Adsorption of alpha amino acids at the water/goethite interface

The adsorption of amino acids onto mineral surfaces plays an important role in a wide range of areas, e.g., low-temperature aqueous geochemistry, bone formation and protein-bone interactions. In this work, the adsorption of three alpha aminoacids (sarcosine, MIDA and EDDA) onto goethite (alpha-FeOOH) was studied as a function of pH and background electrolyte concentration at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The results showed that adsorption of alpha amino acids were strongly dependent on the functionality and structure of the ligands. No adsorption was detected for the zwitterionic sarcosine indicating that simple alpha amino acids without other ionizable and/or functional groups display insignificant affinity for mineral surfaces such as goethite. With respect to the more complex amino acids, which are surface reactive, the number and relative positions of carboxylate and amine groups determine the types of surface interactions. These interactions range from non-specific outer-sphere to specific inner-sphere interactions as shown by the MIDA and EDDA results, respectively. The results presented herein suggest that isomerically-selective adsorption might only occur for amino acids that are capable of specific surface interactions, either through site-specific hydrogen bonding or inner-sphere complexation.     

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments

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.     

Removal of Zn(II) from aqueous solution by natural halloysite nanotubes

Clay minerals have been widely used in wastewater disposal due to their strong sorption and complexation ability towards various environmental pollutants. In this study, the removal of Zn(II) from aqueous solution by natural halloysite nanotubes (HNTs) was studied as a function of various solution chemistry conditions such as contact time, pH, ionic strength, coexisting electrolyte ions and temperature under ambient conditions. The results indicated that the removal of Zn(II) by HNTs was strongly dependent on pH and ionic strength. Langmuir and Freundlich models were used to simulate the sorption isotherms of Zn(II) at three different temperatures of 293, 313 and 333 K. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) calculated from the temperature dependent sorption isotherms indicated that the removal process of Zn(II) by HNTs was endothermic and spontaneous. At low pH, the removal of Zn(II) was dominated by outer-sphere surface complexation and/or cation exchange with Na⁺/H⁺ on HNT surfaces, whereas inner-sphere surface complexation was the main removal mechanism at high pH. From the experimental results, one can conclude that HNTs may have a good potentiality for the disposal of Zn(II)-bearing wastewaters.     

Impact of environmental conditions on sorption of <Superscript>210</Superscript>Pb(II) to NKF-5 zeolite

The sorption of Pb(II) from aqueous solution using NKF-5 zeolite was investigated by batch technique under ambient conditions. The NKF-5 zeolite sample was characterized by using FTIR and X-ray powder diffraction in detail. The sorption of Pb(II) was investigated as a function of pH, ionic strength, foreign ions, and humic substances. The results indicated that the sorption of Pb(II) on NKF-5 zeolite was strongly dependent on pH. The sorption was dependent on ionic strength at low pH, but independent of ionic strength at high pH. At low pH, the sorption of Pb(II) was dominated by outer-sphere surface complexation and ion exchange with H⁺ on NKF-5 zeolite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. From the experimental results, one can conclude that NKF-5 zeolite has good potentialities for cost-effective preconcentration of Pb(II) from large volumes of aqueous solutions.     

Adsorption of organic matter at mineral/water interfaces: 5. Effects of adsorbed natural organic matter analogues on mineral dissolution

The effects of the adsorption of pyromellitate, an analogue for natural organic matter, on the dissolution behavior of corundum (alpha-Al2O3) have been examined over a wide range of pyromellitate concentrations (0-2.5 mM) and pH conditions (2-10). The adsorption modes of pyromellitate on corundum have first been examined using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and are shown to be dominated by a fully deprotonated, outer-sphere pyromellitate species ([triple bond]AlOH2+. . .Pyr4-) at pH >/= 5.0. At lower pH conditions, however, an additional protonated outer-sphere species ([triple bond]AlOH2+. . .H2Pyr2-) and an inner-sphere species are also evident. In accordance with the ATR-FTIR findings, modeling of macroscopic pyromellitate adsorption data using an extended constant capacitance treatment was possible using two outer-sphere ([triple bond]AlOH2+. . .Pyr4- and [triple bond]AlOH2+. . .H2Pyr2-) and one inner-sphere ([triple bond]AlPyr3-) adsorbed pyromellitate species. The presence of adsorbed pyromellitate strongly inhibited the dissolution of corundum under acidic (pH < 5) conditions, consistent with a mechanism previously proposed by Johnson et al. whereby outer-spherically adsorbed Pyr4- species sterically protect dissolution-active surface sites from attack by dissolution-promoting species such as protons. A reduction in the protolytic dissolution rate of corundum results. A reference Suwannee River fulvic acid, which also adsorbs to aluminum (oxyhydr)oxide surfaces in a predominantly outer-sphere manner, was similarly shown to strongly inhibit the dissolution of corundum at pH = 3.     

