; Chiang, Sheau-Yun Dora; Woodward, David; Huang, Qingguo

2016-02-01

The sorption of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluoroheptanoic acid (PFHpA) on granular activated carbon (GAC) was characterized and compared to explore the underlying mechanisms. Sorption of the three perfluoroalkyl acids (PFAAs) on GAC appeared to be a rapid intra-particle diffusion process, which were well represented by the pseudo-second-order rate model with the sorption rate following the order PFOS > PFOA > PFHpA. Sorption isotherm data were well fitted by the Freundlich model with the sorption capacity (Kf) of PFOS, PFOA and PFHpA being 4.45, 2.42 and 1.66 respectively. This suggests that the hydrophilic head group on PFAAs, i.e. sulfonate vs carboxylic, has a strong influence on their sorption. Comparison between PFOA and PFHpA revealed that hydrophobicity could also play a role in the sorption of PFAAs on GAC when the fluorocarbon chain length is different. Analyses using Attenuated Total Reflection (ATR)-Fourier Transform Infrared (FTIR) spectroscopy suggested possible formation of a negative charge-assisted H-bond between PFAAs and the functionalities on GAC surfaces, including non-aromatic ketones, sulfides, and halogenated hydrocarbons. Copyright © 2015 Elsevier Ltd. All rights reserved.

Bridging the gap between batch and column experiments: A case study of Cs adsorption on granite.

PubMed

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

2009-01-15

Both batch and column methods are conventionally utilized to determine some critical parameters for assessing the transport of contaminants of concern. The validity of using these parameters is somewhat confusing, however, since outputs such as distribution coefficient (Kd) from these two approaches are often discrepant. To bridge this gap, all possible factors that might contribute to this discrepancy were thoroughly investigated in this report by a case study of Cs sorption to crushed granite under various conditions. Our results confirm an important finding that solid/liquid (S/L) ratio is the dominant factor responsible for this discrepancy. As long as the S/L ratio exceeds 0.25, a consistent Kd value can be reached by the two methods. Under these conditions (S/L ratios>0.25), the sorption capacity of the solid is about an order of magnitude less than that in low S/L ratios (<0.25). Although low sorption capacity is observed in the cases of high S/L ratios, the sorption usually takes place preferentially on the most favorable (thermodynamically stable) sorption sites to form a stronger binding. This is verified by our desorption experiments in which a linear isotherm feature is shown either in deionized water or in 1M of ammonium acetate solutions. It may be concluded that batch experiment with an S/L ratio exceeding 0.25 is crucial to obtain convincing Kd values for safety assessment of radioactive waste repository.

The modeling of reactive solute transport with sorption to mobile and immobile sorbents 1. Experimental evidence and model development

NASA Astrophysics Data System (ADS)

Knabner, P.; Totsche, K. U.; Kögel-Knabner, I.

Modeling carrier-influenced transport needs to take into account the reactivity of the carrier itself. This paper presents a mathematical model of reactive solute transport with sorption to mobile and immobile sorbents. The mobile sorbent is also considered to be reactive. To justify the assumptions and generality of our modeling approach, experimental findings are reviewed and analyzed. A transformation of the model in terms of total concentrations of solute and mobile sorbents is presented which simplifies the mathematical formulations. Breakthrough data on dissolved organic carbon are presented to exemplify the need to take into account the reactivity of the mobile sorbent. Data on hexachlorobiphenyl and cadmium are presented to demonstrate carrier-introduced increased mobility, whereas data on anthracene and pyrene are presented to demonstrate carrier-introduced reduced mobility. The experimental conditions leading to the different findings are pointed out. The sorption processes considered in the model are both equilibrium and nonequilibrium processes, allowing for different sorption sites and nonlinear isotherms and rate functions. Effective isotherms, which describe the sorption to the immobile sorbent in the presence of a mobile sorbent and rate functions, are introduced and their properties are discussed.

Production and characterization of carbonized sorbent products optimized for anionic contaminants

NASA Astrophysics Data System (ADS)

Viglasova, Eva; Fristak, Vladimir; Galambos, Michal; Hood-Nowotny, Rebecca; Soja, Gerhard

2017-04-01

Processing conditions, production methods and feedstock characteristics have been shown to affect the final sorption properties of biochar-based sorbents that have been produced in pyrolysis reactors. The content of O-containing carboxyl, phenolic and hydroxyl functional groups on the biochar surfaces plays a crucial role in sorption chemistry of hazardous materials. The sorption process can be affected by the presence of non-carbonized fractions in biochar matter as well. All these characteristics indicate that biochar shows good potential as a new tool in removal and separation technologies of various pollutants from waste water or contaminated soils. The sorption potential of wood-based biochars for cationic forms of heavy metals has been studied intensively and has already led to successful pilot applications in the field. However, anionic compounds (e.g. phosphate, nitrate, sulphate, As-, Cr-compounds) do not sorb well to unmodified biochar and need specific surface modification of biochar. Based on this fact, we try to obtain data about the sorptive separation of anionic forms of various contaminants from model aqueous solutions by different types of biochar-derived sorbents, or mineral-enriched biochar-derived sorbents. An important part of this research is the assesment of the effects of varying process parameters during biomass carbonisation, the role of biomass feedstock and pre-and/or post-treatment of the biochars onto sorption processes. We specify the most appropriate application strategies with biochar for remediation purposes of waste water or contaminated waters with elevated toxic metal concentrations that might compromise the quality of surface waters. The main aim of research is the preparation of modified biochar sorbent, the characterization of its surface and the investigation about new possibilities of modified biochar sorbent applications for sorption of various contaminants, mainly their anionic forms (e.g. phosphates, nitrates, arsenates). Modification of bamboo-based biochar with clay minerals, the preparation of its composites, could increase the surface area of bamboo-based biochar from 3 to 5 times. Other ways of modification e.g. by using FeCl3 ṡ 6H2O caused a significant increase of sorption ability for anionic forms

Polymer/Solvent and Polymer/Polymer Interaction Studies

DTIC Science & Technology

1980-09-01

temperatures up to 450 12 before serious degradation occurs. They have good hydrolytic stability, good solvent resistance, and excellent thermo- oxidative ...Concentration for Sorption in Glassy PVC 5 Temperature Dependence of the Flory-Huggins Interaction Parameters 115 6 Solubility of Dichloromethane in Polysulfone...116 7 Test of Applicability of the Langmuir Equation for Describing Sorption Data 117 8 Temperature Dependence of the Specific Volume of an Amorphous

Water Vapour Effects in Mass Measurement

NASA Astrophysics Data System (ADS)

Khélifa, N.

2008-01-01

Water vapour density inside the mass comparator enclosure is a critical parameter whose fluctuations during mass weighing can lead to errors in the determination of an unknown mass. To monitor them, a method using DFB laser diode in the near infrared has been proposed and tested. Preliminary results of our observation of water vapour sorption and de-sorption processes from the walls and the mass standard are reported.

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

DOE PAGES

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

2017-08-17

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

Determination of 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.

Equilibrium, kinetic and thermodynamic studies of uranium biosorption by calcium alginate beads.

PubMed

Bai, Jing; Fan, Fangli; Wu, Xiaolei; Tian, Wei; Zhao, Liang; Yin, Xiaojie; Fan, Fuyou; Li, Zhan; Tian, Longlong; Wang, Yang; Qin, Zhi; Guo, Junsheng

2013-12-01

Calcium alginate beads are potential biosorbent for radionuclides removal as they contain carboxyl groups. However, until now limited information is available concerning the uptake behavior of uranium by this polymer gel, especially when sorption equilibrium, kinetics and thermodynamics are concerned. In present work, batch experiments were carried out to study the equilibrium, kinetics and thermodynamics of uranium sorption by calcium alginate beads. The effects of initial solution pH, sorbent amount, initial uranium concentration and temperature on uranium sorption were also investigated. The determined optimal conditions were: initial solution pH of 3.0, added sorbent amount of 40 mg, and uranium sorption capacity increased with increasing initial uranium concentration and temperature. Equilibrium data obtained under different temperatures were fitted better with Langmuir model than Freundlich model, uranium sorption was dominated by a monolayer way. The kinetic data can be well depicted by the pseudo-second-order kinetic model. The activation energy derived from Arrhenius equation was 30.0 kJ/mol and the sorption process had a chemical nature. Thermodynamic constants such as ΔH(0), ΔS(0) and ΔG(0) were also evaluated, results of thermodynamic study showed that the sorption process was endothermic and spontaneous. Copyright © 2013 Elsevier Ltd. All rights reserved.

Summary report on the evaluation of a 1977--1985 edited sorption data base for isotherm modeling

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

Polzer, W.L.; Beckman, R.J.; Fuentes, H.R.

1993-09-01

Sorption data bases collected by Los Alamos National Laboratory (LANL) from 1977 to 1985 for the Yucca Mountain Project.(YMP) have been inventoried and fitted with isotherm expressions. Effects of variables (e.g., particle size) on the isotherm were also evaluated. The sorption data are from laboratory batch measurements which were not designed specifically for isotherm modeling. However a limited number of data sets permitted such modeling. The analysis of those isotherm data can aid in the design of future sorption experiments and can provide expressions to be used in radionuclide transport modeling. Over 1200 experimental observations were inventoried for their adequacymore » to be modeled b isotherms and to evaluate the effects of variables on isotherms. About 15% of the observations provided suitable data sets for modeling. The data sets were obtained under conditions that include ambient temperature and two atmospheres, air and CO{sub 2}.« less

Formaldehyde sorption and desorption characteristics of gypsum wallboard

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

Matthews, T.G.; Hawthorne, A.R.; Thompson, C.V.

1987-07-01

The sorption and subsequent desorption of formaldehyde (CH/sub 2/O) vapor from unpainted gypsum wallboard have been investigated in environmental chamber experiments conducted at 23 /sup 0/C, 50% relative humidity, an air exchange to board loading ratio of 0.43 m/h, and CH/sub 2/O concentrations ranging from 0 to 0.50 mg/m/sup 3/. Both CH/sub 2/O sorption and CH/sub 2/O desorption processes are described by a three-parameter, single-exponential model with an exponential lifetime of 2.9 +/- 0.1 days. The storage capacity of gypsum board for CH/sub 2/O vapor results in a time-dependent buffer to changes in CH/sub 2/O vapor concentration surrounding the boardmore » but appears to cause only a weak, permanent loss mechanism for CH/sub 2/O vapor. Prior to significant depletion of sorbed CH/sub 2/O, desorption rates from CH/sub 2/O-exposed gypsum board exhibit a linear dependence with negative slope on CH/sub 2/O vapor concentration. Analogous CH/sub 2/O emissions properties have been observed for pressed-wood products bonded with urea-formaldehyde resins. 17 references, 5 figures.« less

Formaldehyde sorption and desorption characteristics of gypsum wallboard

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

Matthews, T.G.; Hawthorne, A.R.; Thompson, C.V.

1986-01-01

The sorption and subsequent desorption of formaldehyde (CH/sub 2/O) vapor from unpainted gypsum wallboard has been investigated in environmental chamber experiments conducted at 23/sup 0/C, 50% relative humidity, an air exchange to board loading ratio of 0.43 m/h, and CH/sub 2/O concentrations ranging from 0 to 0.50 mg/m/sup 3/. Both CH/sub 2/O sorption and desorption processes are described using a three-parameter, single-exponential model with an exponential lifetime of 2.9 +- 0.1 days. The storage capacity of gypsum board for CH/sub 2/O vapor results in a time-dependent buffer to changes in CH/sub 2/O vapor concentration surrounding the board, but appears tomore » cause only a weak, permanent loss mechanism for CH/sub 2/O vapor. Short-term CH/sub 2/O desorption rates from CH/sub 2/O-exposed gypsum board (prior to significant depletion of sorbed CH/sub 2/O) exhibit a linear dependence with negative slope on CH/sub 2/O vapor concentration analogous to CH/sub 2/O emissions from pressed-wood products bonded with urea-formaldehyde resins.« less

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.

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

PubMed

Valderrama, C; Cortina, J L; Farran, A; Gamisans, X; Lao, C

2007-06-01

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.

Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

PubMed

Hong, Yong Seok; Kinney, Kerry A; Reible, Danny D

2011-03-01

Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase. Copyright © 2010 SETAC.

Remote Sensing of Surface Propagation Parameters: Application of Imagery Simulation Model Results.

DTIC Science & Technology

1982-10-31

total at * 10.6um, while that for water vapor continuum ab- sorption is 75%. While visible radiance data may * xi be useful in predicting visible range...data. In a subsequent study undertaken to investigate the relative wavelength depen- dent effects of atmospheric particulates and water vapor con...humidity dependent variations in non- 2-2 aerosol atmospheric transmission due to molecular absorption by water vapor, and (5) radiative transfer

Sorption, desorption and displacement of ibuprofen, estrone, and 17β estradiol in wastewater irrigated and rainfed agricultural soils.

PubMed

Durán-Álvarez, Juan C; Prado, Blanca; Ferroud, Anouck; Juayerk, Narcedalia; Jiménez-Cisneros, Blanca

2014-03-01

Sorption and leaching potential of ibuprofen, estrone and 17β estradiol were tested in two agricultural soils: one irrigated using municipal wastewater and the other used in rainfed agriculture. Batch sorption-desorption experiments and undisturbed soil column assays were carried out using both soils to which were added a mixture of the target compounds. The three compounds were sorbed to a different extent by both soils: estrone>17β estradiol>ibuprofen. Higher sorption was observed in the irrigated soil, which was attributed to the accumulation of organic matter caused by wastewater irrigation. Desorption of hormones was hysteretic in the irrigated soil, while ibuprofen showed low hysteresis in both soils. Retardation of the compounds' displacement was consistent with the sorption pattern observed in the batch tests. Retardation factor (RF) was similar for the three compounds in the two tested soils, indicating that the target compounds are much more mobile in the soil columns than would be predicted based on their equilibrium sorption parameters. The results obtained in the experiments clarify the role of wastewater irrigated soils as a filter and degradation media for the target micropollutants. Copyright © 2013 Elsevier B.V. All rights reserved.

MOLECULAR DYNAMICS MODELING OF SORPTION OF PESTICIDES ONTO THE SURFACES OF KAOLINITE

EPA Science Inventory

To accurately predict the fate of contaminants in the environment and to make sound decisions about environmental remediation, we must accurately understand sorption mechanisms and surface reactivity of environmental particles. Sorption of selected pesticides on kaolinite surface...

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.

Multivariate functions for predicting the sorption of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-tricyclohexane (RDX) among taxonomically distinct soils.

PubMed

Katseanes, Chelsea K; Chappell, Mark A; Hopkins, Bryan G; Durham, Brian D; Price, Cynthia L; Porter, Beth E; Miller, Lesley F

2016-11-01

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed a new solution for modeling the sorption and persistence of these munition constituents as multivariate mathematical functions correlating soil attribute data over a variety of taxonomically distinct soil types to contaminant behavior, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments measuring the sorption of TNT and RDX on taxonomically different soil types that were extensively physical and chemically characterized. Statistical decomposition of the log-transformed, and auto-scaled soil characterization data using the dimension-reduction technique PCA (principal component analysis) revealed a strong latent structure based in the multiple pairwise correlations among the soil properties. TNT and RDX sorption partitioning coefficients (KD-TNT and KD-RDX) were regressed against this latent structure using partial least squares regression (PLSR), generating a 3-factor, multivariate linear functions. Here, PLSR models predicted KD-TNT and KD-RDX values based on attributes contributing to endogenous alkaline/calcareous and soil fertility criteria, respectively, exhibited among the different soil types: We hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished soil types may provide the means for potentially predicting complex phenomena in soils. The development of predictive multivariate models tuned to a local soil's taxonomic designation would have direct benefit to military range managers seeking to anticipate the environmental risks of training activities on impact sites. Published by Elsevier Ltd.

Sorption Phase of Supercritical CO2 in Silica Aerogel: Experiments and Mesoscale Computer Simulations

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

Rother, Gernot; Vlcek, Lukas; Gruszkiewicz, Miroslaw

2014-01-01

Adsorption of supercritical CO2 in nanoporous silica aerogel was investigated by a combination of experiments and molecular-level computer modeling. High-pressure gravimetric and vibrating tube densimetry techniques were used to measure the mean pore fluid density and excess sorption at 35 C and 50 C and pressures of 0-200 bar. Densification of the pore fluid was observed at bulk fluid densities below 0.7 g/cm3. Far above the bulk fluid density, near-zero sorption or weak depletion effects were measured, while broad excess sorption maxima form in the vicinity of the bulk critical density region. The CO2 sorption properties are very similar formore » two aerogels with different bulk densities of 0.1 g/cm3 and 0.2 g/cm3, respectively. The spatial distribution of the confined supercritical fluid was analyzed in terms of sorption- and bulk-phase densities by means of the Adsorbed Phase Model (APM), which used data from gravimetric sorption and small-angle neutron scattering experiments. To gain more detailed insight into supercritical fluid sorption, large-scale lattice gas GCMC simulations were utilized and tuned to resemble the experimental excess sorption data. The computed three-dimensional pore fluid density distributions show that the observed maximum of the excess sorption near the critical density originates from large density fluctuations pinned to the pore walls. At this maximum, the size of these fluctuations is comparable to the prevailing pore sizes.« less

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface.

PubMed

Ng, Kim Choon; Burhan, Muhammad; Shahzad, Muhammad Wakil; Ismail, Azahar Bin

2017-09-06

The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

Radiation grafting of acrylamide and maleic acid on chitosan and effective application for removal of Co(II) from aqueous solutions

NASA Astrophysics Data System (ADS)

Saleh, Alaaeldine Sh.; Ibrahim, Ahmed G.; Elsharma, Emad M.; Metwally, Essam; Siyam, Tharwat

2018-03-01

The graft copolymerization has been proven as a superior polymerization technique because it combines the functional advantages of the grafted and base polymers. In this work, the radiation-induced grafting of acrylamide (AAm) and maleic acid (MA) onto chitosan (CTS) was developed and optimized by determining the grafting percentage and efficiency as a function of grafting conditions such as AAm, MA, and CTS concentrations, and absorbed dose. Fourier transform infrared spectroscopic analysis (FTIR) confirmed the graft copolymerization. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) further characterized the grafted copolymers and showed their high thermal stability. Using batch sorption experiments and 60Co as a radiotracer, poly(CTS-AAm) and poly(CTS-MA) were evaluated for Co(II) removal from aqueous solutions. The Co(II) removal increases with increasing time, pH, polymer, and Co(II) concentrations. Experimentally, P(CTS-AAm) and P(CTS-MA) show high sorption capacities of Co(II), i.e. 150 mg g-1 and 421 mg g-1, respectively, which makes them potential sorbents of Co(II) for water and wastewater treatment. Finally, the Co(II) sorption was examined using sorption isotherm and kinetic models. The sorption was best fitted to Langmuir model which suggests the sorption is of chemisorption type. On the other hand, the sorption kinetics was best represented by Elovich model which also indicates the chemical nature of Co(II) sorption on P(CTS-AAm) and P(CTS-MA).

Impact of the organic coating on nanoparticles stability and reactivity

NASA Astrophysics Data System (ADS)

Gelabert, A.; Sivry, Y.; Ould Boualy, L.; Roselyne, F.; Juillot, F.; Menguy, N.; Benedetti, M. F.

2010-12-01

The strong increase in the use of engineered nanoparticles (NPs) during the last decade may ultimately result in their release in environmental settings, as predicted for different types of NPs by Gottshalk et al.. Most of these NPs incorporate functionalized coatings to gain industrial benefits, which in turn may play a critical rule for the whole NPs reactivity. Thus, along with stability studies focusing on the fate of NPs in natural systems, an accurate understanding of the coating impacts on the NPs behaviour and reactivity is highly required. This study aims to estimate the impact of three different coatings on the NPs dissolution rates in natural water (Seine river water), and their sorption properties onto a model mineral substrate. In this work, ZnO NPs have been coated, either with triethoxycaprylylsilane (hydrophobic), methacryloxypropyltrimethoxysilane (hydrophilic), or aminopropyltriethoxusilane (cationic). The dissolution rates were determined using two protocols: the Donnan Membrane Technique to measure the remaining free metal concentration in solution, and a 1 kDa ultrafiltration procedure to access both the free metal and small organic complexes part. For all three coating types, a fast dissolution step is reached in less than one day, followed by a slow precipitation of new mineral phases to finally reach a steady state. No major differences in the dissolution rates and profiles have been observed. Sorption studies on synthetic microsized goethite have been conducted at pH 7.5. The sorption ratio has been estimated as a function of initial NPs concentrations (from 10-7 M to 10-3 M), and follows a Langmuir shape for the hydrophobic and hydrophilic coatings at concentrations lower than 2.10-4 M. Interestingly, those two NPs exhibit high sorption capacities (10 times higher) compared to free Zn2+ sorption. On the other hand, at those concentrations, the cationic coating only induces a weak sorption without any defined trend. Moreover, for the hydrophobic-coated NPs at higher concentrations, the isotherm sorption shape shifts from a Langmuir type to a linear increase, thus indicating an important change in the sorption mechanism. To explain these differences in sorption as a function of the coating properties, the NPs aggregation state has been investigated for all three suspensions, and this parameter appears to be one of the major controls for the coated NPs sorbing properties. These physico-chemical aspects of manufactured NPs behaviour in natural systems constitute an essential step with great implications for ecotoxicological studies. Gottshalk F., Sonderer T., Scholz R.W., and Nowack B., Environmental Science and Technology, 2009, 43, 9216-9222

Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

PubMed

Kutzner, Susann; Schaffer, Mario; Licha, Tobias; Worch, Eckhard; Börnick, Hilmar

2016-12-15

The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Biosorptive uptake of arsenic(V) by steam activated carbon from mung bean husk: equilibrium, kinetics, thermodynamics and modeling

NASA Astrophysics Data System (ADS)

Mondal, Sandip; Aikat, Kaustav; Halder, Gopinath

2017-12-01

The present investigation emphasizes on the biosorptive removal of toxic pentavalent arsenic from water using steam activated carbon prepared from mung bean husk (SAC-MBH). Characterization of the synthesized sorbent was done using different instrumental techniques, i.e., SEM, BET and point of zero charge. Sorptive uptake of As(V) over steam activated MBH as a function of pH (3-9), agitation speed (40-200 rpm), dosage (50-1000 mg) and temperature (298-313 K) was studied by batch process at arsenic concentration of 2 mg L-1. Lower pH increases the arsenic removal over the pH range of 3-9. Among three adsorption isotherm models examined, Langmuir model was observed to show superior results over Freundlich model. The mean sorption energy (E) estimated by Dubinin-Radushkevich model suggested that the process of adsorption was chemisorption. Thermodynamic parameters confer that the sorption process was spontaneous, exothermic and feasible in nature. The pseudo-second-order rate kinetics of arsenic gave better correlation coefficients as compared to pseudo-first-order kinetics equation. Three process parameters, viz. adsorbent dosage, agitation speed and pH were opted for optimizing As(V) elimination using central composite design matrix of response surface methodology (RSM). The identical design setup was used for artificial neural network (ANN) for comparing its prediction capability with RSM towards As(V) removal. Maximum arsenic removal was observed to be 98.75% at sorbent dosage 0.75 gm L-1, pH 3.0, agitation speed 160 rpm and temperature 308 K. The study concluded that SAC-MBH could be a competent adsorbent for As(V) removal and ANN model was better in arsenic removal predictability results than RSM model.

Spatial Moment Equations for a Groundwater Plume with Degradation and Rate-Limited Sorption

EPA Science Inventory

In this note, we analytically derive the solution for the spatial moments of groundwater solute concentration distributions simulated by a one-dimensional model that assumes advective-dispersive transport with first-order degradation and rate-limited sorption. Sorption kinetics...

Moisture Sorption Isotherms and Properties of Sorbed Water of Neem ( Azadirichta indica A. Juss) Kernels

NASA Astrophysics Data System (ADS)

Ngono Mbarga, M. C.; Bup Nde, D.; Mohagir, A.; Kapseu, C.; Elambo Nkeng, G.

2017-01-01

A neem tree growing abundantly in India as well as in some regions of Asia and Africa gives fruits whose kernels have about 40-50% oil. This oil has high therapeutic and cosmetic qualities and is recently projected to be an important raw material for the production of biodiesel. Its seed is harvested at high moisture contents, which leads tohigh post-harvest losses. In the paper, the sorption isotherms are determined by the static gravimetric method at 40, 50, and 60°C to establish a database useful in defining drying and storage conditions of neem kernels. Five different equations are validated for modeling the sorption isotherms of neem kernels. The properties of sorbed water, such as the monolayer moisture content, surface area of adsorbent, number of adsorbed monolayers, and the percent of bound water are also defined. The critical moisture content necessary for the safe storage of dried neem kernels is shown to range from 5 to 10% dry basis, which can be obtained at a relative humidity less than 65%. The isosteric heats of sorption at 5% moisture content are 7.40 and 22.5 kJ/kg for the adsorption and desorption processes, respectively. This work is the first, to the best of our knowledge, to give the important parameters necessary for drying and storage of neem kernels, a potential raw material for the production of oil to be used in pharmaceutics, cosmetics, and biodiesel manufacturing.

Surface Complexation Modeling of Eu(III) and U(VI) Interactions with Graphene Oxide.

PubMed

Xie, Yu; Helvenston, Edward M; Shuller-Nickles, Lindsay C; Powell, Brian A

2016-02-16

Graphene oxide (GO) has great potential for actinide removal due to its extremely high sorption capacity, but the mechanism of sorption remains unclear. In this study, the carboxylic functional group and an unexpected sulfonate functional group on GO were characterized as the reactive surface sites and quantified via diffuse layer modeling of the GO acid/base titrations. The presence of sulfonate functional group on GO was confirmed using elemental analysis and X-ray photoelectron spectroscopy. Batch experiments of Eu(III) and U(VI) sorption to GO as the function of pH (1-8) and as the function of analyte concentration (10-100, 000 ppb) at a constant pH ≈ 5 were conducted; the batch sorption results were modeled simultaneously using surface complexation modeling (SCM). The SCM indicated that Eu(III) and U(VI) complexation to carboxylate functional group is the main mechanism for their sorption to GO; their complexation to the sulfonate site occurred at the lower pH range and the complexation of Eu(III) to sulfonate site are more significant than that of U(VI). Eu(III) and U(VI) facilitated GO aggregation was observed with high Eu(III) and U(VI) concentration and may be caused by surface charge neutralization of GO after sorption.

Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

PubMed

Chen, Changlun; Wang, Xiangke

2007-02-01

The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.

Predicting subsurface uranium transport: Mechanistic modeling constrained by experimental data

NASA Astrophysics Data System (ADS)

Ottman, Michael; Schenkeveld, Walter D. C.; Kraemer, Stephan

2017-04-01

Depleted uranium (DU) munitions and their widespread use throughout conflict zones around the world pose a persistent health threat to the inhabitants of those areas long after the conclusion of active combat. However, little emphasis has been put on developing a comprehensive, quantitative tool for use in remediation and hazard avoidance planning in a wide range of environments. In this context, we report experimental data on U interaction with soils and sediments. Here, we strive to improve existing risk assessment modeling paradigms by incorporating a variety of experimental data into a mechanistic U transport model for subsurface environments. 20 different soils and sediments from a variety of environments were chosen to represent a range of geochemical parameters that are relevant to U transport. The parameters included pH, organic matter content, CaCO3, Fe content and speciation, and clay content. pH ranged from 3 to 10, organic matter content from 6 to 120 g kg-1, CaCO3 from 0 to 700 g kg-1, amorphous Fe content from 0.3 to 6 g kg-1 and clay content from 4 to 580 g kg-1. Sorption experiments were then performed, and linear isotherms were constructed. Sorption experiment results show that among separate sets of sediments and soils, there is an inverse correlation between both soil pH and CaCO¬3 concentration relative to U sorptive affinity. The geological materials with the highest and lowest sorptive affinities for U differed in CaCO3 and organic matter concentrations, as well as clay content and pH. In a further step, we are testing if transport behavior in saturated porous media can be predicted based on adsorption isotherms and generic geochemical parameters, and comparing these modeling predictions with the results from column experiments. The comparison of these two data sets will examine if U transport can be effectively predicted from reactive transport modeling that incorporates the generic geochemical parameters. This work will serve to show whether a more mechanistic approach offers an improvement over statistical regression-based risk assessment models.

Quantification of Cation Sorption to Engineered Barrier Materials Under Extreme Conditions

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

Powell, Brian; Schlautman, Mark; Rao, Linfeng

The objective of this research is to examine mechanisms and thermodynamics of actinide sorption to engineered barrier materials (iron (oxyhydr)oxides and bentonite clay) for nuclear waste repositories under high temperature and high ionic strength conditions using a suite of macroscopic and microscopic techniques which will be coupled with interfacial reaction models. Gaining a mechanistic understanding of interfacial processes governing the sorption/sequestration of actinides at mineral-water interfaces is fundamental for the accurate prediction of actinide behavior in waste repositories. Although macroscale sorption data and various spectroscopic techniques have provided valuable information regarding speciation of actinides at solid-water interfaces, significant knowledge gapsmore » still exist with respect to sorption mechanisms and the ability to quantify sorption, particularly at high temperatures and ionic strengths. This objective is addressed through three major tasks: (1) influence of oxidation state on actinide sorption to iron oxides and clay minerals at elevated temperatures and ionic strengths; (2) calorimetric titrations of actinide-mineral suspensions; (3) evaluation of bentonite performance under repository conditions. The results of the work will include a qualitative conceptual model and a quantitative thermodynamic speciation model describing actinide partitioning to minerals and sediments, which is based upon a mechanistic understanding of specific sorption processes as determined from both micro-scale and macroscale experimental techniques. The speciation model will be a thermodynamic aqueous and surface complexation model of actinide interactions with mineral surfaces that is self-consistent with macroscopic batch sorption data, calorimetric and potentiometric titrations, X-ray absorption Spectroscopy (XAS, mainly Extended X-ray Absorption Fine Structure (EXAFS)), and electron microscopy analyses. The novelty of the proposed work lies largely in the unique system conditions which will be examined (i.e. elevated temperature and ionic strength) and the manner in which the surface complexation model will be developed in terms of specific surface species identified using XAS. These experiments will thus provide a fundamental understanding of the chemical and physical processes occurring at the solid-solution interface under expected repository conditions. Additionally, the focus on thermodynamic treatment of actinide ion interactions with minerals as proposed will provide information on the driving forces involved and contribute to the overall understanding of the high affinity many actinide ions have for oxide surfaces. The utility of this model will be demonstrated in this work through a series of advective and diffusive flow experiments.« less

Kinetic and thermodynamic studies of the Co(II) and Ni(II) ions removal from aqueous solutions by Ca-Mg phosphates.

PubMed

Ivanets, A I; Srivastava, V; Kitikova, N V; Shashkova, I L; Sillanpää, M

2017-03-01

The aim of this work was to study the sorption kinetics and thermodynamics of Co(II) and Ni(II) from aqueous solutions by sorbents on the basis of hydrogen (PD-1) and tertiary (PD-2) Ca-Mg phosphates depending on the solution temperature and sorbents chemical composition. Kinetic studies of adsorption of Co(II) and Ni(II) ions onto samples of phosphate sorbents were performed in batch experiment at the temperatures 288, 303, 318 and 333 K. The sorbent dose was fixed at 10 g L -1 , initial pH value 2.6, and contact time varied from 5 to 600 min. The kinetics of Co(II) and Ni(II) adsorption were analyzed by using pseudo-first order, pseudo-second order and intraparticle diffusion models. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for the sorption of Co(II) and Ni(II) were determined using the Gibbs-Helmholtz equation. The calculated kinetic parameters and corresponding correlation coefficients revealed that Co(II) and Ni(II) uptake process followed the pseudo-second order rate expression. Thermodynamic studies confirmed the spontaneous and endothermic nature of removal process which indicate that sorption of Co(II) and Ni(II) ions onto both phosphate sorbents is favoured at higher temperatures and has the chemisorptive mechanism. The data thus obtained would be useful for practical application of the low cost and highly effective Ca-Mg phosphate sorbents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Description of sorbing tracers transport in fractured media using the lattice model approach

NASA Astrophysics Data System (ADS)

Jiménez-Hornero, Francisco J.; Giráldez, Juan V.; Laguna, Ana

2005-12-01

The transport of contaminants in fractured media is a complex phenomenon with a great environmental impact. It has been described with several models, most of them based on complex partial differential equations, that are difficult to apply when equilibrium and nonequilibrium dynamics are considered in complex boundaries. With the aim of overcoming this limitation, a combination of two lattice Bathnagar, Gross and Krook (BGK) models, derived from the lattice Boltzmann model, is proposed in this paper. The fractured medium is assumed to be a single fissure in a porous rock matrix. The proposed approach permits us to deal with two processes with different length scales: advection-dispersion in the fissure and diffusion within the rock matrix. In addition to the mentioned phenomena, sorption reactions are also considered. The combined model has been tested using the experimental breakthrough curves obtained by Garnier et al. (Garnier, J.M., Crampon, N., Préaux, C., Porel, G., Vreulx, M., 1985. Traçage par 13C, 2H, I - et uranine dans la nappe de la craie sénonienne en écoulement radial convergent (Béthune, France). J. Hidrol. 78, 379-392.) giving acceptable results. A study on the influence of the lattice BGK models parameters controlling sorption and matrix diffusion on the breakthrough curves shape is included.

Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

PubMed

Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

2017-09-01

The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

Evaluation of INL Supplied MOOSE/OSPREY Model: Modeling Water Adsorption on Type 3A Molecular Sieve

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

Pompilio, L. M.; DePaoli, D. W.; Spencer, B. B.

The purpose of this study was to evaluate Idaho National Lab’s Multiphysics Object-Oriented Simulation Environment (MOOSE) software in modeling the adsorption of water onto type 3A molecular sieve (3AMS). MOOSE can be thought-of as a computing framework within which applications modeling specific coupled-phenomena can be developed and run. The application titled Off-gas SeParation and REcoverY (OSPREY) has been developed to model gas sorption in packed columns. The sorbate breakthrough curve calculated by MOOSE/OSPREY was compared to results previously obtained in the deep bed hydration tests conducted at Oak Ridge National Laboratory. The coding framework permits selection of various options, whenmore » they exist, for modeling a process. For example, the OSPREY module includes options to model the adsorption equilibrium with a Langmuir model or a generalized statistical thermodynamic adsorption (GSTA) model. The vapor solid equilibria and the operating conditions of the process (e.g., gas phase concentration) are required to calculate the concentration gradient driving the mass transfer between phases. Both the Langmuir and GSTA models were tested in this evaluation. Input variables were either known from experimental conditions, or were available (e.g., density) or were estimated (e.g., thermal conductivity of sorbent) from the literature. Variables were considered independent of time, i.e., rather than having a mass transfer coefficient that varied with time or position in the bed, the parameter was set to remain constant. The calculated results did not coincide with data from laboratory tests. The model accurately estimated the number of bed volumes processed for the given operating parameters, but breakthrough times were not accurately predicted, varying 50% or more from the data. The shape of the breakthrough curves also differed from the experimental data, indicating a much wider sorption band. Model modifications are needed to improve its utility and predictive capability. Recommended improvements include: greater flexibility for input of mass transfer parameters, time-variable gas inlet concentration, direct output of loading and temperature profiles along the bed, and capability to conduct simulations of beds in series.« less

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

NASA Astrophysics Data System (ADS)

Moon, Jung-Won; Goltz, Mark N.; Ahn, Kyu-Hong; Park, Jae-Woo

2003-02-01

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient ( K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.

Mono-component versus binary isotherm models for Cu(II) and Pb(II) sorption from binary metal solution by the green alga Pithophora oedogonia.

PubMed

Kumar, Dhananjay; Singh, Alpana; Gaur, J P

2008-11-01

The sorption of Cu(II) and Pb(II) by Pithophora markedly decreased as the concentration of the secondary metal ion, Cu(II) or Pb(II), increased in the binary metal solution. However, the test alga showed a greater affinity to sorb Cu(II) than Pb(II) from the binary metal solution. Mono-component Freundlich, Langmuir, Redlich-Peterson and Sips isotherms successfully predicted the sorption of Cu(II) and Pb(II) from both single and binary metal solutions. None of the tested binary sorption isotherms could realistically predict Cu(II) and Pb(II) sorption capacity and affinity of the test alga for the binary metal solutions of varying composition, which mono-component isotherms could very well accomplish. Hence, mono-component isotherm modeling at different concentrations of the secondary metal ion seems to be a better option than binary isotherms for metal sorption from binary metal solution.

Removal of phosphate from aqueous solution using magnesium-alginate/chitosan modified biochar microspheres derived from Thalia dealbata.

PubMed

Cui, Xiaoqiang; Dai, Xi; Khan, Kiran Yasmin; Li, Tingqiang; Yang, Xiaoe; He, Zhenli

2016-10-01

The objective of this study was to determine the feasibility of using magnesium-alginate/chitosan modified biochar microspheres to enhance removal of phosphate from aqueous solution. The introduction of MgCl2 substantially increased surface area of biochar (116.2m(2)g(-1)), and both granulation with alginate/chitosan and modification with magnesium improved phosphate sorption on the biochars. Phosphate sorption on the biochars could be well described by a simple Langmuir model, and the MgCl2-alginate modified biochar microspheres exhibited the highest phosphate sorption capacity (up to 46.56mgg(-1)). The pseudo second order kinetic model better fitted the kinetic data, and both the Yoon-Nelson and Thomas models were superior to other models in describing phosphate dynamic sorption. Precipitation with minerals and ligand exchange were the possible mechanisms of phosphate sorption on the modified biochars. These results imply that MgCl2-alginate modified biochar microspheres have potential as a green cost-effective sorbent for remediating P contaminated water environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interfacial Mechanisms of Water Vapor Sorption into Cellulose Nanofibril Films as Revealed by Quantitative Models.

PubMed

Hakalahti, Minna; Faustini, Marco; Boissière, Cédric; Kontturi, Eero; Tammelin, Tekla

2017-09-11

Humidity is an efficient instrument for facilitating changes in local architectures of two-dimensional surfaces assembled from nanoscaled biomaterials. Here, complementary surface-sensitive methods are used to collect explicit and precise experimental evidence on the water vapor sorption into (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidized cellulose nanofibril (CNF) thin film over the relative humidity (RH) range from 0 to 97%. Changes in thickness and mass of the film due to water vapor uptake are tracked using spectroscopic ellipsometry and quartz crystal microbalance with dissipation monitoring, respectively. Experimental data is evaluated by the quantitative Langmuir/Flory-Huggins/clustering model and the Brunauer-Emmett-Teller model. The isotherms coupled with the quantitative models unveil distinct regions of predominant sorption modes: specific sorption of water molecules below 10% RH, multilayer build-up between 10 to 75% RH, and clustering of water molecules above 75% RH. The study reveals the sorption mechanisms underlying the well-known water uptake behavior of TEMPO oxidized CNF directly at the gas-solid interface.

Sorption of vanadium (V) onto natural soil colloids under various solution pH and ionic strength conditions.

PubMed

Luo, Xiuhua; Yu, Lin; Wang, Changzhao; Yin, Xianqiang; Mosa, Ahmed; Lv, Jialong; Sun, Huimin

2017-02-01

Batch sorption kinetics and isothermal characteristics of V(V) were investigated on three natural soil colloids (manual loessial soil colloid (MSC), aeolian sandy soil colloid (ASC), and cultivated loessial soil colloid (CSC)) under various solution pH and ionic strength (IS) conditions. Colloids were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). AFM micrographs showed CSC with an aggregated shape with larger particle diameter as compared with ASC and MSC. XRD spectra revealed the presence of different minerals in natural soil colloids including biotite, kaolinite, calcite and quartz, which might contribute to sorption process. The sorption ability decreased with increase of colloidal particle size. The sorption was mainly attributed to complexation by active carboxylate and alcohol groups of colloidal components. Sorption kinetics and isotherms of V(V) onto natural soil colloids were best fitted with Pseudo-second-order and Freundlich models. Langmuir model indicated that sorption capacity of MSC and ASC was comparable (285.7 and 238.1 mg g -1 ); however, CSC exhibited the lowest sorption capacity (41.5 mg g -1 ) due to its larger particle diameter and aggregated shape. The maximum V(V) sorption capacity reached plateau values at a solution pH ranged between 5.0 and 9.0 for MSC and ASC, and 6.0-8.0 for CSC. Sorption capacity of V(V) onto natural soil colloids decreased with increasing IS. Based on result of this study we can conclude that sorption of V(V) onto natural soil colloids is pH- and IS-dependent. These findings provide insights on the remediation of vanadium-contaminated soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

A breakthrough biosorbent in removing heavy metals: Equilibrium, kinetic, thermodynamic and mechanism analyses in a lab-scale study.

PubMed

Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Lu, Shaoyong; Chen, Shiao-Shing; Nguyen, Nguyen Cong; Zhang, Xinbo; Wang, Jie; Wu, Yun

2016-01-15

A breakthrough biosorbent namely multi-metal binding biosorbent (MMBB) made from a combination of tea wastes, maple leaves and mandarin peels, was prepared to evaluate their biosorptive potential for removal of Cd(II), Cu(II), Pb(II) and Zn(II) from multi-metal aqueous solutions. FTIR and SEM were conducted, before and after biosorption, to explore the intensity and position of the available functional groups and changes in adsorbent surface morphology. Carboxylic, hydroxyl and amine groups were found to be the principal functional groups for the sorption of metals. MMBB exhibited best performance at pH 5.5 with maximum sorption capacities of 31.73, 41.06, 76.25 and 26.63 mg/g for Cd(II), Cu(II), Pb(II) and Zn(II), respectively. Pseudo-first and pseudo-second-order models represented the kinetic experimental data in different initial metal concentrations very well. Among two-parameter adsorption isotherm models, the Langmuir equation gave a better fit of the equilibrium data. For Cu(II) and Zn(II), the Khan isotherm describes better biosorption conditions while for Cd(II) and Pb(II), the Sips model was found to provide the best correlation of the biosorption equilibrium data. The calculated thermodynamic parameters indicated feasible, spontaneous and exothermic biosorption process. Overall, this novel MMBB can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Extended sorption partitioning models for pesticide leaching risk assessments: Can we improve upon the koc concept?

PubMed

Jarvis, Nicholas

2016-01-01

Models used to assess leaching of pesticides to groundwater still rely on the sorption koc value, even though its limitations have been known for several decades, especially for soils of low organic carbon content (i.e. subsoils). 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 to test and compare alternative models of 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 785 data entries from 34 different published studies and for 21 different active substances. Overall, the apparent koc value, koc(app), roughly doubled as the soil organic carbon content decreased by a factor of ten. Nevertheless, in nearly half of the individual datasets, a constant koc value proved to be an adequate model. Further analysis showed that significant increases in koc(app) in subsoil were found primarily for the more weakly adsorbing compounds (koc values

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.

Sorption of 4-ethylphenol and 4-ethylguaiacol by suberin from cork.

PubMed

Gallardo-Chacón, Joan-Josep; Karbowiak, Thomas

2015-08-15

Cork shows an active role in the sorption of volatile phenols from wine. The sorption properties of 4-ethylphenol and 4-ethylguaiacol phenols in hydro-alcoholic medium placed in contact with suberin extracted from cork were especially investigated. To that purpose, suberin was immersed in model wine solutions containing several concentrations of each phenol and the amount of the compound remaining in the liquid phase was determined by SPME-GC-MS. Sorption isotherms of 4-ethylguaiacol and 4-ethylphenol by suberin followed the Henry's model. The solid/liquid partition coefficients (KSL) between the suberin and the model wine were also determined for several other volatile phenols. Suberin displayed rather high sorption capacity, which was positively correlated to the hydrophobicity of the volatile. Finally, the capacity of suberin to decrease the concentration of 4-ethylphenol and 4-ethylguaiacol was also tested in real wines affected by a Brettanomyces character. It also lead to a significant reduction of their concentration in wine. Copyright © 2015 Elsevier Ltd. All rights reserved.

Micropore clogging by leachable pyrogenic organic carbon: A new perspective on sorption irreversibility and kinetics of hydrophobic organic contaminants to black carbon.

PubMed

Wang, Bingyu; Zhang, Wei; Li, Hui; Fu, Heyun; Qu, Xiaolei; Zhu, Dongqiang

2017-01-01

Black carbon (BC) plays a crucial role in sequestering hydrophobic organic contaminants in the environment. This study investigated key factors and mechanisms controlling nonideal sorption (e.g., sorption irreversibility and slow kinetics) of model hydrophobic organic contaminants (nitrobenzene, naphthalene, and atrazine) by rice-straw-derived BC. After removing the fraction of leachable pyrogenic organic carbon (LPyOC) (referring to composites of dissoluble non-condensed organic carbon and associated mineral components) with deionized water or 0.5 M NaOH, sorption of these sorbates to BC was enhanced. The sorption enhancement was positively correlated with sorbate molecular size in the order of atrazine > naphthalene > nitrobenzene. The removal of LPyOC also accelerated sorption kinetics and reduced sorption irreversibility. These observations were attributed to increased accessibility of BC micropores initially clogged by the LPyOC. Comparison of BC pore size distributions before and after atrazine sorption further suggested that the sorbate molecules preferred to access the micropores that were more open, and the micropore accessibility was enhanced by the removal of LPyOC. Consistently, the sorption of nitrobenzene and atrazine to template-synthesized mesoporous carbon (CMK3), a model sorbent with homogeneous pore structures, showed decreased kinetics, but increased irreversibility by impregnating sorbent pores with surface-grafted alkylamino groups and by subsequent loading of humic acid. These findings indicated an important and previously unrecognized role of LPyOC (i.e., micropore clogging) in the nonideal sorption of organic contaminants to BC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Improving models for describing phosphorus cycling in agricultural soils

USDA-ARS?s Scientific Manuscript database

The mobility of phosphorus in the environment is controlled to a large extent by its sorption to soil. Therefore, an important component of all P loss models is how the model describes the biogeochemical processes governing P sorption and desorption to soils. The most common approach to modeling P c...

Effect made by the colloids to the sorption behavior of strontium on granite fracture-fillings

NASA Astrophysics Data System (ADS)

Wang, L.; Zuo, R.

2017-12-01

The objective of this study was to investigate the effects made by the colloid to the sorption capacity of colloids in granite fracture-fillings in aqueous solutions. The granite fracture-fillings were collected from three different depth of the research mine in Gansu province. According to the composition of the local soil and groundwater, two colloids were chosen to investigate this sorption process. Batch tests had been investigated at 27° under the air atmosphere as a function of pH(3 11), initial uranium concentration(5 400 mg/L) and water-rock ratio on the sorption of Sr on granite fracture-fillings. The batch experimental results showed that the sorption capacity presented a positive relationship with pH value, which may be caused by the hydrolytic adsorption raised by the reaction between Sr(OH)+ and OH- groups on the surface on the adsorbent. Initial strontium concentration also showed a positive relationship with sorption capacity when the concentration was lower than 200mg/mL, when the concentration was higher than 200mg/ml sorption reached the equilibrium. Sorption percentage showed a positive relationship with water/solid ratios, when the ratio was lower than 1:100 the system got equilibrium. When other experiment parameters were fixed and only the solid-liquid ratio changed, the adsorption capacity increased with the increasing solid-water ratio. The reason was that the total amount of Sr in the adsorption system remained unchanged, the adsorption sites increased with the solid-liquid ratio, and the adsorption capacity increased gradually with the increasing adsorption sites. The experiments data were interpreted in terms of Freundlich and Langmuir isotherms and the data fitted the former better. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of colloid.

Hybrid biosorbents for removal of pollutants and remediation

NASA Astrophysics Data System (ADS)

Burlakovs, Juris; Klavins, Maris; Robalds, Artis; Ansone, Linda

2014-05-01

For remediation of soils and purification of polluted waters, wastewaters, biosorbents might be considered as prospective groups of materials. Amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However, peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes thereby, to expand peat application sphere, the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in understanding of biosorbent means natural, biomass based modified material, covered with another sorbent material, thus combining properties of both such as sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyappatite) and organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area and elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature as the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested.

A critical evaluation of phosphate retardation and leaching in Hapludults

NASA Astrophysics Data System (ADS)

Dao, Thanh

2016-04-01

Nutrients used in production agriculture, in particular bioactive phosphorus (P), continue to present challenges in trying to reverse the degradation of fragile aquatic ecosystems. Soils treated with large amounts of nutrient-enriched animal manure have elevated P levels in regions of intensive animal agriculture and the residual effects of past large P additions were found to be long-lived. Mathematical models are increasingly used in the evaluation and development of mitigation strategies and sustainable management practices. A large number of predictive tools are currently used in the U.S. for simulating phosphorus environmental fate, including models such AGNPS (Agricultural Non-Point Source), FHANTM Field Hydrologic And Nutrient Transport Model (Field Hydrologic And Nutrient Transport Model), SWAT (Soil & Water Assessment Tool), or APEX (Agric. Policy/Environmental EXtender). The P routines in these models have had limited changes in spite of the advances in our understanding of speciation and transport of various P forms in soil and water systems that have occurred over the last three decades. We conducted soil sorption isotherm experiments that yielded basic information for estimating the Phosphorus Sorption coefficient (PSP) a key parameter used to allocate mineral P into soil labile, active, and stable pools. We compare these coefficients to parameters derived from breakthrough curves (BTC) for determining the extent of retardation and transport of phosphate supplied as KH2PO4 under a constant hydraulic head. Sigmoidal and multi-reaction rate models were observed in the BTCs of the anion, which undermine the rationale for using an overall simple partition coefficient to describe the transport and dispersal of phosphate in soil. Minimizing such generalities used in estimating nutrient availability and transport gives a more accurate picture of status of P in soil to conserve nutrients and minimize loss of excess P inputs to the environment.

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.

[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.

Weibull models of fracture strengths and fatigue behavior of dental resins in flexure and shear.

PubMed

Baran, G R; McCool, J I; Paul, D; Boberick, K; Wunder, S

1998-01-01

In estimating lifetimes of dental restorative materials, it is useful to have available data on the fatigue behavior of these materials. Current efforts at estimation include several untested assumptions related to the equivalence of flaw distributions sampled by shear, tensile, and compressive stresses. Environmental influences on material properties are not accounted for, and it is unclear if fatigue limits exist. In this study, the shear and flexural strengths of three resins used as matrices in dental restorative composite materials were characterized by Weibull parameters. It was found that shear strengths were lower than flexural strengths, liquid sorption had a profound effect on characteristic strengths, and the Weibull shape parameter obtained from shear data differed for some materials from that obtained in flexure. In shear and flexural fatigue, a power law relationship applied for up to 250,000 cycles; no fatigue limits were found, and the data thus imply only one flaw population is responsible for failure. Again, liquid sorption adversely affected strength levels in most materials (decreasing shear strengths and flexural strengths by factors of 2-3) and to a greater extent than did the degree of cure or material chemistry.

Elaboration and characterization of solid materials of types zeolite NaA and faujasite NaY exchanged by zinc metallic ions Zn2+

NASA Astrophysics Data System (ADS)

Nibou, D.; Amokrane, S.; Mekatel, H.; Lebaili, N.

2009-11-01

The present work deals with the elaborated of NaA and faujasite NaY solid materials according to a hydrothermal crystallization of amorphous gels composed of solutions of silicon, aluminum and sodium. The process elaboration has been achieved in autoclaves made of steel lined in Teflon under different operating conditions of temperature of heating, time of contact and stirring. After crystallization, the samples were characterized by different techniques such as X ray diffraction, scanning electronic microscopy, infrared spectroscopy, thermal analysis, and chemical analysis. Pure solid materials NaA and NaY zeolites were obtained and were impregnated by (Zn2+) ions by ion exchange process. The effects of various parameters such as initial metal concentration, pH, solid-liquid ratio (R) and temperature on the exchange percentage are studied. The equilibrium isotherms of zinc ions sorption are also evaluated using Langmuir and Freundlich models. Thermodynamic parameters, i.e. enthalpy of adsorption ΔHads∘, entropy change ΔSads∘ and Gibbs free energy ΔGads∘ for the sorption of zinc ions on NaA and NaY zeolites were examined.

Enhanced defluoridation and facile separation of magnetic nano-hydroxyapatite/alginate composite.

PubMed

Pandi, Kalimuthu; Viswanathan, Natrayasamy

2015-09-01

In this research study, a new magnetic biosorbent was developed by the fabrication of magnetic Fe3O4 particles on nano-hydroxyapatite(n-HAp)/alginate (Alg) composite (Fe3O4@n-HApAlg composite) for defluoridation in batch mode. The synthesized Fe3O4@n-HApAlg biocomposite possess an enhanced defluoridation capacity (DC) of 4050 mgF(-)/kg when compare to n-HApAlg composite, Fe3O4@n-HAp composite, n-HAp and Fe3O4 which possesses the DCs of 3870, 2469, 1296 and 1050 mgF(-)/kg respectively. The structural changes of the sorbent, before and after fluoride sorption were studied using FTIR, XRD and SEM with EDAX techniques. There are various physico-chemical parameters such as contact time, pH, co-existing anions, initial fluoride concentration and temperature were optimized for maximum fluoride removal. The equilibrium data was well modeled by Freundlich, Langmuir, Dubinin-Radushkevich (D-R) and Temkin isotherms. The present system follows Dubinin-Radushkevich isotherm model. The thermodynamic parameters reveals that the feasibility, spontaneity and endothermic nature of fluoride sorption. The performance and efficiency of the adsorbent material was examined with water samples collected from fluoride endemic areas namely Reddiyarchatram and Ammapatti in Dindigul District of Tamil Nadu using standard protocols. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Removal of lindane from an aqueous solution by using aminopropyl silica gel-immobilized calix[6]arene.

PubMed

Tor, Ali; Aydin, Mehmet Emin; Aydin, Senar; Tabakci, Mustafa; Beduk, Fatma

2013-11-15

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) has been used for the removal of lindane from an aqueous solution in batch sorption technique. The C[6]APS was synthesized with p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N'-diisopropyl carbodiimide coupling reagent. The sorption study was carried out as functions of solution pH, contact time, initial lindane concentration, C[6]APS dosage and ionic strength of solution. The matrix effect of natural water samples on the sorption efficiency of C[6]APS was also investigated. Maximum lindane removal was obtained at a wide pH range of 2-8 and sorption equilibrium was achieved in 2h. The isotherm analysis indicated that the sorption data can be represented by both Langmuir and Freundlich isotherm models. Increasing ionic strength of the solutions increased the sorption efficiency and matrix of natural water samples had no effect on the sorption of lindane. By using multilinear regression model, regression equation was also developed to explain the effects of the experimental variables. Copyright © 2013 Elsevier B.V. All rights reserved.

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 and Release of Organics by Primary, Anaerobic, and Aerobic Activated Sludge Mixed with Raw Municipal Wastewater

PubMed Central

Modin, Oskar; Saheb Alam, Soroush; Persson, Frank; Wilén, Britt-Marie

2015-01-01

New activated sludge processes that utilize sorption as a major mechanism for organics removal are being developed to maximize energy recovery from wastewater organics, or as enhanced primary treatment technologies. To model and optimize sorption-based activated sludge processes, further knowledge about sorption of organics onto sludge is needed. This study compared primary-, anaerobic-, and aerobic activated sludge as sorbents, determined sorption capacity and kinetics, and investigated some characteristics of the organics being sorbed. Batch sorption assays were carried out without aeration at a mixing velocity of 200 rpm. Only aerobic activated sludge showed net sorption of organics. Sorption of dissolved organics occurred by a near-instantaneous sorption event followed by a slower process that obeyed 1st order kinetics. Sorption of particulates also followed 1st order kinetics but there was no instantaneous sorption event; instead there was a release of particles upon mixing. The 5-min sorption capacity of activated sludge was 6.5±10.8 mg total organic carbon (TOC) per g volatile suspend solids (VSS) for particulate organics and 5.0±4.7 mgTOC/gVSS for dissolved organics. The observed instantaneous sorption appeared to be mainly due to organics larger than 20 kDa in size being sorbed, although molecules with a size of about 200 Da with strong UV absorbance at 215–230 nm were also rapidly removed. PMID:25768429

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.

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)

Modeling intragranular diffusion in low-connectivity granular media

NASA Astrophysics Data System (ADS)

Ewing, Robert P.; Liu, Chongxuan; Hu, Qinhong

2012-03-01

Characterizing the diffusive exchange of solutes between bulk water in an aquifer and water in the intragranular pores of the solid phase is still challenging despite decades of study. Many disparities between observation and theory could be attributed to low connectivity of the intragranular pores. The presence of low connectivity indicates that a useful conceptual framework is percolation theory. The present study was initiated to develop a percolation-based finite difference (FD) model, and to test it rigorously against both random walk (RW) simulations of diffusion starting from nonequilibrium, and data on Borden sand published by Ball and Roberts (1991a,b) and subsequently reanalyzed by Haggerty and Gorelick (1995) using a multirate mass transfer (MRMT) approach. The percolation-theoretical model is simple and readily incorporated into existing FD models. The FD model closely matches the RW results using only a single fitting parameter, across a wide range of pore connectivities. Simulation of the Borden sand experiment without pore connectivity effects reproduced the MRMT analysis, but including low pore connectivity effects improved the fit. Overall, the theory and simulation results show that low intragranular pore connectivity can produce diffusive behavior that appears as if the solute had undergone slow sorption, despite the absence of any sorption process, thereby explaining some hitherto confusing aspects of intragranular diffusion.

Iron and manganese removal: Recent advances in modelling treatment efficiency by rapid sand filtration.

PubMed

Vries, D; Bertelkamp, C; Schoonenberg Kegel, F; Hofs, B; Dusseldorp, J; Bruins, J H; de Vet, W; van den Akker, B

2017-02-01

A model has been developed that takes into account the main characteristics of (submerged) rapid filtration: the water quality parameters of the influent water, notably pH, iron(II) and manganese(II) concentrations, homogeneous oxidation in the supernatant layer, surface sorption and heterogeneous oxidation kinetics in the filter, and filter media adsorption characteristics. Simplifying assumptions are made to enable validation in practice, while maintaining the main mechanisms involved in iron(II) and manganese(II) removal. Adsorption isotherm data collected from different Dutch treatment sites show that Fe(II)/Mn(II) adsorption may vary substantially between them, but generally increases with higher pH. The model is sensitive to (experimentally) determined adsorption parameters and the heterogeneous oxidation rate. Model results coincide with experimental values when the heterogeneous rate constants are calibrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sensitivity of Deep Soil Organic Carbon Age to Sorption, Transport and Microbial Interactions - Insights from a Calibrated Process Model

NASA Astrophysics Data System (ADS)

Ahrens, B.; Schrumpf, M.; Reichstein, M.

2013-12-01

Subsoil soil organic carbon (SOC) is characterized by conventional radiocarbon ages on the order of centuries to millennia. Most vertically explicit SOC turnover models represent this persistence of deep SOC by one pool that has millennial turnover times. This approach lumps different stabilizing mechanisms such as chemical recalcitrance, sorptive stabilization and energy limitation into a single rate constant. As an alternative, we present a continuous, vertically explicit SOC decomposition model that allows for stabilization via sorption and microbial interactions (COMISSION model). We compare the COMISSION model with the SOC profile of a Haplic Podzol under a Norway spruce forest. In the COMISSION model two pools receive aboveground litter input and vertically distributed root litter input. The readily leachable and soluble fraction of litter input enters a dissolved organic carbon pool (DOC), while the rest enters the residue pool which represents polymeric, non-soluble SOC. The residue pool is depolymerized with extracellular enzymes produced by a microbial pool to enter the DOC pool which represents SOC potentially available for assimilation by microbes. The adsorption/desorption of DOC from/to mineral surfaces controls the availability of carbon in the DOC pool for assimilatory uptake by microbes. The sorption of DOC is modeled with dynamic Langmuir equations. The desorbed part of the DOC pool not only constitutes the substrate for the microbial pool, but is also transported via advection. Interactions of microbes with the residue and DOC pool are modeled with Michaelis-Menten kinetics - this not only allows representing ';priming', but also the retardation of decomposition via energy limitation in the deep soil where substrate is scarce. Further, soil organic matter is recycled within the soil profile through microbial processing - dead microbes either enter the DOC or the residue pool, and thereby also contribute to longer residence times with soil depth. First results of a calibration against SOC, SO14C, MOC and MO14C profiles (mineral associated organic carbon, density fraction >1.6 g cm-3) of a Haplic Podzol of the Waldstein site (Germany) show that we can use the maximum sorption capacity (qmax) estimated from batch sorption experiments to parameterize the dynamic Langmuir sorption equation. qmax could potentially be extrapolated to other soil profiles based on relations to iron and aluminum oxide contents. Although we are able to capture the secondary maximum of SOC contents in the Bh horizon with qmax from batch sorption experiments, our results indicate that the adsorption and desorption rates retrieved from batch sorption experiments are too fast to explain the low Δ14C values of the MOC. This could point to other processes apart from DOC sorption that trigger stabilization by organo-mineral associations with a stronger apparent irreversibility (e.g. inclusion in small pores). Alternatively, the conditions of batch sorption experiments (constant shaking in centrifuge tubes) might not be representative for in situ sorption conditions. Overall, we show how effective decomposition rates and 14C ages readily emerge from a combination of known stabilizing and destabilizing mechanisms and we discuss how to identify these processes with a model-data fusion framework.

Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

NASA Astrophysics Data System (ADS)

Evans, K.; Ferris, F.

2009-05-01

At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the prediction of fluoride removal in a wide variety of groundwater systems. Sorption isotherms and affinity constants show the use of BIOS to be a promising technique for the remediation of fluoride in groundwater.

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.

Efficient sorption and reduction of U(VI) on zero-valent iron-polyaniline-graphene aerogel ternary composite.

PubMed

Chen, Lili; Feng, Shaojie; Zhao, Donglin; Chen, Shaohua; Li, Feifei; Chen, Changlun

2017-03-15

In this work, zero-valent iron-polyaniline-graphene aerogel composite (Fe-PANI-GA) was prepared and applied in the removal of U(VI) from aqueous solutions by batch sorption experiments. The experimental results showed that the Fe-PANI-GA composite had an excellent removal capacity for the removal of U(VI) in acidic solutions. The results also showed that the maximum removal capacity of the Fe-PANI-GA toward U(VI) was 350.47mg/g at pH 5.5. The sorption kinetics data were well-described by pseudo-second-order. The sorption isotherms of U(VI) fitted well with Langmuir isotherm and exhibited better removal efficiency with the increase of temperature. The thermodynamic parameters (ΔG, ΔS, ΔH) indicated that the sorption of U(VI) on the Fe-PANI-GA was an endothermic and spontaneous process. Moreover, removal mechanisms were studied based on the results of XRD, FTIR and XPS. Both U(VI) sorption and partially reductive precipitation of U(VI) to U(IV) contributed to the removal of U(VI) on Fe-PANI-GA. Therefore, Fe-PANI-GA was an economic and effective material for the removal of uranium from nuclear waste in practical application. Copyright © 2016 Elsevier Inc. All rights reserved.

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

PubMed

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

2015-06-08

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

Description of gas/particle sorption kinetics with an intraparticle diffusion model: Desorption experiments

USGS Publications Warehouse

Rounds, S.A.; Tiffany, B.A.; Pankow, J.F.

1993-01-01

Aerosol particles from a highway tunnel were collected on a Teflon membrane filter (TMF) using standard techniques. Sorbed organic compounds were then desorbed for 28 days by passing clean nitrogen through the filter. Volatile n-alkanes and polycyclic aromatic hydrocarbons (PAHs) were liberated from the filter quickly; only a small fraction of the less volatile ra-alkanes and PAHs were desorbed. A nonlinear least-squares method was used to fit an intraparticle diffusion model to the experimental data. Two fitting parameters were used: the gas/particle partition coefficient (Kp and an effective intraparticle diffusion coefficient (Oeff). Optimized values of Kp are in agreement with previously reported values. The slope of a correlation between the fitted values of Deff and Kp agrees well with theory, but the absolute values of Deff are a factor of ???106 smaller than predicted for sorption-retarded, gaseous diffusion. Slow transport through an organic or solid phase within the particles or preferential flow through the bed of particulate matter on the filter might be the cause of these very small effective diffusion coefficients. ?? 1993 American Chemical Society.

Biosorption of formic and acetic acids from aqueous solution using activated carbon from shea butter seed shells

NASA Astrophysics Data System (ADS)

Adekola, Folahan A.; Oba, Ismaila A.

2017-10-01

The efficiency of prepared activated carbon from shea butter seed shells (SB-AC) for the adsorption of formic acid (FA) and acetic acid (AA) from aqueous solution was investigated. The effect of optimization parameters including initial concentration, agitation time, adsorbent dosage and temperature of adsorbate solution on the sorption capacity were studied. The SB-AC was characterized for the following parameters: bulk density, moisture content, ash content, pH, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The optimal conditions for the adsorption were established and the adsorption data for AA fitted Dubinin-Radushkevich (D-R) isotherm well, whereas FA followed Langmuir isotherm. The kinetic data were examined. It was found that pseudo-second-order kinetic model was found to adequately explain the sorption kinetic of AA and FA from aqueous solution. It was again found that intraparticle diffusion was found to explain the adsorption mechanism. Adsorption thermodynamic parameters were estimated and the negative values of Δ G showed that the adsorption process was feasible and spontaneous in nature, while the negative values of Δ H indicate that the adsorption process was exothermic. It is therefore established that SB-AC has good potential for the removal of AA and FA from aqueous solution. Hence, it should find application in the regular treatment of polluted water in aquaculture and fish breeding system.

Monitoring the startup of a wet detention pond equipped with sand filters and sorption filters.

PubMed

Vollertsen, J; Lange, K H; Pedersen, J; Hallager, P; Bruus, A; Laustsen, A; Bundesen, V W; Brix, H; Nielsen, A H; Nielsen, N H; Wium-Andersen, T; Hvitved-Jacobsen, T

2009-01-01

The startup of a wet retention pond designed for extended stormwater treatment was monitored by more than one year of continual measurement of hydraulic parameters, nutrients and quality parameters in the pond itself (pH, temperature, dissolved oxygen, turbidity). The data revealed that photosynthesis played an important role for dissolved oxygen and pH for most of the year. Another important observation was that the pond behaved more like a completely mixed reactor than like a plug flow reactor--even though the length to width ratio was as high as 4.5:1. The pond was equipped with sand filters and sorption filters whereby very good nutrient removal efficiencies were achieved.

Anomalous toluene transport in model segmented polyurethane-urea/clay nanocomposites.

PubMed

Rath, Sangram K; Bahadur, Jitendra; Panda, Himanshu S; Sen, Debasis; Patro, T Umasankar; S, Praveen; Patri, Manornajan; Khakhar, Devang V

2018-05-16

The kinetics of liquid solvent sorption in polymeric systems and their nanocomposites often deviate from normal Fickian behaviour. This needs to be understood and interpreted, in terms of their underlying mechanistic origins. In the present study, the results of time dependent toluene sorption measurements in model segmented polyurethane-urea/clay nanocomposites have been analysed at room temperature. The studies revealed pronounced S-shaped sorption curves and unusually higher swelling of the nanocomposites compared to the neat polyurethane-urea matrix. Dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS) measurements on the nanocomposites in the dry and liquid toluene saturated state have been carried out. The DMA studies revealed a significant decrease in the α relaxation temperature and storage modulus of the nanocomposites in the swollen state compared to the dry samples. The SAXS results showed that the nanoclay dispersion morphology transformed from intercalation in the dry state to exfoliation in the swollen state and the interdomain distance between hard segments increased upon swelling. Thermodynamic analysis of the Flory-Huggins interaction parameter (χ) of nanocomposite/toluene systems revealed increasingly negative χ values with increased clay loading. These results imply a significant plasticization effect of toluene on the nanocomposites. An interpretation of these data, which relates the abovementioned results, is presented in the framework of differential swelling stress (DSS) induced deviation from Fickian transport characteristics. We expect that these findings and methods may provide new insight into the analysis of the solvent diffusion process in heterogeneous polymers and their nanocomposites.

Adsorption Properties of Tetracycline onto Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies

PubMed Central

Ghadim, Ehsan Ezzatpour; Manouchehri, Firouzeh; Soleimani, Gholamreza; Hosseini, Hadi; Kimiagar, Salimeh; Nafisi, Shohreh

2013-01-01

Graphene oxide (GO) nanoparticle is a high potential effective absorbent. Tetracycline (TC) is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π–π interaction and cation–π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742–0.5362 g/mg min (at different temperatures). The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K). The mean energy of adsorption was determined 1.83 kJ/mol (298 K) based on the Dubinin–Radushkevich (D–R) adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet. PMID:24302989

Adsorption properties of tetracycline onto graphene oxide: equilibrium, kinetic and thermodynamic studies.

PubMed

Ghadim, Ehsan Ezzatpour; Manouchehri, Firouzeh; Soleimani, Gholamreza; Hosseini, Hadi; Kimiagar, Salimeh; Nafisi, Shohreh

2013-01-01

Graphene oxide (GO) nanoparticle is a high potential effective absorbent. Tetracycline (TC) is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π-π interaction and cation-π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742-0.5362 g/mg min (at different temperatures). The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K). The mean energy of adsorption was determined 1.83 kJ/mol (298 K) based on the Dubinin-Radushkevich (D-R) adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet.

Removal of barium and strontium from aqueous solution using zeolite 4A.

PubMed

Araissi, Manel; Ayed, Imen; Elaloui, Elimame; Moussaoui, Younes

2016-01-01

The adsorption efficiency of Sr(2+) and Ba(2+) from aqueous solutions by zeolite 4A was investigated. Adsorption studies were carried out both in single and binary component systems. The single ion equilibrium adsorption data were fitted to three isotherm models: Langmuir, Freundlich and Dubinin-Radushkevich. The Langmuir model represents the equilibrium data better than the Freundlich model in the studied initial metal concentration (0.3-25 mmol L(-1)) in both the single and binary component systems. The obtained RL (separation factor or Langmuir parameter) values were in the range of 0-1 indicating that Sr(2+) and Ba(2+) sorption were favorable. The obtained mean free energy value for adsorption of Ba(2+) and Sr(2+) was 8.45 kJ mol(-1) and 9.12 kJ mol(-1), respectively, indicating that both ions were uptaken through an ion exchange process. The maximum adsorption capacities (Qmax) were 2.25 mmol g(-1) and 2.34 mmol g(-1) for Ba(2+) and Sr(2+) ions, respectively. Also, the study of the competitive sorption of ions in the binary system showed that zeolite 4A preferentially adsorbs cations in the following order: Ba(2+) < Sr(2+).

Computational Identification and Analysis of the Key Biosorbent Characteristics for the Biosorption Process of Reactive Black 5 onto Fungal Biomass

PubMed Central

Yang, Yu-Yi; Li, Ze-Li; Wang, Guan; Zhao, Xiao-Ping; Crowley, David E.; Zhao, Yu-Hua

2012-01-01

The performances of nine biosorbents derived from dead fungal biomass were investigated for their ability to remove Reactive Black 5 from aqueous solution. The biosorption data for removal of Reactive Black 5 were readily modeled using the Langmuir adsorption isotherm. Kinetic analysis based on both pseudo-second-order and Weber-Morris models indicated intraparticle diffusion was the rate limiting step for biosorption of Reactive Black 5 on to the biosorbents. Sorption capacities of the biosorbents were not correlated with the initial biosorption rates. Sensitivity analysis of the factors affecting biosorption examined by an artificial neural network model showed that pH was the most important parameter, explaining 22%, followed by nitrogen content of biosorbents (16%), initial dye concentration (15%) and carbon content of biosorbents (10%). The biosorption capacities were not proportional to surface areas of the sorbents, but were instead influenced by their chemical element composition. The main functional groups contributing to dye sorption were amine, carboxylic, and alcohol moieties. The data further suggest that differences in carbon and nitrogen contents of biosorbents may be used as a selection index for identifying effective biosorbents from dead fungal biomass. PMID:22442697

Fate and Transport of CL-20 and RDX in Unsaturated Laboratory Columns

NASA Astrophysics Data System (ADS)

Lemond, L. A.; Gamerdinger, A. P.; Szecsody, J. E.

2005-05-01

This research examines the fate and transport of two explosive compounds, Hexanitrohexaazaisowurtzitane (CL-20) and Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in unsaturated laboratory columns. The transport and fate of these compounds were studied under saturated and unsaturated conditions in three natural soils: coarse sand, sandy loam, and a silt loam. Unsaturated column experiments were conducted using an ultra-centrifugation method. Sorption and degradation parameters were determined by moment analysis and hydrodynamic parameters were assessed with a two-region flow model. Differences in these parameters were evaluated as a function of water content. The fate and transport of CL-20 is highly dependent on 1) the soil type and 2) the compound's residence time in the soil and 3) water content of the media. Sorption of CL-20 was rate-limited. CL-20 degradation in saturated columns produced a half-life of as much as 22hr, but in unsaturated columns the degradation rate increased considerably, producing a half life of as little as 2hr. The fate and transport of RDX are also affected by the soil type, but sorption appeared to be instantaneous. Degradation of RDX was negligible. Our results suggest that at very low water content immobile water regions may become (at least in effect) isolated water regions and significantly alter the retardation of the tracer. In the sandy loam, there was as much as a 20-fold over-prediction of the retardation factor in the unsaturated saturated columns when predicted by Kd values derived from saturated columns. In the coarse sand, Kd values derived from saturated columns over-predicted retardation in the unsaturated columns by as much as 30%. In the silt loam, retardation factors were over-predicted by as much as 80%. At very low water contents, predictions of tracer behavior become very difficult because of changes in the flow regime that cannot be directly accounted for.

Assessment of suitability of some chosen functions for describing of sorption isotherms in building materials

NASA Astrophysics Data System (ADS)

Stolarska, Agata; Garbalińska, Halina

2017-05-01

This paper presents results of tests and studies conducted on six common building materials, used for constructing and finishing of external walls. These included: ceramic brick, silicate brick, autoclaved aerated concrete, cement mortar, cement-lime mortar and cement mortar modified with polypropylene fibers. Each of these materials is distinguished by the other structure of porousness, affecting both the course of sorption processes and the isotherms obtained. At first, measurements of moisture sorption kinetics at temperatures of 5, 20 and 35 °C were performed, each time at six levels of relative humidity. Then, when the sorption processes expired, equilibrium moisture sorption values were determined for the materials in 18 individual temperature and humidity conditions. The experimental data were used to determine the sorption isotherm courses for each material at the three temperatures. Then, theoretical analysis was performed in order to determine, which of the models available in the literature described the sorption isotherms of the concerned building materials the best. For each material and each of the three temperature values, twenty-four equations were tested. In each case, those of them were identified which ensured the best matching between the theoretical courses and the experimental data. The obtained results indicate that the Chen's model proved to be the most versatile. It ensured a detailed description of the sorption isotherms for each material and temperature tested.

Determination of Chlorinated Solvent Sorption by Porous Material-Application to Trichloroethene Vapor on Cement Mortar.

PubMed

Musielak, Marion; Brusseau, Mark L; Marcoux, Manuel; Morrison, Candice; Quintard, Michel

2014-08-01

Experiments have been performed to investigate the sorption of trichloroethene (TCE) vapor by concrete material or, more specifically, the cement mortar component. Gas-flow experiments were conducted using columns packed with small pieces of cement mortar obtained from the grinding of typical concrete material. Transport and retardation of TCE at high vapor concentrations (500 mg L -1 ) was compared to that of a non-reactive gas tracer (Sulfur Hexafluoride, SF6). The results show a large magnitude of retardation (retardation factor = 23) and sorption (sorption coefficient = 10.6 cm 3 g -1 ) for TCE, compared to negligible sorption for SF6. This magnitude of sorption obtained with pollutant vapor is much bigger than the one obtained for aqueous-flow experiments conducted for water-saturated systems. The considerable sorption exhibited for TCE under vapor-flow conditions is attributed to some combination of accumulation at the air-water interface and vapor-phase adsorption, both of which are anticipated to be significant for this system given the large surface area associated with the cement mortar. Transport of both SF6 and TCE was simulated successfully with a two-region physical non-equilibrium model, consistent with the dual-medium structure of the crushed cement mortar. This work emphasizes the importance of taking into account sorption phenomena when modeling transport of volatile organic compounds through concrete material, especially in regard to assessing vapor intrusion.

Reactive Transport Modeling of Subsurface Arsenic Removal Systems in Rural Bangladesh

NASA Astrophysics Data System (ADS)

Bakker, M.; Rahman, M. M.; van Breukelen, B. M.; Ahmed, K. M.

2014-12-01

Elevated concentrations of arsenic (As) in the groundwater of the shallow aquifers of Bangladesh are a major public health concern. Subsurface Arsenic Removal (SAR) is a relatively new treatment option that can potentially be a cost effective method for arsenic removal for community-based drinking water supplies. The basic idea of SAR is to extract water, aerate it, and re-inject it, after which groundwater with reduced arsenic concentrations may be extracted. The main process for As reduction is sorption to Hydrous Ferric Oxides (HFO) that forms after injection of the aerated water. The purpose of this poster is to investigate the major geochemical processes responsible for the (im)mobilization of As during SAR operation. SAR was applied at a test site in Muradnagar upazila in Comilla district about 100 km southeast of Dhaka in Bangladesh. Multiple extraction/aeration/re-injection cycles were performed and water samples were analyzed. A PHREEQC reactive transport model (RTM) was used in a radial flow setting to try to reproduce the measurements. Kinetic oxidation/dissolution reactions, cation exchange, and surface complexation were simulated. The simulation of different reactions enables the possibility to discern the reaction parameters involved in the im(mobilization) of As. The model fit has reasonable agreement with the observed data for major ions and trace elements. The model suggests an increasing sorption capacity due to the gradual development of HFO precipitates resulting from the injection phases. Modeled breakthrough curves of As, Fe(II), and Mn, match the measured increase of As, Fe(II), and Mn removal with successive cycles. The model illustrates that the pH of groundwater during SAR operation has a great impact on As sorption in the subsurface. The surface complexation modeling suggests that competitive displacement of As by H4SiO4 is an important factor limiting As removal during SAR operation.

Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

PubMed

Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

2013-11-19

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

Effects of pH, dissolved organic matter, and salinity on ibuprofen sorption on sediment.

PubMed

Oh, Sanghwa; Shin, Won Sik; Kim, Hong Tae

2016-11-01

Ibuprofen is well known as one of the most frequently detected pharmaceuticals and personal care products (PPCPs) in rivers. However, sorption of ibuprofen onto sediment has not been considered in spite of its high K ow (3.5). In this study, the effects of various environmental conditions such as pH (4, 5.3, and 7), the concentrations of dissolved organic matters (0 to 1.0 mM citrate and urea), salinity (0, 10, 20, and 30 part per thousand), and presence of other PPCP (salicylic acid) on ibuprofen sorption were investigated. Linear model mainly fitted the experimental data for analysis. The distribution coefficient (K d ) in the linear model decreased from 6.76 at pH 4 to near zero at pH 7, indicating that neutral form of ibuprofen at pH below pKa (5.2) was easily sorbed onto the sediment whereas the sorption of anionic form at pH over pKa was not favorable. To investigate the effect of dissolved organic matters (DOMs) on ibuprofen sorption, citrate and urea were used as DOMs. As citrate concentration increased, the K d value decreased but urea did not interrupt the ibuprofen sorption. Citrate has three carboxyl functional groups which can attach easily ibuprofen and hinder its sorption onto sediment. Salinity also affected ibuprofen sorption due to decrease of the solubility of ibuprofen as salinity increased. In competitive sorption experiment, the addition of salicylic acid also led to enhance ibuprofen sorption. Conclusively, ibuprofen can be more easily sorbed onto the acidified sediments of river downstream, especially estuaries or near-shore environment with low DOM concentration.

Sorption of selected pharmaceuticals by a river sediment: role and mechanisms of sediment or Aldrich humic substances.

PubMed

Le Guet, Thibaut; Hsini, Ilham; Labanowski, Jérôme; Mondamert, Leslie

2018-05-01

Sorption of pharmaceuticals onto sediments is frequently related to organic matter content. Thus, the present work aimed to compare the effect of humic substances (HS) extracted from a river sediment versus Aldrich (HS) on the sorption of selected pharmaceuticals onto this river sediment. The results exhibited no "unique" effect of the presence of HS from the same origin. Thus, the sediment HS increased the sorption of sulfamethoxazole (SMX), diclofenac (DCF), and trimethoprim (TMP), but reduced the sorption of atenolol (ATN). The presence of Aldrich HS increased the sorption of TMP and ATN and decreased the sorption of SMX and DCF. Fluorescence quenching measurements revealed that these effects cannot be explained only by the presence of pharmaceutical HS associations. The use of several sorption models suggested that the sorption of SMX, DCF, and ATN involves multilayer mechanisms. Furthermore, it was pointed out that the presence of HS does not change the sorption mechanisms although it was observed interaction between HS and the sediment. Indeed, the sediment HS sorbs onto the sediment whereas the Aldrich HS tends to mobilize organic compounds from the sediment to the solution.

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.

Ultrasound-assisted xanthation of cellulose from lignocellulosic biomass optimized by response surface methodology for Pb(II) sorption.

PubMed

Wang, Chongqing; Wang, Hui; Gu, Guohua

2018-02-15

Alkali treatment of lignocellulosic biomass is conducted to remove hemi-cellulose and lignin, further increasing the reactivity and accessibility of cellulose. Ultrasound-assisted xanthation of alkali cellulose is optimized by response surface methodology (RSM) with a Box-Behnken design. A predicting mathematical model is obtained by fitting experimental data, and it is verified by analysis of variance. Response surface plots and the contour plots obtained from the model are applied to determine the interactions of experimental variables. The optimum conditions are NaOH concentration 1.3mol/L, ultrasonic time 71.6min and CS 2 dosage 1.5mL. FTIR, SEM and XPS characterizations confirm the synthesis and sorption mechanism of cellulose xanthate (CX). Biosorption of Pb (II) onto CX obeys pseudo-second order model and Langmuir model. The sorption mechanism is attributed to surface complexation or ion exchange. CX shows good reusability for Pb (II) sorption. The maximum sorption capacity of Pb(II) is 134.41mg/g, higher than that of other biosorbents. CX has great potential as an efficient and low-cost biosorbent for wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption of chlorophenols from aqueous solution by granular activated carbon, filter coal, pine and hardwood.

PubMed

Hossain, G S M; McLaughlan, R G

2012-09-01

Wood and coal, as low-cost sorbents, have been evaluated as an alternative to commercial granular activated carbon (GAC) for chlorophenol removal. Kinetic experiments indicated that filter coal had a significantly lower rate of uptake (approximately 10% of final uptake was achieved after three hours) than the other sorbents, owing to intra-particle diffusion limitations. The data fitted a pseudo-second-order model. Sorption capacity data showed that GAC had a high sorption capacity (294-467 mg g(-1)) compared with other sorbents (3.2-7.5 mg(g-1)). However, wood and coal had a greater sorption capacity per unit surface area than GAC. Sorption equilibrium data was best predicted using a Freundlich adsorption model. The sorption capacity for all sorbents was 2-chlorophenol < 4-chlorophenol < 2, 4-dichlorophenol, which correlates well with solute hydrophobicity, although the relative differences were much less for coal than the other sorbents. The results showed that pine, hardwood and filter coal can be used as sorbent materials for the removal of chlorophenol from water; however, kinetic considerations may limit the application of filter coal.

Analysis of efficiency of phosphates sorption by different granulation of selected reactive material

NASA Astrophysics Data System (ADS)

Kasprzyk, Magda; Węgler, Jarosław; Gajewska, Magdalena

2018-01-01

In the light of the need to find an effective way to remove phosphorus from wastewater, studies on the suitability of sorption materials in this process should be conducted. The aim of the study was to examine the potential benefits of using selected adsorbents to reduce orthophosphates from the model solution under steady conditions. The study was conducted on a laboratory scale using synthetic wastewater with concentration of P-PO4 in the range of 5-100 mg/dm3. Experiment has shown that fine-grained material M1 (0-2 mm) is highly effective at removal of phosphorus compounds at the level of 97.8% at the highest concentration of P-PO4. The sorption capacity achieved during the investigation was 9.6 mg/g, while the maximum sorption capacity from the Langmuir model could reach up to 256 mg/g. Material M2 (2-8 mm) did not show satisfactory sorption capacity (maximum calculated sorption capacity: 0.36 mg/g) and the effectiveness of phosphate reduction did not exceeded 6% at the lowest concentration of P-PO4.

Design, characterization and evaluation of hydroxyethylcellulose based novel regenerable supersorbent for heavy metal ions uptake and competitive adsorption.

PubMed

Abbas, Azhar; Hussain, Muhammad Ajaz; Sher, Muhammad; Irfan, Muhammad Imran; Tahir, Muhammad Nawaz; Tremel, Wolfgang; Hussain, Syed Zajif; Hussain, Irshad

2017-09-01

Hydroxyethylcellulose succinate-Na (HEC-Suc-Na) was designed and evaluated for removal of some heavy metal ions from aqueous solution. Pristine sorbent HEC-Suc-Na was thoroughly characterized by FTIR and solid-state CP/MAS 13 C NMR spectroscopy, SEM-EDS and zero point charge analyses. Langmuir isotherm, pseudo second order kinetic and ion exchange models provided best fit to the experimental data of sorption of metal ions. Maximum sorption capacities of supersorbent HEC-Suc-Na for sorption of heavy metal ions from aqueous solution as calculated by Langmuir isotherm model were found to be 1000, 909.09, 666.6, 588 and 500mgg -1 for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. Competitive sorption of these heavy metal ions was carried out from galvanic and nuclear waste water simulated environment. The negative values of ΔG° and ΔH° indicated spontaneity and exothermic nature of sorption. The sorbent was efficiently regenerated with no significant decrease in sorption capacity after five cycles. Copyright © 2017 Elsevier B.V. All rights reserved.

Metals sorption from aqueous solutions by Kluyveromyces marxianus: process optimization, equilibrium modeling and chemical characterization.

PubMed

Pal, Rama; Tewari, Saumyata; Rai, Jai P N

2009-10-01

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0-1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.

Rapid removal of uranium from aqueous solutions using magnetic Fe3O4@SiO2 composite particles.

PubMed

Fan, Fang-Li; Qin, Zhi; Bai, Jing; Rong, Wei-Dong; Fan, Fu-You; Tian, Wei; Wu, Xiao-Lei; Wang, Yang; Zhao, Liang

2012-04-01

Rapid removal of U(VI) from aqueous solutions was investigated using magnetic Fe(3)O(4)@SiO(2) composite particles as the novel adsorbent. Batch experiments were conducted to study the effects of initial pH, amount of adsorbent, shaking time and initial U(VI) concentrations on uranium sorption efficiency as well as the desorbing of U(VI). The sorption of uranium on Fe(3)O(4)@SiO(2) composite particles was pH-dependent, and the optimal pH was 6.0. In kinetics studies, the sorption equilibrium can be reached within 180 min, and the experimental data were well fitted by the pseudo-second-order model, and the equilibrium sorption capacities calculated by the model were almost the same as those determined by experiments. The Langmuir sorption isotherm model correlates well with the uranium sorption equilibrium data for the concentration range of 20-200 mg/L. The maximum uranium sorption capacity onto magnetic Fe(3)O(4)@SiO(2) composite particles was estimated to be about 52 mg/g at 25 °C. The highest values of uranium desorption (98%) was achieved using 0.01 M HCl as the desorbing agent. Fe(3)O(4)@SiO(2) composite particles showed a good selectivity for uranium from aqueous solution with other interfering cation ions. Present study suggested that magnetic Fe(3)O(4)@SiO(2) composite particles can be used as a potential adsorbent for sorption uranium and also provided a simple, fast separation method for removal of heavy metal ion from aqueous solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

A Novel Method for Measuring the Diffusion, Partition and Convective Mass Transfer Coefficients of Formaldehyde and VOC in Building Materials

PubMed Central

Xiong, Jianyin; Huang, Shaodan; Zhang, Yinping

2012-01-01

The diffusion coefficient (D m) and material/air partition coefficient (K) are two key parameters characterizing the formaldehyde and volatile organic compounds (VOC) sorption behavior in building materials. By virtue of the sorption process in airtight chamber, this paper proposes a novel method to measure the two key parameters, as well as the convective mass transfer coefficient (h m). Compared to traditional methods, it has the following merits: (1) the K, D m and h m can be simultaneously obtained, thus is convenient to use; (2) it is time-saving, just one sorption process in airtight chamber is required; (3) the determination of h m is based on the formaldehyde and VOC concentration data in the test chamber rather than the generally used empirical correlations obtained from the heat and mass transfer analogy, thus is more accurate and can be regarded as a significant improvement. The present method is applied to measure the three parameters by treating the experimental data in the literature, and good results are obtained, which validates the effectiveness of the method. Our new method also provides a potential pathway for measuring h m of semi-volatile organic compounds (SVOC) by using that of VOC. PMID:23145156

Polyurethane foam (PUF) passive samplers for monitoring phenanthrene in stormwater.

PubMed

Dou, Yueqin; Zhang, Tian C; Zeng, Jing; Stansbury, John; Moussavi, Massoum; Richter-Egger, Dana L; Klein, Mitchell R

2016-04-01

Pollution from highway stormwater runoff has been an increasing area of concern. Many structural Best Management Practices (BMPs) have been implemented for stormwater treatment and management. One challenge for these BMPs is to sample stormwater and monitor BMP performance. The main objective of this study was to evaluate the feasibility of using polyurethane foam (PUF) passive samplers (PSs) for sampling phenanthrene (PHE) in highway stormwater runoff and BMPs. Tests were conducted using batch reactors, glass-tube columns, and laboratory-scale BMPs (bioretention cells). Results indicate that sorption for PHE by PUF is mainly linearly relative to time, and the high sorption capacity allows the PUF passive sampler to monitor stormwater events for months or years. The PUF passive samplers could be embedded in BMPs for monitoring influent and effluent PHE concentrations. Models developed to link the results of batch and column tests proved to be useful for determining removal or sorption parameters and performance of the PUF-PSs. The predicted removal efficiencies of BMPs were close to the real values obtained from the control columns with errors ranging between -8.46 and 1.52%. This research showed that it is possible to use PUF passive samplers for sampling stormwater and monitoring the performance of stormwater BMPs, which warrants the field-scale feasibility studies in the future.

Solid phase extraction of uranium(VI) onto benzoylthiourea-anchored activated carbon.

PubMed

Zhao, Yongsheng; Liu, Chunxia; Feng, Miao; Chen, Zhen; Li, Shuqiong; Tian, Gan; Wang, Li; Huang, Jingbo; Li, Shoujian

2010-04-15

A new solid phase extractant selective for uranium(VI) based on benzoylthiourea anchored to activated carbon was developed via hydroxylation, amidation and reaction with benzoyl isothiocyanate in sequence. Fourier transform infrared spectroscopy and total element analysis proved that benzoylthiourea had been successfully grafted to the surface of the activated carbon, with a loading capacity of 1.2 mmol benzoylthiourea per gram of activated carbon. The parameters that affect the uranium(VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, adsorbent dose and temperature, have been investigated. Results have been analyzed by Langmuir and Freundlich isotherm; the former was more suitable to describe the sorption process. The maximum sorption capacity (82 mg/g) for uranium(VI) was obtained at experimental conditions. The rate constant for the uranium sorption by the as-synthesized extractant was 0.441 min(-1) from the first order rate equation. Thermodynamic parameters (DeltaH(0)=-46.2 kJ/mol; DeltaS(0)=-98.0 J/mol K; DeltaG(0)=-17.5 kJ/mol) showed the adsorption of an exothermic process and spontaneous nature, respectively. Additional studies indicated that the benzoylthiourea-anchored activated carbon (BT-AC) selectively sorbed uranyl ions in the presence of competing ions, Na(+), Co(2+), Sr(2+), Cs(+) and La(3+). 2009 Elsevier B.V. All rights reserved.

Determination of thermodynamic properties of poly (cyclohexyl methacrylate) by inverse gas chromatography.

PubMed

Kaya, Ismet; Pala, Cigdem Yigit

2014-07-01

In this work, some thermodynamic properties of poly (cyclohexyl methacrylate) were studied by inverse gas chromatography (IGC). For this purpose, the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times (t(r)) of the probes were determined from the interactions of poly (cyclohexyl methacrylate) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, methanol, ethanol, 2-propanol, butanol, acetone, ethyl methyl ketone, benzene, toluene and o-xylene by IGC technique. Then, the specific volume (Vg(0)) was determined for each probe molecule. By using (1/T; lnVg(0)) graphics, the glass transition temperature of poly (cyclohexyl methacrylate) was found to be 373 K. The adsorption heat under the glass transition temperature (deltaH(a)), and partial molar heat of sorption above the glass transition (deltaH1(S)), partial molar free energy of sorption (deltaG1(S)) and partial molar entropy of sorption (deltaS1(S)) belonging to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution (deltaH1(infinity)), partial molar free energy of mixing at infinite dilution (deltaG1(infinity)), Flory-Huggins interaction parameter (chi12(infinity)) and weight fraction activity coefficient (a1/w1)(infinity) values of polymer-solute systems were calculated at different column temperatures. The solubility parameters (delta2) of the polymer were obtained by IGC technique.

Impact of rainfall intensity on the transport of two herbicides in undisturbed grassed filter strip soil cores

NASA Astrophysics Data System (ADS)

Pot, V.; Šimůnek, J.; Benoit, P.; Coquet, Y.; Yra, A.; Martínez-Cordón, M.-J.

2005-12-01

Two series of displacement experiments with isoproturon and metribuzin herbicides were performed on two undisturbed grassed filter strip soil cores, under unsaturated steady-state flow conditions. Several rainfall intensities (0.070, 0.147, 0.161, 0.308 and 0.326 cm h - 1 ) were used. A water tracer (bromide) was simultaneously injected in each displacement experiment. A descriptive analysis of experimental breakthrough curves of bromide and herbicides combined with a modeling analysis showed an impact of rainfall intensity on the solute transport. Two contrasting physical non-equilibrium transport processes occurred. Multiple (three) porosity domains contributed to flow at the highest rainfall intensities, including preferential flow through macropore pathways. Macropores were not active any longer at intermediate and lowest velocities, and the observed preferential transport was described using dual-porosity-type models with a zero or low flow in the matrix domain. Chemical non-equilibrium transport of herbicides was found at all rainfall intensities. Significantly higher estimated values of degradation rate parameters as compared to batch data were correlated with the degree of non-equilibrium sorption. Experimental breakthrough curves were analyzed using different physical and chemical equilibrium and non-equilibrium transport models: convective-dispersive model (CDE), dual-porosity model (MIM), dual-permeability model (DP), triple-porosity, dual permeability model (DP-MIM); each combined with both chemical instantaneous and kinetic sorption.

Sorption Isotherm of Southern Yellow Pine-High Density Polyethylene Composites.

PubMed

Liu, Feihong; Han, Guangping; Cheng, Wanli; Wu, Qinglin

2015-01-20

Temperature and relative humidity (RH) are two major external factors, which affect equilibrium moisture content (EMC) of wood-plastic composites (WPCs). In this study, the effect of different durability treatments on sorption and desorption isotherms of southern yellow pine (SYP)-high density polyethylene (HDPE) composites was investigated. All samples were equilibriumed at 20 °C and various RHs including 16%, 33%, 45%, 66%, 75%, 85%, 93%, and100%. EMCs obtained from desorption and absorption for different WPC samples were compared with Nelson's sorption isotherm model predictions using the same temperature and humidity conditions. The results indicated that the amount of moisture absorbed increased with the increases in RH at 20 °C. All samples showed sorption hysteresis at a fixed RH. Small difference between EMC data of WPC samples containing different amount of ultraviolet (UV) stabilizers were observed. Similar results were observed among the samples containing different amount of zinc borate (ZB). The experimental data of EMCs at various RHs fit to the Nelson's sorption isotherm model well. The Nelson's model can be used to predicate EMCs of WPCs under different RH environmental conditions.

Tracer Movement in a Single Fissure in Granitic Rock: Some Experimental Results and Their Interpretation

NASA Astrophysics Data System (ADS)

Neretnieks, Ivars; Eriksen, Tryggve; TäHtinen, PäIvi

1982-08-01

Radionuclide migration was studied in a natural fissure in a granite core. The fissure was oriented parallel to the axis in a cylindrical core 30 cm long and 20 cm in diameter. The traced solution was injected at one end of the core and collected at the other. Breakthrough curves were obtained for the nonsorbing tracers, tritiated water, and a large-molecular-weight lignosulphonate molecule and for the sorbing tracers, cesium and strontium. From the breakthrough curves for the nonsorbing tracers it could be concluded that channeling occurs in the single fissure. A `dispersion' model based on channeling is presented. The results from the sorbing tracers indicate that there is substantial diffusion into and sorption in the rock matrix. Sorption on the surface of the fissure also accounts for a part of the retardation effect of the sorbing species. A model which includes the mechanisms of channeling, surface sorption, matrix diffusion, and matrix sorption is presented. The experimental breakthrough curves can be fitted fairly well by this model by use of independently obtained data on diffusivities and matrix sorption.

Competitive sorption affinity of sulfonamides and chloramphenicol antibiotics toward functionalized biochar for water and wastewater treatment.

PubMed

Ahmed, Mohammad Boshir; Zhou, John L; Ngo, Huu Hao; Guo, Wenshan; Johir, Md Abu Hasan; Belhaj, Dalel

2017-08-01

Competitive sorption of sulfamethazine (SMT), sulfamethoxazole (SMX), sulfathiazole (STZ) and chloramphenicol (CP) toward functionalized biochar (fBC) was highly pH dependent with maximum sorption at pH ∼4.0-4.25. Equilibrium data were well represented by the Langmuir and Freundlich models in the order STZ>SMX>CP>SMT. Kinetics data were slightly better fitted by the pseudo second-order model than pseudo first-order and intra-particle-diffusion models. Maximum sorptive interactions occurred at pH 4.0-4.25 through H-bonds formations for neutral sulfonamides species and through negative charge assisted H-bond (CAHB) formation for CP, in addition to π-π electron-donor-acceptor (EDA) interactions. EDA was the main mechanism for the sorption of positive sulfonamides species and CP at pH<2.0. Sorption of negative sulfonamides species and CP at pH>7.0 was regulated by H-bond formation and proton exchange with water by forming CAHB, respectively. The results suggested fBC to be highly efficient in removing antibiotics mixture. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption Isotherm of Southern Yellow Pine—High Density Polyethylene Composites

PubMed Central

Liu, Feihong; Han, Guangping; Cheng, Wanli; Wu, Qinglin

2015-01-01

Temperature and relative humidity (RH) are two major external factors, which affect equilibrium moisture content (EMC) of wood-plastic composites (WPCs). In this study, the effect of different durability treatments on sorption and desorption isotherms of southern yellow pine (SYP)-high density polyethylene (HDPE) composites was investigated. All samples were equilibriumed at 20 °C and various RHs including 16%, 33%, 45%, 66%, 75%, 85%, 93%, and100%. EMCs obtained from desorption and absorption for different WPC samples were compared with Nelson’s sorption isotherm model predictions using the same temperature and humidity conditions. The results indicated that the amount of moisture absorbed increased with the increases in RH at 20 °C. All samples showed sorption hysteresis at a fixed RH. Small difference between EMC data of WPC samples containing different amount of ultraviolet (UV) stabilizers were observed. Similar results were observed among the samples containing different amount of zinc borate (ZB). The experimental data of EMCs at various RHs fit to the Nelson’s sorption isotherm model well. The Nelson’s model can be used to predicate EMCs of WPCs under different RH environmental conditions. PMID:28787943

Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Lewan, Mike; Sun, Xun; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

2013-01-01

A series of CH4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH4 molecules for sorption on organic matter is stronger than for most common clay minerals. Thus, it is expected that CH4 molecules may preferentially occupy surface sites on organic matter. However, active sites on clay mineral surfaces are easily blocked by water. As a consequence, organic-rich shales possess a larger CH4-sorption capacity than clay-rich rocks lacking organic matter. The thermodynamic parameters obtained in this study can be incorporated into model predictions of the maximum Langmuir pressure and CH4- sorption capacity of shales under reservoir temperature and pressure conditions.

Evaluation of Sorption Mechanism of Pb (II) and Ni (II) onto Pea (Pisum sativum) Peels.

PubMed

Haq, Atta Ul; Saeed, Muhammad; Anjum, Salma; Bokhari, Tanveer Hussain; Usman, Muhammad; Tubbsum, Saiqa

2017-07-01

The present study was carried out to know the sorption mechanism of Pb (II) and Ni (II) in aqueous solution using pea peels under the influence of sorbent dose, pH, temperature, initial metal ion concentration and contact time. SEM and FTIR were used for characterization of pea peels. The study showed that solution pH affects sorption process and the optimum pH for Pb (II) was 6.0 while for that of Ni (II) was 7.0. Pseudo-second order kinetic model was found to be the most suitable one to explain the kinetic data not only due to high value of R 2 (>0.99) but also due to the closeness of the experimental sorption capacity values to that of calculated sorption capacity values of pseudo second order kinetic model. It can be seen from the results that Freundlich isotherm explains well the equilibrium data (R 2 >0.99). Sorption capacity of pea peels was 140.84 and 32.36 for Pb (II) and Ni (II) mg g -1 respectively. The positive value of ΔH° and negative values of ΔG° suggest that sorption of Pb (II) and Ni (II) onto pea peels is an endothermic and spontaneous process respectively.

Pressure impact of autoclave treatment on water sorption and pectin composition of flax cellulosic-fibres.

PubMed

Alix, S; Colasse, L; Morvan, C; Lebrun, L; Marais, S

2014-02-15

The tensile properties of flax fibres might permit them to be used in composites as reinforcement in organic resin, as long as their mechanical properties are reproducible and their water sorption are reduced. In this study, to minimise the variability of mechanical properties, several samples of flax fibres were blended as a non-woven fabric. In order to reduce the water absorption of this non-woven technical fibres, an autoclave treatment was performed which was expected to remove the pectins and then to reduce the water sorption on their negative charges. The impact of autoclave pressure (0.5, 1 and 2 bars) on water sorption was investigated by using a gravimetric static equilibrium method. The Park model based on the three sorption modes: Langmuir, Henry's law and clustering, was successfully used to simulate the experimental sorption data. The lowest pressure treatments impacted only the Langmuir contribution while the 2 bar autoclave-treatment positively impacted the water resistance in the core of fibres by reducing Henry's absorption rate. This was shown to be related to the chemical modifications at the surface and in the core of fibres. A schematic model is presented relating the water sorption and the pectic composition of the fabric. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Sorption of ionic and nonionic organic solutes onto giant Miscanthus-derived biochar from methanol-water mixtures.

PubMed

Kim, Juhee; Hyun, Seunghun

2018-02-15

The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) onto giant Miscanthus-derived biochar was investigated in methanol volume fractions (f c ) of 0-0.6 as a function of ionic composition (5mM CaCl 2 and 10mM KCl) and liquid pH (2 and 7). The sorption onto biochar was nonlinear with 0.42≤N≤0.95; thus, a concentration-specific sorption constant (K m ) was compared. The K m log linearly decreased with increasing f c , except for 1-NAPA from a CaCl 2 mixture at pH7. Isotherm data was fitted with a cosolvency sorption model through which the slope (ασ) of the inverse log linear K m -f c plot and empirical constant (α) were obtained. NAP sorption was well described by the cosolvency model with the α value being 0.41-0.53, indicating a methanol-biochar interaction favoring more sorption than the cosolvency based prediction. In particular, the slope (ασ) of 1-NAPA was lower than that of NAP, indicating less reduction of 1-NAPA sorption (i.e., lower α value) by methanol. In comparison with other sorbents, the α value was approximately intermediate between a humic substance and kaolinite clay. An analysis of FT-IR spectra suggested the transformation of O-containing functional groups by methanol, which will subsequently boost the π-π interaction between an organic solute and biochar. Moreover, Ca 2+ -induced sorption between anionic 1-NAPA and a negatively charged biochar surface was also fortified in the methanol mixture. The results revealed unexplored cosolvent effects on organic solute sorption onto biochar and identified the hydrophobic and hydrophilic sorption moieties of biochar as affected by the cosolvent. Copyright © 2017 Elsevier B.V. All rights reserved.

Positron Spectroscopy of Nanodiamonds after Hydrogen Sorption

PubMed Central

Laptev, Roman; Abzaev, Yuri; Lider, Andrey; Ivashutenko, Alexander

2018-01-01

The structure and defects of nanodiamonds influence the hydrogen sorption capacity. Positronium can be used as a sensor for detecting places with the most efficient capture of hydrogen atoms. Hydrogenation of carbon materials was performed from gas atmosphere. The concentration of hydrogen absorbed by the sample depends on the temperature and pressure. The concentration 1.2 wt % is achieved at the temperature of 243 K and the pressure of 0.6 MPa. The hydrogen saturation of nanodiamonds changes the positron lifetime. Increase of sorption cycle numbers effects the positron lifetime, as well as the parameters of the Doppler broadening of annihilation line. The electron-positron annihilation being a sensitive method, it allows detecting the electron density fluctuation of the carbon material after hydrogen saturation. PMID:29324712

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 representation of pesticide sorption in subsoil. The model tested in this study appears to be widely applicable and simple enough to parameterize for risk assessment purposes. However, more data on subsoil sorption should first be included in the analysis to enable reliable estimation of worst-case percentile values of the power law exponent in the model.

Measurement of Moisture Sorption Isotherm by DVS Hydrosorb

NASA Astrophysics Data System (ADS)

Kurniawan, Y. R.; Purwanto, Y. A.; Purwanti, N.; Budijanto, S.

2018-05-01

Artificial rice made from corn flour, sago, glycerol monostearate, vegetable oil, water and jelly powder was developed by extrusion method through the process stages of material mixing, extrusion, drying, packaging and storage. Sorption isotherm pattern information on food ingredients used to design and optimize the drying process, packaging, storage. Sorption isotherm of water of artificial rice was measured using humidity generating method with Dynamic Vapor Sorption device that has an advantage of equilibration time is about 10 to 100 times faster than saturated salt slurry method. Relative humidity modification technique are controlled automatically by adjusting the proportion of mixture of dry air and water saturated air. This paper aims to develop moisture sorption isotherm using the Hydrosorb 1000 Water Vapor Sorption Analyzer. Sample preparation was conducted by degassing sample in a heating mantle of 65°C. Analysis parameters need to be fulfilled were determination of Po, sample data, selection of water activity points, and equilibrium conditions. The selected analytical temperatures were 30°C and 45°C. Analysis lasted for 45 hours and curves of adsorption and desorption were obtained. Selected bottom point of water activity 0.05 at 30°C and 45°C yielded adsorbed mass of 0.1466 mg/g and 0.3455 mg/g, respectively, whereas selected top water activity point 0.95 at 30°C and 45°C yielded adsorbed mass of 190.8734 mg/g and 242.4161mg/g, respectively. Moisture sorption isotherm measurements of articial rice made from corn flour at temperature of 30°C and 45°C using Hydrosorb showed that the moisture sorption curve approximates sigmoid-shaped type II curve commonly found in corn-based foodstuffs (high- carbohydrate).

Effect of mineral surface properties (alumina, kaolinite) on the sorptive fractionation mechanisms of soil fulvic acids: Molecular-scale ESI-MS studies

NASA Astrophysics Data System (ADS)

Fleury, Guillaume; Del Nero, Mirella; Barillon, Rémi

2017-01-01

We addressed the effects of mineral surface properties (kaolinite versus Al-oxide) on the sorption-driven fractionation of a soil fulvic acid (FA) at acidic pH, mainly by means of ESI(-)-FTMS analysis of initial and supernatant solutions of FA sorption batch experiments. The MS data provided clear molecular-scale evidence of distinct mechanisms and molecular parameters controlling the FA fractionation upon its sorption on clay and oxide surfaces, respectively. Identification of sorbing and not-sorbing FA compounds in kaolinite-solution systems revealed a weak fractionation among members of sbnd CO2 series of aliphatics or not-condensed aromatics (NCAs) at pH 3.8, and almost no sorption of poorly-oxygenated polycyclic aromatic compounds (PACs) and NCAs. This first molecular-scale description of a FA fractionation in a clay-solution system suggests that H-bonding with low affinity sites (aluminol/silanol) on the basal planes of the clay particles is the main mechanism of sorption. Due to the predominance of such weak and poorly-selective mechanism, the sorption of aliphatic and NCA molecules bearing oxygenated functionalities was prevented at pH 5, due to dissolved Al competing successfully for their coordination. In contrast, a strong FA fractionation was observed onto alumina, with a preferential retention of PACs and highly-oxygenated aliphatics and NCAs. The major part of the poorly oxygenated aliphatics was left in solution. The sorption degree of NCAs and aliphatics was strongly correlated with molecular acidity. For PACs and poorly-oxygenated NCAs, the sorption was driven by reactions of surface ligand exchange (for the most oxygenated compounds) or by hydrophobic interactions (for the least oxygenated compounds).

Kinetics of Methylmercury Production Revisited

DOE PAGES

Olsen, Todd A.; Muller, Katherine A.; Painter, Scott L.; ...

2018-01-27

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show in this paper that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature includingmore » those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Finally, simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.« less

Multi-Scale Multi-Physics Modeling of Matrix Transport Properties in Fractured Shale Reservoirs

NASA Astrophysics Data System (ADS)

Mehmani, A.; Prodanovic, M.

2014-12-01

Understanding the shale matrix flow behavior is imperative in successful reservoir development for hydrocarbon production and carbon storage. Without a predictive model, significant uncertainties in flowback from the formation, the communication between the fracture and matrix as well as proper fracturing practice will ensue. Informed by SEM images, we develop deterministic network models that couple pores from multiple scales and their respective fluid physics. The models are used to investigate sorption hysteresis as an affordable way of inferring the nanoscale pore structure in core scale. In addition, restricted diffusion as a function of pore shape, pore-throat size ratios and network connectivity is computed to make correct interpretation of the 2D NMR maps possible. Our novel pore network models have the ability to match sorption hysteresis measurements without any tuning parameters. The results clarify a common misconception of linking type 3 nitrogen hysteresis curves to only the shale pore shape and show promising sensitivty for nanopore structre inference in core scale. The results on restricted diffusion shed light on the importance of including shape factors in 2D NMR interpretations. A priori "weighting factors" as a function of pore-throat and throat-length ratio are presented and the effect of network connectivity on diffusion is quantitatively assessed. We are currently working on verifying our models with experimental data gathered from the Eagleford formation.

Sorption Modeling of Strontium, Plutonium, Uranium and Neptunium Adsorption on Monosodium Titanate

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

Fondeur, F.F.

2003-10-30

We examined the ability of various equilibrium isotherms to replicate the available data for the adsorption of strontium (Sr), plutonium (Pu), uranium (U) and neptunium (Np) on monosodium titanate (MST) during the treatment of simulated and actual Savannah River Site high-level waste. The analysis considered 29 isotherm models from the literature. As part of this study, we developed a general method for selecting the best isotherm models. The selection criteria for rating the isotherms considered the relative error in predicting the experimental data, the complexity of the mathematical expressions, the thermodynamic validity of the expressions, and statistical significance for themore » expressions. The Fowler Guggenheim-Jovanovic Freundlich (FG-JF), the Fowler Guggenheim-Langmuir Freundlich (FG-LF) and the Dubinin-Astashov (DA) models each reliably predicted the actinide and strontium adsorption on MST. The first two models describe the adsorption process by single layer formation and later al interactions between adsorbed sorbates while the Dubinin-Astashov model assumes volume filling of micropores (by osmotic pressure difference). These two mechanisms include mutually exclusive assumptions. However, we can not determine which model best represents the various adsorption mechanisms on MST. Based on our analysis, the DA model predicted the data well. The DA model assumes that an initial sorption layer forms after which networking begins in the pore spaces, filling the volume by a second mechanism. If this mechanism occurs in MST, as the experimental data suggests, then we expect all the empty and closed spaces of MST to contain actinides and strontium when saturated. Prior microstructure analyses determined that the MST surface is best described as heterogeneous (i.e., a semi-crystalline outer layer on an amorphous core) or composite material for adsorption. Therefore, we expect the empty spaces (of nanometer size) between the crystalline units in the fibrous material to provide sorption area for the actinides and strontium. Since each of the three models work reliably, we recommend use of the computationally simplest model as the primary tool until future work can differentiate between the two mechanisms. The Dubinin-Astashov model possesses a simpler mathematical form with fewer parameters and operations.« less

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Biosorption of Basic Green 4 from aqueous solution by Ananas comosus (pineapple) leaf powder.

PubMed

Chowdhury, Shamik; Chakraborty, Sagnik; Saha, Papita

2011-06-01

Biosorption characteristics of Ananas comosus (pineapple) leaf powder was investigated for decolorization of Basic Green 4 (BG 4), a cationic dye from its aqueous solutions employing a batch experimental set-up. Parameters that influence the sorption process such as pH, biosorbent dosage, contact time, initial dye concentration and temperature were systematically studied. The optimum conditions for removal of BG 4 were found to be pH 9.0, contact time=150 min, biosorbent dosage=5.0 g L(-1), initial dye concentration=50 mg L(-1). The temperature had a strong influence on the biosorption process. Further, the biosorbent was characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Brunauer, Emmett, Teller (BET) surface area and pore size analysis. Experimental biosorption data were modeled by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The biosorption process followed the Langmuir isotherm model with high coefficients of correlation (R(2)>0.99) at different temperatures. The pseudo second order kinetic model fitted well in correlation to the experimental results. Activation energy of the biosorption process (E(a)) was found to be 45.79 kJ mol(-1) by using the Arrhenius equation, indicating chemisorption nature of BG 4 sorption onto pineapple leaf powder. Thermodynamic parameters suggest that the biosorption process is spontaneous and exothermic in nature. Overall, the present findings suggest that this environmentally friendly, efficient and low-cost biosorbent may be useful for the removal of BG 4 from aqueous media. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of pyrolysis temperature on polycyclic aromatic hydrocarbons toxicity and sorption behaviour of biochars prepared by pyrolysis of paper mill effluent treatment plant sludge.

PubMed

Devi, Parmila; Saroha, Anil K

2015-09-01

The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs). Copyright © 2015 Elsevier Ltd. All rights reserved.

Modeling Fission Product Sorption in Graphite Structures

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

Szlufarska, Izabela; Morgan, Dane; Allen, Todd

2013-04-08

The goal of this project is to determine changes in adsorption and desorption of fission products to/from nuclear-grade graphite in response to a changing chemical environment. First, the project team will employ principle calculations and thermodynamic analysis to predict stability of fission products on graphite in the presence of structural defects commonly observed in very high- temperature reactor (VHTR) graphites. Desorption rates will be determined as a function of partial pressure of oxygen and iodine, relative humidity, and temperature. They will then carry out experimental characterization to determine the statistical distribution of structural features. This structural information will yield distributionsmore » of binding sites to be used as an input for a sorption model. Sorption isotherms calculated under this project will contribute to understanding of the physical bases of the source terms that are used in higher-level codes that model fission product transport and retention in graphite. The project will include the following tasks: Perform structural characterization of the VHTR graphite to determine crystallographic phases, defect structures and their distribution, volume fraction of coke, and amount of sp2 versus sp3 bonding. This information will be used as guidance for ab initio modeling and as input for sorptivity models; Perform ab initio calculations of binding energies to determine stability of fission products on the different sorption sites present in nuclear graphite microstructures. The project will use density functional theory (DFT) methods to calculate binding energies in vacuum and in oxidizing environments. The team will also calculate stability of iodine complexes with fission products on graphite sorption sites; Model graphite sorption isotherms to quantify concentration of fission products in graphite. The binding energies will be combined with a Langmuir isotherm statistical model to predict the sorbed concentration of fission products on each type of graphite site. The model will include multiple simultaneous adsorbing species, which will allow for competitive adsorption effects between different fission product species and O and OH (for modeling accident conditions).« less

Effect of humic acid on the sorption of perfluorooctane sulfonate (PFOS) and perfluorobutane sulfonate (PFBS) on boehmite.

PubMed

Wang, Fei; Shih, Kaimin; Leckie, James O

2015-01-01

The sorption of PFOS and PFBS on boehmite was significantly retarded by the competitive sorption of humic acid (HA), implying that PFOS and PFBS are likely more mobile in water and groundwater systems enriched with HA. The sorption behavior of PFOS and PFBS on the HA-modified boehmite surface were also found to differ due to their different chain lengths. For a partially HA-modified boehmite surface, the isotherm study showed that PFOS had a much higher maximum sorption capacity than PFBS and that PFOS might possess additional surface interactions besides electrostatic interaction. For a HA-saturated boehmite, a linear sorption isotherm was found for PFOS while nearly no PFBS sorption was observed. This indicates that sorption behavior between PFOS and the sorbed HA on boehmite was dominated by hydrophobic interactions, instead of electrostatic interaction. In addition, a conceptual model combining hydrophobic and electrostatic interaction was established to explain the sorption behavior of PFOS and PFBS on HA-modified boehmite. Finally, the results revealed that the sorption of PFOS and PFBS on HA-modified boehmite is pH-dependent. The neutralization of negative sites on HA-modified boehmite reduced the electrostatic repulsion and enhanced the partitioning of PFBS on the sorbed HA. Copyright © 2014 Elsevier Ltd. All rights reserved.

Zeolite in horizontal permeable reactive barriers for artificial groundwater recharge

NASA Astrophysics Data System (ADS)

Leal, María; Martínez-Hernández, Virtudes; Lillo, Javier; Meffe, Raffaella; de Bustamante, Irene

2013-04-01

The Spanish Water Reuse Royal Decree 1620/2007 considers groundwater recharge as a feasible use of reclaimed water. To achieve the water quality established in the above-mentioned legislation, a tertiary wastewater treatment is required. In this context, the infiltration of effluents generated by secondary wastewater treatments through a Horizontal Permeable Reactive Barrier (HPRB) may represent a suitable regeneration technology. Some nutrients (phosphate and ammonium) and some Pharmaceutical and Personal Care Products (PPCPs) are not fully removed in conventional wastewater treatment plants. To avoid groundwater contamination when effluents of wastewater treatments plants are used in artificial recharge activities, these contaminants have to be removed. Due to its sorption capacities, zeolite is among the most used reactive materials in Permeable Reactive Barrier (PRB). Therefore, the main goal of this study is to evaluate the zeolite retention effectiveness of nutrients and PPCPs occurring in treated wastewater. Batch sorption experiments using synthetic wastewater (SWW) and zeolite were performed. A 1:4 zeolite/SWW ratio was selected due to the high sorption capacity of the reactive material.The assays were carried out by triplicate. All the bottles containing the SWW-zeolite mixture were placed on a mechanical shaker during 24 hours at 140 rpm and 25 °C. Ammonium and phosphate, as main nutrients, and a group of PPCPs were selected as compounds to be tested during the experiments. Nutrients were analyzed by ion chromatography. For PPCPs determination, Solid Phase Extraction (SPE) was applied before their analysis by liquid chromatography-mass spectrometry time of flight (LC-MS/ TOF). The experimental data were fitted to linearized Langmuir and Freundlich isotherm equations to obtain sorption parameters. In general, Freundlich model shows a greater capability of reproducing experimental data. To our knowledge, sorption of the investigated compounds on zeolite has rarely been addressed and this holds true especially for PPCPs. Therefore, the obtained results will be useful for the design and characterization of those HPRBs in which zeolite will be employed to regenerate treated wastewater for artificial recharge activities.

TWO-DIMENSIONAL MODELING OF AQUIFER REMEDIATION INFLUENCED BY SORPTION NONEQUILIBRIUM AND HYDRAULIC CONDUCTIVITY HETEROGENEITY

EPA Science Inventory

A computational model was developed to simulate aquifer remediation by pump and treat for a confined, perfectly stratified aquifer. plit-operator finite element numerical technique was utilized to incorporate flow field heterogeneity and nonequilibrium sorption into a two-dimensi...

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...

Determination of hyporheic travel time distributions and other parameters from concurrent conservative and reactive tracer tests by local-in-global optimization

NASA Astrophysics Data System (ADS)

Knapp, Julia L. A.; Cirpka, Olaf A.

2017-06-01

The complexity of hyporheic flow paths requires reach-scale models of solute transport in streams that are flexible in their representation of the hyporheic passage. We use a model that couples advective-dispersive in-stream transport to hyporheic exchange with a shape-free distribution of hyporheic travel times. The model also accounts for two-site sorption and transformation of reactive solutes. The coefficients of the model are determined by fitting concurrent stream-tracer tests of conservative (fluorescein) and reactive (resazurin/resorufin) compounds. The flexibility of the shape-free models give rise to multiple local minima of the objective function in parameter estimation, thus requiring global-search algorithms, which is hindered by the large number of parameter values to be estimated. We present a local-in-global optimization approach, in which we use a Markov-Chain Monte Carlo method as global-search method to estimate a set of in-stream and hyporheic parameters. Nested therein, we infer the shape-free distribution of hyporheic travel times by a local Gauss-Newton method. The overall approach is independent of the initial guess and provides the joint posterior distribution of all parameters. We apply the described local-in-global optimization method to recorded tracer breakthrough curves of three consecutive stream sections, and infer section-wise hydraulic parameter distributions to analyze how hyporheic exchange processes differ between the stream sections.

Effective use of iron-aluminum rich laterite based soil mixture for treatment of landfill leachate.

PubMed

Nayanthika, I V K; Jayawardana, D T; Bandara, N J G J; Manage, P M; Madushanka, R M T D

2018-04-01

Landfill leachate poses environmental threats worldwide and causes severe issues on adjacent water bodies and soil by direct discharge. The primary objective of this study is to analyze the efficient use of compost and laterite mixtures (0, 10, 20, 30 and 40 wt% compost/laterite) on leachate treatment and to investigate the associated removal efficiencies under different sorption processes. Therefore, in the experimental design, laterite is used for providing adsorption characteristics, and compost for activating biological properties of the filter. The filtering process is continued until major physical changes occur in the filter at approximately 100 days. The raw leachate used for the experiment shows higher average values for many analyzed parameters. Parameters for the experiment are selected based on their availability in raw leachate in the Sri Lanka. During filtering, removal efficiencies of BOD (>90%), COD (>85%), phosphate (>90%) and nitrate (75-95%) show higher values for all filters. These removals are mainly associated with biodegradation, which is activated by the added compost. Perhaps the removal of nitrate steadily increases with time, which indicates in denitrification by the added excess carbon from the leachate. The removal of total suspended solids (TSS) is moderate to high, but conversely, the electric conductivity (EC) is unsteady, indicating an association between iron exchange and carbonate degradation. A very high removal efficiency is reported in Fe (90-100%), and wide ranges of efficiencies in Mn (30-90%), Cu (45-85%), Ni (30-93%), Cd (37-98%), Zn (15-98%), and Pb (35-98%) involve heterogeneous sorption processes. Furthermore, the normalization of raw leachate by the liquid filtrate has apparent improvements. The differences (p > .05) in removal efficiencies between the filters are significant. It can be concluded that the filter with laterite mixed with 20% of compost has the optimum conditions. Further, the Fourier-transforminfrared (FT-IR) models for filter media conclude multiple sorptions and reveal evidence on vacant sites. X-ray diffraction (XRD) analyses indicate secondary minerals gibbsite, hematite, goethite and kaolinite as the major minerals that involved on the sorption process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kinetic modeling of antimony(III) oxidation and sorption in soils.

PubMed

Cai, Yongbing; Mi, Yuting; Zhang, Hua

2016-10-05

Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. Copyright © 2016 Elsevier B.V. All rights reserved.

Sensitivity analysis of conservative and reactive stream transient storage models applied to field data from multiple-reach experiments

USGS Publications Warehouse

Gooseff, M.N.; Bencala, K.E.; Scott, D.T.; Runkel, R.L.; McKnight, Diane M.

2005-01-01

The transient storage model (TSM) has been widely used in studies of stream solute transport and fate, with an increasing emphasis on reactive solute transport. In this study we perform sensitivity analyses of a conservative TSM and two different reactive solute transport models (RSTM), one that includes first-order decay in the stream and the storage zone, and a second that considers sorption of a reactive solute on streambed sediments. Two previously analyzed data sets are examined with a focus on the reliability of these RSTMs in characterizing stream and storage zone solute reactions. Sensitivities of simulations to parameters within and among reaches, parameter coefficients of variation, and correlation coefficients are computed and analyzed. Our results indicate that (1) simulated values have the greatest sensitivity to parameters within the same reach, (2) simulated values are also sensitive to parameters in reaches immediately upstream and downstream (inter-reach sensitivity), (3) simulated values have decreasing sensitivity to parameters in reaches farther downstream, and (4) in-stream reactive solute data provide adequate data to resolve effective storage zone reaction parameters, given the model formulations. Simulations of reactive solutes are shown to be equally sensitive to transport parameters and effective reaction parameters of the model, evidence of the control of physical transport on reactive solute dynamics. Similar to conservative transport analysis, reactive solute simulations appear to be most sensitive to data collected during the rising and falling limb of the concentration breakthrough curve. ?? 2005 Elsevier Ltd. All rights reserved.

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 .

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments.

PubMed

Brechbühl, Yves; Christl, Iso; Elzinga, Evert J; Kretzschmar, Ruben

2012-07-01

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures. Copyright © 2012 Elsevier Inc. All rights reserved.

High adsorption performance for As(III) and As(V) onto novel aluminum-enriched biochar derived from abandoned Tetra Paks.

PubMed

Ding, Zhuhong; Xu, Xuebin; Phan, Thihongnhung; Hu, Xin; Nie, Guangze

2018-06-12

In order to develop promising sorbents for value-added application of solid wastes, low-cost aluminum-enriched biochar was prepared from abandoned Tetra Pak used to hold milks, a paper-polyethylence-Al foil laminated package box, after acid pretreatment and subsequent slow pyrolysis under an oxygen-limited environment at 600 °C. The basic physicochemical properties of the resultant biochar were characterized and the sorption performance of aqueous As(III) and As(V) was investigated via batch and column sorption experiments. Carbon (49.1%), Ca (7.41%) and Al (13.5%) were the most abundant elements in the resultant biochar; and the specific surface area and the pH value at the point of zero charge (pHPZC) were 174 m 2  g -1 and 9.3, respectively. Batch sorption showed excellent sorption performance for both As(III) (24.2 mg g -1 ) and As(V) (33.2 mg g -1 ) and experimental data were fitted well with Langmuir model for the sorption isotherms and pseudo-second order kinetic model for the sorption kinetics. The residual concentrations of As(V) after sorption were below the limited value of arsenic in WHO Guidelines for Drinking water Quality (0.01 mg L -1 ) even if coexistence of PO 4 3- . Column sorption confirmed the high sorption performance for As(III) and As(V). So the slow pyrolysis of abandoned Tetra Paks as low-cost and value-added sorbents is a sustainable strategy for solid waste disposal and wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Iron and manganese oxides modified maize straw to remove tylosin from aqueous solutions.

PubMed

Yin, Yongyuan; Guo, Xuetao; Peng, Dan

2018-08-01

Maize straw modified by iron and manganese oxides was synthesized via a simple and environmentally friendly method. Three maize straw materials, the original maize straw, maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides, were detected by SEM, BET, XPS, XRD and FTIR. The results showed that maize straw was successfully modified and maize straw modified by iron and manganese oxides has a larger surface area than MS. According to the experimental data, the sorption trend could conform to the pseudo-second-order kinetic model well, and the sorption ability of tylosin on sorbents followed the order of original maize straw < maize straw modified by manganese oxides < maize straw modified by iron and manganese oxides. The study indicated that manganese oxides and iron-manganese oxides could significantly enhance the sorption capacity of original maize straw. The sorption isotherm data of tylosin on original maize straw fit a linear model well, while Freundlich models were more suitable for maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides. The pH, ionic strength and temperature can affect the sorption process. The sorption mechanisms of tylosin on iron and manganese oxides modified maize straw were attribute to the surface complexes, electrostatic interactions, H bonding and hydrophobic interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Copper (II) adsorption by the extracellular polymeric substance extracted from waste activated sludge after short-time aerobic digestion.

PubMed

Zhang, Zhiqiang; Zhou, Yun; Zhang, Jiao; Xia, Siqing

2014-02-01

The extracellular polymeric substance (EPS) extracted from waste activated sludge (WAS) after short-time aerobic digestion was investigated to be used as a novel biosorbent for Cu(2+) removal from water. The EPS consisted of protein (52.6 %, w/w), polysaccharide (30.7 %, w/w), and nucleic acid (16.7 %, w/w). Short-time aerobic digestion process of WAS for about 4 h promoted the productivity growth of the EPS for about 10 %. With a molecular weight of about 1.9 × 10(6) Da, the EPS showed a linear structure with long chains, and contained carboxyl, hydroxyl, and amino groups. The sorption kinetics was well fit for the pseudo-second-order model, and the maximum sorption capacity of the EPS (700.3 mg Cu(2+)/g EPS) was markedly greater than those of the reported biosorbents. Both Langmuir model and Freundlich model commendably described the sorption isotherm. The Gibbs free energy analysis of the adsorption showed that the sorption process was feasible and spontaneous. According to the complex results of multiple analytical techniques, including scanning electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy, etc., the adsorption process took place via both physical and chemical sorption, but the electrostatic interaction between sorption sites with the functional groups and Cu(2+) is the major mechanism.

Improved retention of imidacloprid (Confidor) in soils by adding vermicompost from spent grape marc.

PubMed

Fernández-Bayo, Jesús D; Nogales, Rogelio; Romero, Esperanza

2007-05-25

Batch sorption experiments of the insecticide imidacloprid by ten widely different Spanish soils were carried out. The sorption was studied for the active ingredient and its registered formulation Confidor. The temperature effect was studied at 15 degrees C and 25 degrees C. The addition of a vermicompost from spent grape marc (natural and ground), containing 344 g kg(-1) organic carbon, on the sorption of imidacloprid by two selected soils, a sandy loam and a silty clay loam, having organic carbon content of 3.6 g kg(-1) and 9.3 g kg(-1), respectively, was evaluated. Prior to the addition of this vermicompost, desorption isotherms with both selected soils, were also performed. The apparent hysteresis index (AHI) parameter was used to quantify sorption-desorption hysteresis. Sorption coefficients, K(d) and K(f), for the active ingredient and Confidor(R) in the different soils were similar. Sorption decreased with increasing temperature, this fact has special interest in greenhouse systems. A significant correlation (R(2)=0.965; P<0.01) between K(f) values and the organic carbon (OC) content was found, but some soils showed higher sorption coefficients than that expected from their OC values. The normalized sorption coefficients with the soil organic carbon content (K(oc)) were dispersed and low, implying that other characteristics of soils could contribute to the retention capacity as well. The spent grape marc vermicompost was an effective sorbent of this insecticide (K(f)=149). The sorption of imidacloprid increased significantly in soils amended with this vermicompost. The most pronounced effect was found in the sandy loam soil with low OC content, where the addition of 5% and 10% of vermicompost increased K(f) values by 8- and 15-fold, respectively. Soil desorption of imidacloprid was slower for the soil with the higher OC and clay content.

Peat hybrid sorbents for treatment of wastewaters and remediation of polluted environment

NASA Astrophysics Data System (ADS)

Klavins, Maris; Burlakovs, Juris; Robalds, Artis; Ansone-Bertina, Linda

2015-04-01

For remediation of soils and purification of polluted waters, wastewaters, sorbents might be considered as an prospective group of materials and amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes. To expand peat application possibilities the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in our understanding means natural, biomass based sorbent modified, covered with another sorbent material, thus combining two types of sorbent properties, sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyapatite) both organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area, elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature, and the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested. Acknowledgement: Support from a project 2014/0009/1DP/1.1.1.2.0/13/APIA/VIAA/044

Phosphorus sorption on marine carbonate sediment: phosphonate as model organic compounds.

PubMed

Huang, Xiao-Lan; Zhang, Jia-Zhong

2011-11-01

Organophosphonate, characterized by the presence of a stable, covalent, carbon to phosphorus (C-P) bond, is a group of synthetic or biogenic organophosphorus compounds. The fate of these organic phosphorus compounds in the environment is not well studied. This study presents the first investigation on the sorption of phosphorus (P) in the presence of two model phosphonate compounds, 2-aminothylphosphonoic acid (2-AEP) and phosphonoformic acid (PFA), on marine carbonate sediments. In contrast to other organic P compounds, no significant inorganic phosphate exchange was observed in seawater. P was found to adsorb on the sediment only in the presence of PFA, not 2-AEP. This indicated that sorption of P from phosphonate on marine sediment was compound specific. Compared with inorganic phosphate sorption on the same sediments, P sorption from organic phosphorus is much less in the marine environment. Further study is needed to understand the potential role of the organophosphonate compounds in biogeochemical cycle of phosphorus in the environment. Copyright © 2011 Elsevier Ltd. All rights reserved.

Preparation and characterization of a novel graphene/biochar composite for aqueous phenanthrene and mercury removal.

PubMed

Tang, Jingchun; Lv, Honghong; Gong, Yanyan; Huang, Yao

2015-11-01

A graphene/biochar composite (G/BC) was synthesized via slow pyrolysis of graphene (G) pretreated wheat straw, and tested for the sorption characteristics and mechanisms of representative aqueous contaminants (phenanthrene and mercury). Structure and morphology analysis showed that G was coated on the surface of biochar (BC) mainly through π-π interactions, resulting in a larger surface area, more functional groups, greater thermal stability, and higher removal efficiency of phenanthrene and mercury compared to BC. Pseudo second-order model adequately simulated sorption kinetics, and sorption isotherms of phenanthrene and mercury were simulated well by dual-mode and BET models, respectively. FTIR and SEM analysis suggested that partitioning and surface sorption were dominant mechanisms for phenanthrene sorption, and that surface complexation between mercury and C-O, CC, -OH, and OC-O functional groups was responsible for mercury removal. The results suggested that the G/BC composite is an efficient, economic, and environmentally friendly multifunctional adsorbent for environmental remediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Solid structures with bioorganic films on silicon

NASA Astrophysics Data System (ADS)

Tutov, E. A.

2012-06-01

The electrophysical parameters of ovalbumin/silicon and propolis/silicon heterostructures are studied using impedance spectroscopy and high-frequency capacitance-voltage characteristics under water vapor sorption conditions.

Distribution of phenanthrene between soil and an aqueous phase in the presence of anionic micelle-like amphiphilic polyurethane particles.

PubMed

Lee, Kangtaek; Choi, Heon-Sik; Kim, Ju-Young; Ahn, Ik-Sung

2003-12-12

Sorption of micelle-like amphiphilic polyurethane (APU) particles to soil was studied and compared to that of a model anionic surfactant, sodium dodecyl sulfate (SDS). Three types of APU particles with different hydrophobicity were synthesized from urethane acrylate anionomers (UAA) and used in this study. Due to the chemically cross-linked structure, APU exhibited less sorption to the soil than SDS and a greater reduction in the sorption of phenanthrene, a model soil contaminant, to the soil was observed in the presence of APU than SDS even though the solubility of phenanthrene was higher in the presence of SDS than APU. A mathematical model was developed to describe the phenanthrene distribution between soil and an aqueous phase containing APU particles. The sorption of phenanthrene to the test soil could be well described by Linear isotherm. APU sorption to the soil was successfully described by Langmuir and Freundlich isotherms. The partition of phenanthrene between water and APU were successfully explained with a single partition coefficient. The model, which accounts for the limited solubilization of phenanthrene in sorbed APU particles, successfully described the experimental data for the distribution of phenanthrene between the soil and the aqueous phase in the presence of APU.

TWO-DIMENSIONAL MODELING OF AQUIFER REMEDIATION INFLUENCED BY SORPTION NONEQUILIBRIUM AND HYDRAULIC CONDUCTIVITY HETEROGENEITY

EPA Science Inventory

A computational model was developed to simulate aquifer remediation by pump and treat for a confined, perfectly stratified aquifer. A split-operator finite element numerical technique was utilized to incorporate flow field heterogeneity and nonequilibrium sorption into a two-dime...

Experimental study of Pb (II) solution sorption behavior onto Coffee Husk Bioactivated Carbon

NASA Astrophysics Data System (ADS)

Fona, Z.; Habibah, U.

2018-04-01

Coffee husk which is abundantly produced in the coffee plantations is potential to be a challenging adsorbent. The fate of Pb (II) solution in the sorption mechanism onto the adsorbent has been investigated. This paper aimed to study the efficiency of Pb (II) aqueous solution removal using activated carbon from coffee husk (CAC). The sorption characteristics were using two isotherm models, Langmuir and Freundlich, were also reported. The coffee husk from local plantations in Middle Aceh was carbonized and sieved to 120/140 mesh. The charcoal was activated using hydrochloric acid before contacted with the different initial concentrations of Pb (II) solution. The remaining concentrations of the metal in the specified contact times were determined using Atomic Adsorption Spectrophotometer at 283.3 wavelength. The result showed that the equilibrium concentrations were obtained in about 30 minutes which depended on the initial concentration. The sorption mechanism followed Freundlich isotherm model where the adsorption constant and capacity were accordingly 1.353 and 1.195 mgg‑1. The iodine sorption was up to 1,053 mgg‑1. Based on the ash and moisture content, as well as iodine sorption, the activated carbon met the national standard.

Transport of polar and non-polar volatile compounds in polystyrene foam and oriented strand board

NASA Astrophysics Data System (ADS)

Yuan, Huali; Little, John C.; Hodgson, Alfred T.

Transport of hexanal and styrene in polystyrene foam (PSF) and oriented strand board (OSB) was characterized. A microbalance was used to measure sorption/desorption kinetics and equilibrium data. While styrene transport in PSF can be described by Fickian diffusion with a symmetrical and reversible sorption/desorption process, hexanal transport in both PSF and OSB exhibited significant hysteresis, with desorption being much slower than sorption. A porous media diffusion model that assumes instantaneous local equilibrium governed by a nonlinear Freundlich isotherm was found to explain the hysteresis in hexanal transport. A new nonlinear sorption and porous diffusion emissions model was, therefore, developed and partially validated using independent chamber data. The results were also compared to the more conventional linear Fickian-diffusion emissions model. While the linear emissions model predicts styrene emissions from PSF with reasonable accuracy, it substantially underestimates the rate of hexanal emissions from OSB. Although further research and more rigorous validation is needed, the new nonlinear emissions model holds promise for predicting emissions of polar VOCs such as hexanal from porous building materials.

Treatment of model solutions and wastewater containing selected hazardous metal ions using a chitin/lignin hybrid material as an effective sorbent.

PubMed

Bartczak, Przemysław; Klapiszewski, Łukasz; Wysokowski, Marcin; Majchrzak, Izabela; Czernicka, Weronika; Piasecki, Adam; Ehrlich, Hermann; Jesionowski, Teofil

2017-12-15

A chitin/lignin material with defined physicochemical and morphological properties was used as an effective adsorbent of environmentally toxic metals from model systems. Particularly significant is its use in the neutralization of real industrial wastes. The ions Ni 2+ , Cu 2+ , Zn 2+ and Pb 2+ were adsorbed on the functional sorbent, confirming the high sorption capacity of the newly obtained product, primarily due to the presence on its surface of numerous active functional groups from the component biopolymers. The kinetics of the process of ion adsorption from model solution were investigated, and the experimental data were found to fit significantly better to a type 1 pseudo-second-order kinetic model, as confirmed by the high correlation coefficient of 0.999 for adsorption of both nickel(II) copper(II) zinc(II) and lead(II) ions. The experimental data obtained on the basis of adsorption isotherms corresponded to the Langmuir model. The sorption capacity of the chitin/lignin material was measured at 70.41 mg(Ni 2+ )/g, 75.70 mg(Cu 2+ )/g, 82.41 mg(Zn 2+ )/g and 91.74 mg(Pb 2+ )/g. Analysis of thermodynamic parameters confirmed the endothermic nature of the process. It was also shown that nitric acid is a very effective desorbing (regenerating) agent, enabling the chitin/lignin material to be reused as an effective sorbent of metal ions. The sorption abilities of the chitin/lignin system with respect to particular metal ions can be ordered in the sequence Ni 2+

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.

Feasibility study on the application of coal gangue as landfill liner material.

PubMed

Wu, Hui; Wen, Qingbo; Hu, Liming; Gong, Meng; Tang, Zili

2017-05-01

Coal gangue is one of the largest industrial solid waste all over the world, and many methods have been proposed for the recycling of coal gangue. In the present study, the feasibility of using coal gangue as landfill liner material is studied through a series of laboratory tests in terms of hydraulic conductivity, sorption characteristics and leaching behavior. The results indicated that the hydraulic conductivity of coal gangue could be smaller than the regulatory requirement 1×10 -7 cm/s with a void ratio less than 0.60. The batch sorption experiments performed on Pb 2+ and Zn 2+ illustrated that the coal gangue showed remarkable sorption capacity for the two heavy metals, and the sorption capacity for Pb 2+ was larger than that for Zn 2+ . Both the pseudo first-order and pseudo second-order models fitted well with the sorption kinetics data of the Pb 2+ and Zn 2+ on the coal gangue, and the Langmuir model was found to best-fit the sorption isotherms. The sorption capacity decreased in presence of multiple heavy metals, both for Pb 2+ and Zn 2+ . Concentrations of heavy metals leached from the coal gangue were all below the regulatory limits from China MEP and U.S. EPA. These desirable characteristics indicated that the coal gangue has potential to be used as landfill liner materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

As(III) and As(V) sorption on iron-modified non-pyrolyzed and pyrolyzed biomass from Petroselinum crispum (parsley).

PubMed

Jiménez-Cedillo, M J; Olguín, M T; Fall, C; Colin-Cruz, A

2013-03-15

The sorption of As(III) and As(V) from aqueous solutions onto iron-modified Petroselinum crispum (PCFe) and iron-modified carbonaceous material from the pyrolysis of P. crispum (PCTTFe) was investigated. The modified sorbents were characterized with scanning electron microscopy. The sorbent elemental composition was determined with energy-dispersive X-ray spectroscopy (EDS). The principal functional groups from the sorbents were determined with FT-IR. The specific surfaces and points of zero charge (pzc) of the materials were also determined. As(III) and As(V) sorption onto the modified sorbents were performed in a batch system. After the sorption process, the As content in the liquid and solid phases was determined with atomic absorption and neutron activation analyses, respectively. After the arsenic sorption processes, the desorption of Fe from PCFe and PCTTFe was verified with atomic absorption spectrometry. The morphology of PC changed after iron modification. The specific area and pzc differed significantly between the iron-modified non-pyrolyzed and pyrolyzed P. crispum. The kinetics of the arsenite and arsenate sorption processes were described with a pseudo-second-order model. The Langmuir-Freundlich model provided the isotherms with the best fit. Less than 0.02% of the Fe was desorbed from the PCFe and PCTTFe after the As(III) and As(V) sorption processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Immobilization of Magnetic Nanoparticles onto Amine-Modified Nano-Silica Gel for Copper Ions Remediation

PubMed Central

Elkady, Marwa; Hassan, Hassan Shokry; Hashim, Aly

2016-01-01

A novel nano-hybrid was synthesized through immobilization of amine-functionalized silica gel nanoparticles with nanomagnetite via a co-precipitation technique. The parameters, such as reagent concentrations, reaction temperature and time, were optimized to accomplish the nano-silica gel chelating matrix. The most proper amine-modified silica gel nanoparticles were immobilized with magnetic nanoparticles. The synthesized magnetic amine nano-silica gel (MANSG) was established and characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and vibrating sample magnetometry (VSM). The feasibility of MANSG for copper ions’ remediation from wastewater was examined. MANSG achieves a 98% copper decontamination from polluted water within 90 min. Equilibrium sorption of copper ions onto MANSG nanoparticles obeyed the Langmuir equation compared to the Freundlich, Temkin, Elovich and Dubinin-Radushkevich (D-R) equilibrium isotherm models. The pseudo-second-order rate kinetics is appropriate to describe the copper sorption process onto the fabricated MANSG. PMID:28773583

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.

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. The results are essentially in keeping with the model that was previously proposed for sorption on the soil from water and from organic solvents.

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 for the three sludge types investigated.

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

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 environment afforded by n-hexadecane permits evaluation of direct electrostatic forces in NOM that contribute to sorption.

Biodegradation of sorbed chemicals in soil

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

Scow, K.M.; Fan, S.; Johnson, C.

Rates of biodegradation of sorbed chemicals are usually lower in soil than in aqueous systems, in part because sorption reduces the availability of the chemical to microorganisms. Biodegradation, sorption, and diffusion occur simultaneously and are tightly coupled. In soil, the rate of biodegradation is a function of a chemical`s diffusion coefficient, sorption partition coefficient, the distance it must diffuse from the site of sorption to microbial populations that can degrade it, and its biodegradation rate constant. A model (DSB model) was developed that describes biodegradation of chemicals limited in the availability by sorption and diffusion. Different kinetics expressions describe biodegradationmore » depending on whether the reaction is controlled by mass transfer (diffusion and sorption) or the intrinsic biodegradation rate, and whether biodegradation begins during or after the majority of sorption has occurred. We tested the hypothesis that there is a direct relationship between how strongly a chemical is sorbed and the chemical`s biodegradation rate. In six soils with different organic carbon contents, there was no relationship between the extent or rate of biodegradation and the sorption partition coefficient for phenanthrene. Aging of phenanthrene residues in soil led to a substantial reduction in the rate of biodegradation compared to biodegradation rates of recently added phenanthrene. Considerable research has focused on identification and development of techniques for enhancing in situ biodegradation of sorbed chemicals. Development of such techniques, especially those involving inoculation with microbial strains, should consider physical mass transfer limitations and potential decreases in bioavailability over time. 4 refs., 3 figs., 1 tab.« less

Selective separation of uranium using alizarin red S (ARS)-modified anion-exchange resin or by flotation of U-ARS chelate

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

Khalifa, M.E.

An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II),more » Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH {approx} 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.« less

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

PubMed

Reinoso-Maset, Estela; Worsfold, Paul J; Keith-Roach, Miranda J

2013-05-01

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand. The caesium sorption rate and equilibrium were unaffected by the complexing agents. Strontium however showed greater interaction with EDTA and NTA in the presence of desorbed matrix cations than geochemical modelling predicted, with SrNTA(-) enhancing sorption and SrEDTA(2-) showing lower sorption than Sr(2+). Complexing agents reduced UO2(2+) sorption to silica and enhanced the sorption rate in the natural sand system. Elevated concentrations of picolinate reduced the sorption of Sr(2+) and increased the sorption rate of UO2(2+), demonstrating the potential importance of this complexing agent. These experiments provide a direct comparison of the sorption behaviour of Cs(+), Sr(2+) and UO2(2+)onto natural sand and an assessment of the relative effects of EDTA, NTA and picolinate on the selected elements. Copyright © 2013 Elsevier Ltd. All rights reserved.

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 uncertainties of measured Eu concentrations in the range of analytical detection limits.

A surface complexation model of YREE sorption on Ulva lactuca in 0.05-5.0 M NaCl solutions

NASA Astrophysics Data System (ADS)

Zoll, Alison M.; Schijf, Johan

2012-11-01

We present distribution coefficients, log iKS, for the sorption of yttrium and the rare earth elements (YREEs) on BCR-279, a dehydrated tissue homogenate of a marine macroalga, Ulva lactuca, resembling materials featured in chemical engineering studies aimed at designing renewable biosorbents. Sorption experiments were conducted in NaCl solutions of different ionic strength (0.05, 0.5, and 5.0 M) at T = 25 °C over the pH range 2.7-8.5. Distribution coefficients based on separation of the dissolved and particulate phase by conventional filtration (<0.22 μm) were corrected for the effect of colloid-bound YREEs (>3 kDa) using an existing pH-dependent model. Colloid-corrected values were renormalized to free-cation concentrations by accounting for YREE hydrolysis and chloride complexation. At each ionic strength, the pH dependence of the renormalized values is accurately described with a non-electrostatic surface complexation model (SCM) that incorporates YREE binding to three monoprotic functional groups, previously characterized by alkalimetric titration, as well as binding of YREE-hydroxide complexes (MOH2+) to the least acidic one (pKa ∼ 9.5). In non-linear regressions of the distribution coefficients as a function of pH, each pKa was fixed at its reported value, while stability constants of the four YREE surface complexes were used as adjustable parameters. Data for a single fresh U. lactuca specimen in 0.5 M NaCl show generally the same pH-dependent behavior but a lower degree of sorption and were excluded from the regressions. Good linear free-energy relations (LFERs) between stability constants of the YREE-acetate and YREE-hydroxide solution complex and surface complexes with the first and third functional group, respectively, support their prior tentative identifications as carboxyl and phenol. A similar confirmation for the second group is precluded by insufficient knowledge of the stability of YREE-phosphate complexes and a perceived lack of YREE binding in 0.05 M NaCl; this issue awaits further study. The results indicate that SCMs can be successfully applied to sorbents as daunting as marine organic matter. Despite remnant challenges, for instance resolving the contributions of individual groups to the aggregate sorption signal, our approach helps formalize seaweed’s avowed promise as an ideal biomonitor or biofilter of metal pollution in environments ranging from freshwaters to brines by uncovering what chemical mechanisms underlie its pronounced affinity for YREEs and other surface-reactive elements.

Turbulent coagulation of particles smaller than the length scales of turbulence and equilibrium sorption of phenanthrene to clay: Implications for pollutant transport in the estuarine water column

NASA Astrophysics Data System (ADS)

Brunk, Brett Kenneth

1997-11-01

Pollutant and particle transport in estuaries is affected by a multitude of physical, chemical and biological processes. In this research the importance of equilibrium sorption and turbulent coagulation were studied. Sorption in estuaries was modeled using phenanthrene, bacterial extracellular polymer and kaolinite clay as surrogates for a hydrophobic organic pollutant, dissolved organic matter and inorganic suspended sediment, respectively. Experiments over a range of estuarine salinities showed that ionic strength had the largest effect on the extent of sorption, while the effect of extracellular polymer coatings on the mineral surfaces was insignificant. Further calculations using typical estuarine suspended sediment concentrations indicated that equilibrium sorption could not fully account for the solid/solution phase distribution of hydrophobic organic compounds in the estuarine water column. For particles that are small compared to the length scales of turbulence, the rate of coagulation is related to the dynamics of the smallest turbulent eddies since they have the highest shear rate. Experimental and theoretical effort focused on determining the coagulation rate of spherical particles in isotropic turbulence. A pair diffusion approximation valid for rapidly fluctuating flows was used to calculate the rate of coagulation in a randomly varying isotropic linear flow field. Dynamic simulations of particle coagulation in Gaussian turbulence were computed over a range of representative values of particle-particle interactions (i.e, hydrodynamic interactions and van der Waals attraction) and total strain (i.e., the product of the strain rate and its time scale). The computed coagulation rates for isotropic turbulence differed from analytical approximations valid at large and small total strain. As expected, particle interactions were found to be significant. Experimental measurements of coagulation in grid-generated turbulence were obtained by measuring the loss of singlet particles from an initially monodisperse suspension as a function of turbulence intensity. Model predictions based on the particle Hamaker constant and spatial distribution of turbulence in the reactor agreed well with the experiments without the use of any fitting parameters. The close agreement of simulations and observations indicate the numerical model has successfully captured the relevant physics that governs the aggregation of colloidal particles in turbulent flows. This work is the first successful description of turbulent coagulation. Given the ubiquity of turbulent suspensions in engineered and natural systems, the ability to quantitatively describe particle behavior under these conditions is expected to have considerable utility.

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.

Pb(II) sorption from aqueous solution by novel biochar loaded with nano-particles.

PubMed

Wang, Chongqing; Wang, Hui

2018-02-01

Novel sorbent (HBC) is prepared by introducing nano-particles (Maghemite and EDTA functionalized layered double hydroxides) on biochar surface. FTIR, XRD, SEM and EDS are used to characterize the biochar nanocomposites. Pb(II) sorption is highly dependent on solution pH. Sorption kinetics and isotherms indicate that Pb(II) sorption onto the sorbents follows pseudo-second order model and Langmuir isotherm. The maximum sorption capacity of Pb(II) onto HBC is up to146.84 mg g -1 , higher than previously reported sorbents. The magnetic particles enable easy separation of HBC from aqueous solution by external magnetic fields. HBC can be used as effective sorbent for removal of heavy metals from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange - Influence of material properties, sorption mechanism and modeling.

PubMed

Schuricht, Falk; Borovinskaya, Ekaterina S; Reschetilowski, Wladimir

2017-04-01

Perfluorooctane sulfonate (PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N 2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force (LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient β s . The big difference in the initial mass transfer coefficient β s,0 , when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate. But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range. Copyright © 2016. Published by Elsevier B.V.

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

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.

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.

Quaternized Cellulose Hydrogels as Sorbent Materials and Pickering Emulsion Stabilizing Agents

PubMed Central

Udoetok, Inimfon A.; Wilson, Lee D.; Headley, John V.

2016-01-01

Quaternized (QC) and cross-linked/quaternized (CQC) cellulose hydrogels were prepared by cross-linking native cellulose with epichlorohydrin (ECH), with subsequent grafting of glycidyl trimethyl ammonium chloride (GTMAC). Materials characterization via carbon, hydrogen and nitrogen (CHN) analysis, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR)/13C solid state NMR spectroscopy provided supportive evidence of the hydrogel synthesis. Enhanced thermal stability of the hydrogels was observed relative to native cellulose. Colloidal stability of octanol and water mixtures revealed that QC induces greater stabilization over CQC, as evidenced by the formation of a hexane–water Pickering emulsion system. Equilibrium sorption studies with naphthenates from oil sands process water (OSPW) and 2-naphthoxy acetic acid (NAA) in aqueous solution revealed that CQC possess higher affinity relative to QC with the naphthenates. According to the Langmuir isotherm model, the sorption capacity of CQC for OSPW naphthenates was 33.0 mg/g and NAA was 69.5 mg/g. CQC displays similar affinity for the various OSPW naphthenate component species in aqueous solution. Kinetic uptake of NAA at variable temperature, pH and adsorbent dosage showed that increased temperature favoured the uptake process at 303 K, where Qm = 76.7 mg/g. Solution conditions at pH 3 or 9 had a minor effect on the sorption process, while equilibrium was achieved in a shorter time at lower dosage (ca. three-fold lower) of hydrogel (100 mg vs. 30 mg). The estimated activation parameters are based on temperature dependent rate constants, k1, which reveal contributions from enthalpy-driven electrostatic interactions. The kinetic results indicate an ion-based associative sorption mechanism. This study contributes to a greater understanding of the adsorption and physicochemical properties of cellulose-based hydrogels. PMID:28773767

Synthesis of hydrophobic cross-linked polyzwitterionic acid for simultaneous sorption of Eriochrome black T and chromium ions from binary hazardous waters.

PubMed

Saleh, Tawfik A; Muhammad, Auwal M; Ali, Shaikh A

2016-04-15

Hydrophobic cross-linked polyzwitterionic acid (HCPZA) containing long chain (C18) hydrophobes and residues of a glutamic acid having unquenched nitrogen valency was synthesized. Exploiting the chelating ability of the amino acid residues to scavenge toxic metals and the hydrophobic surface to scoop up the organic contaminants, the resin HCPZA was evaluated for simultaneous removal of chromium and Eriochrome black T (EBT) from wastewaters. The structure and morphology of the polymer before and after sorption were characterized by using FTIR, TGA, EDX and SEM. The effect of various parameters such as contact time, pH and initial concentrations were investigated to arrive at optimum conditions. The adsorption of Eriochrome black T and Cr (III) on HCPZA reached equilibrium in 30 min. The mechanism of adsorption was investigated using kinetic, diffusion and isotherm models. The adsorption kinetic data were described well by the pseudo-second order model and by the Freundlich isotherm model. EDX analysis confirmed the adsorption of Cr (III) and EBT on the polymer. The hydrophobic resin exhibited a remarkable simultaneous adsorption capacity for EBT and Cr (III) and thus demonstrated its potential to be a promising adsorbent for removal of dyes and heavy metal ions from wastewaters. Copyright © 2016 Elsevier Inc. All rights reserved.

Calcium-alginate/carbon nanotubes/TiO2 composite beads for removal of bisphenol A.

PubMed

Hartono, Maria R; Kushmaro, Ariel; Marks, Robert S; Chen, Xiaodong

2016-10-01

In this study, composite calcium-alginate/carbon nanotubes/TiO 2 beads were prepared and tested for their potential in the removal of bisphenol A (BPA) from aqueous solutions. The removal traits were inspected using a fixed-bed sorption column. By varying parameters such as bed height (15-20 cm), flow rate (2.0-6.0 mL.min -1 ) and inlet BPA concentration (10-30 mg.L -1 ) we assessed the removal capacity of these composites. The highest sorption capacity of 5.46 mg.g -1 was achieved at 10 mg.L -1 BPA concentration, 2.0 mL.min -1 flow rate and 20 cm bed height at saturation. Adams-Bohart, Yoon-Nelson and Dose-Response isotherm models were applied to evaluate the performance of the column at different inlet concentrations. The experimental data satisfactorily fit the Dose-Response model with high correlation (r 2 > 0.97) across the breakthrough curve. Regeneration of the used adsorbent beads were performed by immersion in the desorption solvent followed by light irradiation. It was postulated that inclusion of TiO 2 facilitates the desorbed pollutant degradation from the used adsorbent beads.

Scaling Effects of Cr(VI) Reduction Kinetics. The Role of Geochemical Heterogeneity

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

Wang, Li; Li, Li

2015-10-22

The natural subsurface is highly heterogeneous with minerals distributed in different spatial patterns. Fundamental understanding of how mineral spatial distribution patterns regulate sorption process is important for predicting the transport and fate of chemicals. Existing studies about the sorption was carried out in well-mixed batch reactors or uniformly packed columns, with few data available on the effects of spatial heterogeneities. As a result, there is a lack of data and understanding on how spatial heterogeneities control sorption processes. In this project, we aim to understand and develop modeling capabilities to predict the sorption of Cr(VI), an omnipresent contaminant in naturalmore » systems due to its natural occurrence and industrial utilization. We systematically examine the role of spatial patterns of illite, a common clay, in determining the extent of transport limitation and scaling effects associated with Cr(VI) sorption capacity and kinetics using column experiments and reactive transport modeling. Our results showed that the sorbed mass and rates can differ by an order of magnitude due to of the illite spatial heterogeneities and transport limitation. With constraints from data, we also developed the capabilities of modeling Cr(VI) in heterogeneous media. The developed model is then utilized to understand the general principles that govern the relationship between sorption and connectivity, a key measure of the spatial pattern characteristics. This correlation can be used to estimate Cr(VI) sorption characteristics in heterogeneous porous media. Insights gained here bridge gaps between laboratory and field application in hydrogeology and geochemical field, and advance predictive understanding of reactive transport processes in the natural heterogeneous subsurface. We believe that these findings will be of interest to a large number of environmental geochemists and engineers, hydrogeologists, and those interested in contaminant fate and transport, water quality and water composition, and natural attenuation processes in natural systems.« less

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 dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.

The effect of mineral composition on the sorption of cesium ions on geological formations.

PubMed

Kónya, József; Nagy, Noémi M; Nemes, Zoltán

2005-10-15

The sorption of cesium-137 on rock samples, mainly on clay rocks, is determined as a function of the mineral composition of the rocks. A relation between the mineral groups (tectosilicates, phyllosilicates, clay minerals, carbonates) and their cesium sorption properties is shown. A linear model is constructed by which the distribution coefficients of the different minerals can be calculated from the mineral composition and the net distribution coefficient of the rock. On the basis of the distribution coefficients of the minerals the cesium sorption properties of other rocks can be predicted.

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 glass chromatography columns, homogenously packed with soil, saturated with 5 mM CaCl2 solution, and injected with 100 mg/L sildenafil. The effluent solution concentrations were plotted as a function of time to plot breakthrough curves. Sildenafil was significantly retarded in clay-rich soil column experiments confirming trends observed in sorption experiments. Overall data indicate very strong sorption of sildenafil to both organic- rich and clay-rich soils, but stronger sorption to clay-rich soils. Strong soil sorption acts as a filter for water, leaving the PC behind in the soils. These results suggest that little sildenafil will reside in groundwater once exposed to natural soils. Further research is needed to better understand how sildenafil's metabolites respond in ecosystems. Given the high metabolic rate and long shelf life of sildenafil, these metabolites may be more prevalent in natural soils.

Site energy distribution analysis and influence of Fe3O4 nanoparticles on sulfamethoxazole sorption in aqueous solution by magnetic pine sawdust biochar.

PubMed

Reguyal, Febelyn; Sarmah, Ajit K

2018-02-01

Magnetisation of carbonaceous adsorbents using iron oxides has been found to be one of the potential solutions for easy recovery of adsorbent after use. We evaluated the effects of Fe 3 O 4 nanoparticle addition on the physico-chemical properties of biochar and its sorption properties. Five adsorbents with varying amount of Fe 3 O 4 per mass of adsorbent (0%, 25%, 50%, 75% and 100%) were used to adsorb sulfamethoxazole (SMX), an emerging micropollutant. Five isotherm models were used to evaluate the sorption behaviour of SMX onto the adsorbents where Redlich-Peterson model was found to best describe the data. Based on this model, the approximate site energy distribution for each adsorbent was determined. Surface area and sorption capacity had strong negative linear relationship with the amount of Fe 3 O 4 per mass of adsorbent while the pore volume and saturation magnetisation of the adsorbent increased with increasing percentage of Fe 3 O 4 . The results of the approximate site energy distribution analysis showed that the addition of Fe 3 O 4 on biochar reduced the area under the frequency distribution curve of sorption site energies leading to the lowering of the sorption sites available for SMX. This could be attributed to the blockage of the hydrophobic surface of biochar reducing the hydrophobic interaction between SMX and biochar. Copyright © 2017 Elsevier Ltd. All rights reserved.

Use of metallurgical dust for removal chromium ions from aqueous solutions

NASA Astrophysics Data System (ADS)

Pająk, Magdalena; Dzieniszewska, Agnieszka; Kyzioł-Komosińska, Joanna; Chrobok, Michał

2018-01-01

The aim of the study was to determine the potential for the application of dust from steel plant as an effective sorbent for removing Cr(III) and Cr(VI) in the form of simple and complex ions - Acid Blue 193 dye from aqueous solutions. Three isotherms models were used to interpret the experimental results namely: Langmuir, Freundlich, and Dubinin-Radushkevich. Estimated equations parameters allowed to determine the binding mechanism. Based on laboratory studies it was found that the dust was characterized by high sorption capacities for Cr ions and dye from the aqueous solution. The sorption capacity of the dust for Cr(III) and Cr(VI) ions depended on the degree of oxidation, pH of solution and kind of anion and changed in series: Cr(III)-Cl pH=5.0> Cr(III)-SO4 pH=5.0> Cr(III)-Cl pH=3.0> Cr(III)-SO4 pH=3.0> Cr(VI) pH=5.0> Cr(VI) pH=3.0. Dust was also characterized by a high maximum sorption capacity of dye at a range of 38.2 - 91.7 mg/g, depending on the dose of dust. Based on the study it was found that dust from a steel plant, containing iron oxides, can be used as low-cost and effective sorbent to remove pollutions containing chromium ions, especially from acidic wastewater.

Facile functionalized of SBA-15 via a biomimetic coating and its application in efficient removal of uranium ions from aqueous solution.

PubMed

Gao, Jun-Kai; Hou, Li-An; Zhang, Guang-Hui; Gu, Ping

2015-04-09

A novel dopamine-functionalized mesoporous silica (DMS), synthesized by grafting dopamine onto a mesoporous molecular sieve (SBA-15), was developed as a sorbent to extract U(VI) from aqueous solution. The method used to modify SBA-15 was simple, facile and cost-effective. The DMS was characterized by SEM, TEM, XRD and BET, showing that the material had an ordered mesoporous structure and a large surface area. The effect of contact time, pH, ionic strength, temperature, and solid-liquid ratio on the sorption process was investigated. It was demonstrated that the adsorption of U(VI) by DMS was fast and that it can be described by the pseudo-second order-equation where the equilibrium time was 20 min. Additionally, the adsorption isotherm data were fitted well by the Langmuir model with the maximum adsorption capacity of DMS of 196 mg/g at pH 6.0. Furthermore, the influence of the K(+) and Na(+) concentrations and solid-to-liquid ratio on the sorption was very weak, and the values of the thermodynamic parameters revealed that the sorption process was exothermic and spontaneous. All the results suggested that the DMS could be used as an excellent adsorbent to remove U(VI) from aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Modification of a method-of-characteristics solute-transport model to incorporate decay and equilibrium-controlled sorption or ion exchange

USGS Publications Warehouse

Goode, D.J.; Konikow, Leonard F.

1989-01-01

The U.S. Geological Survey computer model of two-dimensional solute transport and dispersion in ground water (Konikow and Bredehoeft, 1978) has been modified to incorporate the following types of chemical reactions: (1) first-order irreversible rate-reaction, such as radioactive decay; (2) reversible equilibrium-controlled sorption with linear, Freundlich, or Langmuir isotherms; and (3) reversible equilibrium-controlled ion exchange for monovalent or divalent ions. Numerical procedures are developed to incorporate these processes in the general solution scheme that uses method-of- characteristics with particle tracking for advection and finite-difference methods for dispersion. The first type of reaction is accounted for by an exponential decay term applied directly to the particle concentration. The second and third types of reactions are incorporated through a retardation factor, which is a function of concentration for nonlinear cases. The model is evaluated and verified by comparison with analytical solutions for linear sorption and decay, and by comparison with other numerical solutions for nonlinear sorption and ion exchange.

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.

Phase I Contaminant Transport Parameters for the Groundwater Flow and Contaminant Transport Model of Corrective Action Unit 97: Yucca Flat/Climax Mine, Nevada Test Site, Nye County, Nevada, Revision 0

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

John McCord

2007-09-01

This report documents transport data and data analyses for Yucca Flat/Climax Mine CAU 97. The purpose of the data compilation and related analyses is to provide the primary reference to support parameterization of the Yucca Flat/Climax Mine CAU transport model. Specific task objectives were as follows: • Identify and compile currently available transport parameter data and supporting information that may be relevant to the Yucca Flat/Climax Mine CAU. • Assess the level of quality of the data and associated documentation. • Analyze the data to derive expected values and estimates of the associated uncertainty and variability. The scope of thismore » document includes the compilation and assessment of data and information relevant to transport parameters for the Yucca Flat/Climax Mine CAU subsurface within the context of unclassified source-term contamination. Data types of interest include mineralogy, aqueous chemistry, matrix and effective porosity, dispersivity, matrix diffusion, matrix and fracture sorption, and colloid-facilitated transport parameters.« less

Biochar: a green sorbent to sequester acidic organic contaminants

NASA Astrophysics Data System (ADS)

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

2015-04-01

Biochar is a carbon rich product of biomass pyrolysis that exhibits a high sorption potential towards a wide variety of inorganic and organic contaminants. Because it is a valuable soil additive and a potential carbon sink that can be produced from renewable resources, biochar has gained growing attention for the development of more sustainable remediation strategies. A lot of research efforts have been dedicated to the sorption of hydrophobic contaminants and metals to biochar. Conversely, the understanding of the sorption of acidic organic contaminants remains limited, and questions remain on the influence of biochar characteristics (e.g. ash content) on the sorption behaviour of acidic organic contaminants. To address this knowledge gap, sorption batch experiments were conducted with a series of structurally similar acidic organic contaminants covering a range of dissociation constant (2,4-D, MCPA, 2,4-DB and triclosan). The sorbents selected for experimentation included a series of 10 biochars covering a range of characteristics, multiwalled carbon nanotubes as model for pure carbonaceous phases, and an activated carbon as benchmark. Overall, sorption coefficient [L/kg] covered six orders of magnitude and generally followed the order 2,4-D < MCPA < 2,4-DB < triclosan. Combining comprehensive characterization of the sorbents with the sorption dataset allowed the discussion of sorption mechanisms and driving factors of sorption. Statistical analysis suggests that (i) partitioning was the main driver for sorption to sorbents with small specific surface area (< 25 m²/g), whereas (ii) specific mechanisms dominated sorption to sorbents with larger specific surface area. Results showed that factors usually not considered for the sorption of neutral contaminants play an important role for the sorption of organic acids. The pH dependent lipophilicity ratio (i.e. D instead of Kow), ash content and ionic strength are key factors influencing the sorption of acidic organic contaminants to biochars. Overall, the identified factors, as well as the environmental matrix, should be carefully considered when selecting the type of biochar for sequestration purposes.

Microplastics play a minor role in tetracycline sorption in the presence of dissolved organic matter.

PubMed

Xu, Baile; Liu, Fei; Brookes, Philip C; Xu, Jianming

2018-09-01

Microplastics have a great potential to sorb organic pollutants from the adjacent environment. In this study, the sorption of tetracycline, a polar and ionizable antibiotic, on three types of microplastics (polyethylene (PE), polypropylene (PP) and polystyrene (PS)) were investigated in batch sorption experiments. The sorption isotherms were well fitted by the Langmuir model, indicating that not only hydrophobic interactions but also other interactions (e.g. electrostatic interactions) played important roles in the sorption process. PS had the maximum sorption capacity, following the order PS > PP > PE, which can be attributed to polar interactions and π-π interactions. The sorption of tetracycline on microplastics was significantly influenced by pH, with sorption capacity increasing gradually, peaking at pH 6.0 and then decreasing, likely due to the influence of tetracycline speciation with the change of pH. Fulvic acid was selected as representative dissolved organic matter (DOM) to examine the effect on sorption. The increasing concentration of fulvic acid inhibited the sorption of tetracycline on three microplastics, decreasing them by more than 90% at the fulvic acid concentration of 20 mg/L, which implied a greater affinity of tetracycline to fulvic acid than to microplastics. Increasing salinity from 0.05 to 3.5% had negligible effects on the sorption of tetracycline on the three microplastics. Our results highlight the importance of pH and DOM on the sorption of tetracycline on microplastics, and suggest the relatively minor role of microplastics in the fate and transport of tetracycline in the aquatic environment in the presence of DOM. Copyright © 2018 Elsevier Ltd. All rights reserved.

Porous nano-cerium oxide wood chip biochar composites for aqueous levofloxacin removal and sorption mechanism insights.

PubMed

Yi, Shengze; Sun, Yuanyuan; Hu, Xin; Xu, Hongxia; Gao, Bin; Wu, Jichun

2017-01-14

The adsorption removal of levofloxacin (LEV), a widely used fluoroquinolone antibiotic, by using the biochars derived from the pyrolysis of pine wood chip pretreated with cerium trichloride was investigated through batch sorption experiments and multiple characterization techniques. The differences in the basic physicochemical properties between Ce-impregnated biochars and the pristine biochars were confirmed by the analysis of elemental compositions, specific surface areas, energy dispersive spectrometry, X-ray diffraction, and thermo-gravimetry. FT-IR spectra of the pre- and post-sorption biochars confirmed the chemical adsorption for LEV sorption onto the biochars. Large shifts in the binding energy of Ce 3d , O 1s , C 1s , and N 1s regions on the pre- and post-sorption biochars indicated the surface complexation of LEV molecule onto the biochars. The binding species of Ce 4+ and Ce 3+ identified by X-ray photoelectron spectroscopy reflect the role of Ce oxides during sorption. Batch adsorption showed the significant enhancement of adsorption capacity for LEV after the Ce modification. Batch adsorption kinetic data fitted well with the pseudo-second-order model. Both the Langmuir and the Freundlich models reproduced the isotherm data well. Findings from this work indicated that Ce-impregnated biochars can be effective for the removal of aqueous LEV.

Chemically modified biochar produced from conocarpus waste increases NO3 removal from aqueous solutions.

PubMed

Usman, Adel R A; Ahmad, Mahtab; El-Mahrouky, Mohamed; Al-Omran, Abdulrasoul; Ok, Yong Sik; Sallam, Abdelazeem Sh; El-Naggar, Ahmed H; Al-Wabel, Mohammad I

2016-04-01

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO3 removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO3 sorption capacity of 45.36 mmol kg(-1) predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO3 sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m(2) g(-1)) and formation of strong ionic complexes with NO3. At an initial pH of 2, more than 89 % NO3 removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.

Algal Foams Applied in Fixed-Bed Process for Lead(II) Removal Using Recirculation or One-Pass Modes

PubMed Central

Wang, Shengye; Vincent, Thierry; Faur, Catherine; Guibal, Eric

2017-01-01

The incorporation of brown algae into biopolymer beads or foams for metal sorption has been previously reported. However, the direct use of these biomasses for preparing foams is a new approach. In this study, two kinds of porous foams were prepared by ionotropic gelation using algal biomass (AB, Laminaria digitata) or alginate (as the reference) and applied for Pb(II) sorption. These foams (manufactured as macroporous discs) were packed in filtration holders (simulating fixed-bed column) and the system was operated in either a recirculation or a one-pass mode. Sorption isotherms, uptake kinetics and sorbent reuse were studied in the recirculation mode (analogous to batch system). In the one-pass mode (continuous fixed-bed system), the influence of parameters such as flow rate, feed metal concentration and bed height were investigated on both sorption and desorption. In addition, the effect of Cu(II) on Pb(II) recovery from binary solutions was also studied in terms of both sorption and desorption. Sorption isotherms are well fitted by the Langmuir equation while the pseudo-second order rate equation described well both sorption and desorption kinetic profiles. The study of material regeneration confirms that the reuse of the foams was feasible with a small mass loss, even after 9 cycles. In the one-pass mode, for alginate foams, a slower flow rate led to a smaller saturation volume, while the effect of flow rate was less marked for AB foams. Competitive study suggests that the foams have a preference for Pb(II) over Cu(II) but cannot selectively remove Pb(II) from the binary solution. PMID:29039806

Modeling the influence of coupled mass transfer processes on mass flux downgradient of heterogeneous DNAPL source zones

NASA Astrophysics Data System (ADS)

Yang, Lurong; Wang, Xinyu; Mendoza-Sanchez, Itza; Abriola, Linda M.

2018-04-01

Sequestered mass in low permeability zones has been increasingly recognized as an important source of organic chemical contamination that acts to sustain downgradient plume concentrations above regulated levels. However, few modeling studies have investigated the influence of this sequestered mass and associated (coupled) mass transfer processes on plume persistence in complex dense nonaqueous phase liquid (DNAPL) source zones. This paper employs a multiphase flow and transport simulator (a modified version of the modular transport simulator MT3DMS) to explore the two- and three-dimensional evolution of source zone mass distribution and near-source plume persistence for two ensembles of highly heterogeneous DNAPL source zone realizations. Simulations reveal the strong influence of subsurface heterogeneity on the complexity of DNAPL and sequestered (immobile/sorbed) mass distribution. Small zones of entrapped DNAPL are shown to serve as a persistent source of low concentration plumes, difficult to distinguish from other (sorbed and immobile dissolved) sequestered mass sources. Results suggest that the presence of DNAPL tends to control plume longevity in the near-source area; for the examined scenarios, a substantial fraction (43.3-99.2%) of plume life was sustained by DNAPL dissolution processes. The presence of sorptive media and the extent of sorption non-ideality are shown to greatly affect predictions of near-source plume persistence following DNAPL depletion, with plume persistence varying one to two orders of magnitude with the selected sorption model. Results demonstrate the importance of sorption-controlled back diffusion from low permeability zones and reveal the importance of selecting the appropriate sorption model for accurate prediction of plume longevity. Large discrepancies for both DNAPL depletion time and plume longevity were observed between 2-D and 3-D model simulations. Differences between 2- and 3-D predictions increased in the presence of sorption, especially for the case of non-ideal sorption, demonstrating the limitations of employing 2-D predictions for field-scale modeling.

The sorption kinetics and isotherms of sulfamethoxazole with polyethylene microplastics.

PubMed

Xu, Baile; Liu, Fei; Brookes, Philip C; Xu, Jianming

2018-06-01

Microplastics and sulfamethoxazole coexist ubiquitously in the marine environment, and microplastics tend to sorb organic pollutants from the surrounding environment. Here, the sorption kinetics and isotherms of sulfamethoxazole on polyethylene (PE) microplastics closely fitted a pseudo-second-order model (R 2  = 0.98) and linear model (R 2  = 0.99), respectively, indicating that the sorption process was partition-dominant interaction. The main binding mechanism was possibly the van der Waals interaction for hydrophilic sulfamethoxazole onto hydrophobic PE microplastics. The effects of pH, dissolved organic matter and salinity on sorption behavior were also studied. The sorption behavior of sulfamethoxazole on PE microplastics was not significantly influenced by pH and salinity, probably because the electrostatic repulsion played a minor role. In addition, the negligible effect of dissolved organic matter was attributed to the greater affinity of sulfamethoxazole to PE microplastics than to dissolved organic matter. Our results demonstrated that PE microplastics may serve as a carrier for sulfamethoxazole in the aquatic environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigation of Fission Product Transport into Zeolite-A for Pyroprocessing Waste Minimization

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

James R. Allensworth; Michael F. Simpson; Man-Sung Yim

Methods to improve fission product salt sorption into zeolite-A have been investigated in an effort to reduce waste associated with the electrochemical treatment of spent nuclear fuel. It was demonstrated that individual fission product chloride salts were absorbed by zeolite-A in a solid-state process. As a result, recycling of LiCl-KCl appears feasible via adding a zone-freezing technique to the current treatment process. Ternary salt molten-state experiments showed the limiting kinetics of CsCl and SrCl2 sorption into the zeolite. CsCl sorption occurred rapidly relative to SrCl2 with no observed dependence on zeolite particle size, while SrCl2 sorption was highly dependent onmore » particle size. The application of experimental data to a developed reaction-diffusion-based sorption model yielded diffusivities of 8.04 × 10-6 and 4.04 × 10-7 cm2 /s for CsCl and SrCl2, respectively. Additionally, the chemical reaction term in the developed model was found to be insignificant compared to the diffusion term.« less

Quantitative high-resolution mapping of phenanthrene sorption to black carbon particles.

PubMed

Obst, Martin; Grathwohl, Peter; Kappler, Andreas; Eibl, Oliver; Peranio, Nicola; Gocht, Tilman

2011-09-01

Sorption of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) to black carbon (BC) particles has been the focus of numerous studies. Conclusions on sorption mechanisms of PAH on BC were mostly derived from studies of sorption isotherms and sorption kinetics, which are based on batch experiments. However, mechanistic modeling approaches consider processes at the subparticle scale, some including transport within the pore-space or different spatial pore-domains. Direct evidence based on analytical techniques operating at the submicrometer scale for the location of sorption sites and the adsorbed species is lacking. In this work, we identified, quantified, and mapped the sorption of PAHs on different BC particles (activated carbon, charcoal and diesel soot) on a 25-100 nm scale using scanning transmission X-ray microscopy (STXM). In addition, we visualized the pore structure of the particles by transmission electron microscopy (TEM) on the 1-10 nm-scale. The combination of the chemical information from STXM with the physical information from TEM revealed that phenanthrene accumulates in the interconnected pore-system along primary "cracks" in the particles, confirming an adsorption mechanism.

Evaluating phenanthrene sorption on various wood chars

USGS Publications Warehouse

James, G.; Sabatini, D.A.; Chiou, C.T.; Rutherford, D.; Scott, A.C.; Karapanagioti, H.K.

2005-01-01

A certain amount of wood char or soot in a soil or sediment sample may cause the sorption of organic compounds to deviate significantly from the linear partitioning commonly observed with soil organic matter (SOM). Laboratory produced and field wood chars have been obtained and analyzed for their sorption isotherms of a model solute (phenanthrene) from water solution. The uptake capacities and nonlinear sorption effects with the laboratory wood chars are similar to those with the field wood chars. For phenanthrene aqueous concentrations of 1 ??gl-1, the organic carbon-normalized sorption coefficients (log Koc) ranging from 5.0 to 6.4 for field chars and 5.4-7.3 for laboratory wood chars, which is consistent with literature values (5.6-7.1). Data with artificial chars suggest that the variation in sorption potential can be attributed to heating temperature and starting material, and both the quantity and heterogeneity of surface-area impacts the sorption capacity. These results thus help to corroborate and explain the range of log Koc values reported in previous research for aquifer materials containing wood chars. ?? 2004 Elsevier Ltd. All rights reserved.

Treatment of model and galvanic waste solutions of copper(II) ions using a lignin/inorganic oxide hybrid as an effective sorbent.

PubMed

Ciesielczyk, Filip; Bartczak, Przemysław; Klapiszewski, Łukasz; Jesionowski, Teofil

2017-04-15

A study was made concerning the removal of copper(II) ions from model and galvanic waste solutions using a new sorption material consisting of lignin in combination with an inorganic oxide system. Specific physicochemical properties of the material resulted from combining the activity of the functional groups present in the structure of lignin with the high surface area of the synthesized oxide system (585m 2 /g). Analysis of the porous structure parameters, particle size and morphology, elemental composition and characteristic functional groups confirmed the effective synthesis of the new type of sorbent. A key element of the study was a series of tests of adsorption of copper(II) ions from model solutions. It was determined how the efficiency of the adsorption process was affected by the process time, mass of sorbent, concentration of adsorbate, pH and temperature. Potential regeneration of adsorbent, which provides the possibility of its reusing and recovering the adsorbed copper, was also analyzed. The sorption capacity of the material was measured (83.98mg/g), and the entire process was described using appropriate kinetic models. The results were applied to the design of a further series of adsorption tests, carried out on solutions of real sewage from a galvanizing plant. Copyright © 2017 Elsevier B.V. All rights reserved.

Biosorption of lead ions from aqueous effluents by rapeseed biomass.

PubMed

Morosanu, Irina; Teodosiu, Carmen; Paduraru, Carmen; Ibanescu, Dumitrita; Tofan, Lavinia

2017-10-25

Lead, as well as other heavy metals, is regarded as priority pollutant due to its non-biodegradability, toxicity and persistence in the environment. In this study, rapeseed biomass was used in the biosorption of Pb(II) ions in batch and dynamic conditions, as well as with tests for industrial wastewater. The influence of initial concentration (5-250mg/L), pH and contact time (0.5-6h) was investigated. The kinetic data modeling resulted in good correlations with the pseudo-second order and intraparticle diffusion models. The maximum sorption capacities of Pb(II) were 18.35, 21.29 and 22.7mg/L at 4, 20 and 50°C, respectively. Thermodynamic parameters indicated the spontaneity and endothermic nature of lead biosorption on rapeseed biomass. The biosorption mechanism involves both physical and chemical interactions. The breakthrough curves at 50 and 100mg/L were determined and evaluated under dynamic conditions. The breakthrough time lowered with increasing the influent Pb(II) concentration. The experimental data obtained from fixed-bed column tests were well fitted by Thomas and Yoon-Nelson models. The calculated sorption capacities were in good agreement with the uptake capacity of Langmuir model. The applicability of rapeseed to be used as a sorbent for Pb(II) ions from real wastewater was tested, and Pb(II) removal efficiency of 94.47% was obtained. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite.

PubMed

Guimarães, Vanessa; Rodríguez-Castellón, Enrique; Algarra, Manuel; Rocha, Fernando; Bobos, Iuliu

2016-11-05

The UO2(2+) adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I=0.02M) and pH 6 (I=0.2M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8nm (sample PS2), to 5.1nm (sample PS3) and, to 7.4nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO2(2+) sorption on smectite. The amount of UO2(2+) adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8±0.3 and 382.2±0.3eV, assigned to hydrated UO2(2+) adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f7/2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3±0.3 and 381.8±0.3eV assigned to AlOUO2(+) and SiOUO2(+) surface species were observed at pH 6. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Thermodynamic studies for adsorption of ionizable pharmaceuticals onto soil.

PubMed

Maszkowska, Joanna; Wagil, Marta; Mioduszewska, Katarzyna; Kumirska, Jolanta; Stepnowski, Piotr; Białk-Bielińska, Anna

2014-09-01

Although pharmaceutical compounds (PCs) are being used more and more widely, and studies have been carried out to assess their presence in the environment, knowledge of their fate and behavior, especially under different environmental conditions, is still limited. The principle objective of the present work, therefore, is to evaluate the adsorption behavior of three ionizable, polar compounds occurring in different forms: cationic (propranolol - PRO), anionic (sulfisoxazole - SSX) and neutral (sulfaguanidine - SGD) onto soil under various temperature conditions. The adsorption thermodynamics of these researched compounds were extensively investigated using parameters such as enthalpy change (ΔH°), Gibbs free energy change (ΔG°) as well as entropy change (ΔS°). These calculations reveal that sorption of PRO is exothermic, spontaneous and enthalpy driven, sorption of SGD is endothermic, spontaneous and entropy driven whereas sorption of SSX is endothermic, spontaneous only above the temperature of 303.15K and entropy driven. Furthermore, we submit that the calculated values yield valuable information regarding the sorption mechanism of PRO, SGD and SSX onto soils. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sorption isotherm characteristics of aonla flakes.

PubMed

Alam, Md Shafiq; Singh, Amarjit

2011-06-01

The equilibrium moisture content was determined for un-osmosed and osmosed (salt osmosed and sugar osmosed) aonla flakes using the static method at temperatures of 25, 40,50, 60 and 70 °C over a range of relative humidities from 20 to 90%. The sorption capacity of aonla decreased with an increase in temperature at constant water activity. The sorption isotherms exhibited hysteresis, in which the equilibrium moisture content was higher at a particular equilibrium relative humidity for desorption curve than for adsorption. The hysteresis effect was more pertinent for un-osmosed and salt osmosed samples in comparison to sugar osmosed samples. Five models namely the modified Chung Pfost, modified Halsey, modified Henderson, modified Exponential and Guggenheim-Anderson-de Boer (GAB) were evaluated to determine the best fit for the experimental data. For both adsorption and desorption process of aonla fruit, the equilibrium moisture content of un-osmosed and osmosed aonla samples can be predicted well by GAB model as well as modified Exponential model. Moreover, the modified Exponential model was found to be the best for describing the sorption behaviour of un-osmosed and salt osmosed samples while, GAB model for sugar osmosed aonla samples.

Biosorption of molybdenum and chromium

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

Pryfogle, P.A.; Maiers, D.T.; Wichlacz, P.L.

1989-01-01

The effects of metal solution concentration, biomass density, length of exposure time, and pH were determined for biosorption of molybdenum (Mo) and chromium (Cr) by three organisms. Results indicate that it is possible to sorb Mo and Cr from dilute solutions. Differences were observed in the abilities of an organism to sorb Mo and Cr as well as among respective abilities of the three microorganisms. This suggests an inherent selectivity of the organism which may afford the selectivity of the organism which may afford the means to control a sorption-based process. Results also indicate that the metal sorption abilities ofmore » these microorganisms depend on duration of exposure, biomass density, solution pH, and the metal concentration of the solution. Each of these parameters suggests an additional means of controlling the sorption process. 20 refs., 6 figs., 3 tabs.« less

Water sorption studies of hybrid biofiber-reinforced natural rubber biocomposites.

PubMed

Jacob, Maya; Varughese, K T; Thomas, Sabu

2005-01-01

Hybrid biofibers (sisal and oil palm) were incorporated into natural rubber matrix. The water absorption characteristics of the composites were evaluated with reference to fiber loading. The influence of temperature on water sorption of the composites is also analyzed. Moisture uptake was found to be dependent on the properties of the biofibers. The mechanism of diffusion in the gum sample was found to be Fickian in nature, while in the loaded composites, it was non-Fickian. Sisal and oil palm fibers were subjected to different treatments such as mercerization and silanation. The effect of chemical modification on moisture uptake was also analyzed. Chemical modification was seen to decrease the water uptake in the composites. The thermodynamic parameters of the sorption process were also evaluated. Activation energy was found to be maximum for the gum sample.

Fabrication and investigation of MnFe2O4/MWCNTs nanocomposite by hydrothermal technique and adsorption of cationic and anionic dyes

NASA Astrophysics Data System (ADS)

Kafshgari, Leila Asadi; Ghorbani, Mohsen; Azizi, Asghar

2017-10-01

In present study, MnFe2O4/MWCNT nanocomposite synthesized using the hydrothermal technique and has been used for removal of DR16 and Y40 dyes from aqueous solutions. The characteristics results of FTIR, XRD, FESEM and TEM indicated that the nanoadsorbent was successfully fabricated. Magnetic sensitivity results demonstrated that the nanoparticles with saturation magnetization (Ms) value of 8.93 emu g-1 would have a fast magnetic response. The performance of adsorption was investigated in a batch reactor employing parameters expected to affect the maximum adsorption capacity (qm) such as pH, contact time, initial dye concentration and temperature. The highest sorption capacities of DR16 and Y40 after 300 min at 328 K were found to be 607.79 mg/g and 280 mg/g at pH of 2 and 6, respectively. The adsorption behavior over the time was assessed through pseudo-first, pseudo-second and Weber-Morris intra particle diffusion models. It was found that the pseudo-second order model gave the best agreement to the experimental data. Adsorbate-adsorbent interactions as a function of temperature was evaluated by Langmuir, Freundlich, Temkin and Sips isotherm models from which Sips isotherm had the highest consistency with the experimental data. Thermodynamic parameters including ΔG°, ΔS° and ΔH° were determined over the temperature range of 298-328 K. The results revealed that the adsorption reaction of DR16 onto MnFe2O4/MWCNT was spontaneous and exothermic, whilst the sorption process of Y40 was spontaneous and endothermic. In addition, activation energy values implied that the removal process of DR16 and Y40 was physical in nature.

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 approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

PubMed

Rakowska, M I; Kupryianchyk, D; Smit, M P J; Koelmans, A A; Grotenhuis, J T C; Rijnaarts, H H M

2014-03-15

Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene. Copyright © 2013 Elsevier Ltd. All rights reserved.

Combining sorption experiments and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to study the adsorption of propranolol onto environmental solid matrices - Influence of copper(II).

PubMed

Smith, Rose-Michelle; Sayen, Stéphanie; Nuns, Nicolas; Berrier, Elise; Guillon, Emmanuel

2018-05-23

The bioavailability of pharmaceuticals is governed by their sorption in soils/sediments, as the retention processes determine their concentration in surface- and ground-water. The adsorption of these contaminants can involve various solid components such as organic matter, clays and metallic oxides, and their distribution among these solid components depends on contaminant and solid properties. In this paper we studied the adsorption of the pharmaceutical propranolol - a beta-blocker - on eight different solids (six soils, one sediment and one kaolinite-based sample) by batch experiments. The influence of contact time, propranolol concentration and pH was considered, as well as the presence of copper(II). The investigated solids displayed a wide variability in terms of CEC (cationic exchange capacity) and organic carbon and carbonates contents. The influence of pH was negligible in the pH range from 5.5 to 8.6. The adsorbed amounts were greatly dependent on the solid and two groups of solids were evidenced: three soils of high CEC and organic carbon contents which retained high amounts of propranolol, and three soils, the sediment and the kaolinite-based sample (low CEC and organic carbon content) displaying a low adsorption capacity for the beta-blocker. A linear model enabling the determination of the sorption parameters K d and K oc was pertinent to describe the adsorption isotherms but the K oc values showed a great variability. It was shown that organic carbon content alone could not explain propranolol adsorption. The CEC value was identified as influent parameter and a simple empirical model was proposed to describe propranolol adsorption. At microscopic and molecular scales, ToF-SIMS experiments indicated (i) a decrease of potassium on the surface upon propranolol adsorption with a distribution of the beta-blocker similarly to alumino-silicates, iron and organic carbon on the surface confirming a cation exchange mechanism and (ii) the absence of degradation products and copper-propranolol complexes. Copyright © 2018. Published by Elsevier B.V.

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.

Biodegradation of organic chemicals in soil/water microcosms system: Model development

USGS Publications Warehouse

Liu, L.; Tindall, J.A.; Friedel, M.J.; Zhang, W.

2007-01-01

The chemical interactions of hydrophobic organic contaminants with soils and sediments may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. In order to illustrate the recalcitrance of chemical to degradation on sites, a sorption mechanism of intraparticle sequestration was postulated to operate on chemical remediation sites. Pseudo-first order sequestration kinetics is used in the study with the hypothesis that sequestration is an irreversibly surface-mediated process. A mathematical model based on mass balance equations was developed to describe the fate of chemical degradation in soil/water microcosm systems. In the model, diffusion was represented by Fick's second law, local sorption-desorption by a linear isotherm, irreversible sequestration by a pseudo-first order kinetics and biodegradation by Monod kinetics. Solutions were obtained to provide estimates of chemical concentrations. The mathematical model was applied to a benzene biodegradation batch test and simulated model responses correlated well compared to measurements of biodegradation of benzene in the batch soil/water microcosm system. A sensitivity analysis was performed to assess the effects of several parameters on model behavior. Overall chemical removal rate decreased and sequestration increased quickly with an increase in the sorption partition coefficient. When soil particle radius, a, was greater than 1 mm, an increase in radius produced a significant decrease in overall chemical removal rate as well as an increase in sequestration. However, when soil particle radius was less than 0.1 mm, an increase in radius resulted in small changes in the removal rate and sequestration. As pseudo-first order sequestration rate increased, both chemical removal rate and sequestration increased slightly. Model simulation results showed that desorption resistance played an important role in the bioavailability of organic chemicals in porous media. Complete biostabilization of chemicals on remediation sites can be achieved when the concentration of the reversibly sorbed chemical reduces to zero (i.e., undetectable), with a certain amount of irreversibly sequestrated chemical left inside the soil particle solid phase. ?? 2006 Springer Science + Business Media B.V.

Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.

PubMed

Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C

2016-08-01

The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.