Solid-state preparation of hybrid organometallic-organic macrocyclic adducts with long chain dicarboxylic acids

The supramolecular macrocyclic adducts of general formula {[Fe(eta5-C5H4-C5H4N)2].[HOOC(CH2)nCOOH]}2 with n = 4 (adipic acid), n = 6 (suberic acid), n = 7 (azelaic acid) and n = 8 (sebacic acid) have been obtained quantitatively by kneading powdered samples of the crystalline organometallic and organic reactants with drops of MeOH (for n = 4, 6 and 7) and by direct crystallization from MeOH for n = 8, while the adduct with n = 5 represents an isomeric open chain alternative to the macrocycle.     

Effect of environmental conditions on 109Cd(II) sorption to MnO2

The sorption of Cd(II) from aqueous solution on MnO₂ was investigated under ambient conditions. Experiments were carried out as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid and temperature. The results indicated that the sorption of Cd(II) was strongly dependent on pH and ionic strength. At low pH, the sorption of Cd(II) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on MnO₂ surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin–Radushkevich models were used to simulate the sorption isotherms at three different temperatures. The thermodynamic data (ΔG ⁰, ΔS ⁰, ΔH ⁰) calculated from the temperature dependent sorption isotherms suggested that the sorption of Cd(II) on MnO₂ was an spontaneous and endothermic process.     

Removal of U(VI) from aqueous solutions by using attapulgite/iron oxide magnetic nanocomposites

The attapulgite/iron oxide magnetic nanocomposites were prepared by coprecipitation method and characterized by scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer and Fourier transform infrared sorption spectroscopy. The results of characterization showed that iron oxides were successfully deposited on the surfaces of attapulgite. The prepared magnetic nanocomposites were applied to remove radionuclide U(VI) ions from aqueous solutions by using batch technique and magnetic separation method. The results showed that the sorption of U(VI) on attapulgite/iron oxide magnetic composites was strongly dependent on ionic strength and pH at low pH values, and was independent of ionic strength at high pH values. The interaction of U(VI) with the magnetic nanocomposites was mainly dominated by outer-sphere surface complexation or ion exchange at low pH values, and was controlled by inner-sphere surface complexation or multinuclear surface complexation at high pH values. With increasing temperature, the sorption of U(VI) on attapulgite/iron oxide magnetic composites increased and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on the magnetic nanocomposites was a spontaneous and endothermic process. The high sorption capacity and easy magnetic separation of the attapulgite/iron oxide magnetic composites make the material as suitable sorbent in nuclear waste management.     

Impact of environmental conditions on the sorption behavior of Co(II) on Na-rectorite studied by batch experiments

The sorption of Co(II) from aqueous solution on Na-rectorite was investigated under ambient conditions. Experiments were carried out as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid and temperature. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH the sorption was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms at three different temperatures. The thermodynamic data (∆G ⁰, ∆S ⁰, ∆H ⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Co(II) on Na-rectorite was spontaneous and endothermic. Experimental results indicate that Na-rectorite is a suitable adsorbent for preconcentration and solidification of Co(II) from large volumes of aqueous solutions.     

Sorption of uranium(VI) on Na-attapulgite as a function of contact time,solid content,pH, ionic strength,temperature and humic acid

Sorption of U(VI) from aqueous solution to Na-attapulgite was investigated at different experimental chemistry conditions by using batch technique. The attapulgite sample was characterized by FTIR and XRD. Sorption of U(VI) on attapulgite was strongly dependent on pH and ionic strength. The sorption of U(VI) on attapulgite increased quickly with rising pH at pH < 6, and decreased with increasing pH at pH > 7. The presence of humic acid (HA) enhanced the sorption of U(VI) on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA with U(VI) on attapulgite surface. Sorption of U(VI) on attapulgite was mainly dominated by ion exchange and/or outer-sphere surface complexation at low pH values, whereas the sorption was attributed to the inner-sphere surface complexation or precipitation at high pH values. The sorption increased with increasing temperature and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on attapulgite was a spontaneous and endothermic process. The results indicate that attapulgite is a very suitable material for the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

Light scattering studies on Ficoll PM70 solutions reveal two distinct diffusive modes

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs相似文献   

Sorption of 63Ni(II) to montmorillonite as a function of pH, ionic strength, foreign ions and humic substances

Different kinds of clay minerals have been studied extensively in the removal of radionuclides from large volumes of aqueous solutions because of their high sorption capacity. Herein, the Na-montmorillonite was characterized by using XRD and FTIR in detail. The sorption of ⁶³Ni(II) from aqueous solution to montmorillonite as a function of pH, ionic strength, foreign ions, humic substances and temperature was studied by batch technique. The sorption of ⁶³Ni(II) on montmorillonite achieved equilibration quickly. The sorption of ⁶³Ni(II) to montmorillonite was strongly dependent on pH, and dependent on ionic strength at low pH and independent of ionic strength at high pH values. The sorption of ⁶³Ni(II) on montmorillonite was enhanced at low pH in the presence of humic acid (HA), while a negative effect of HA on ⁶³Ni(II) sorption was found at high pH values. At low pH values, the sorption of ⁶³Ni(II) was attributed to outer-sphere surface complexation or ion exchange, whereas the sorption was dominated by inner-sphere surface complexation at high pH values. The montmorillonite sample is a suitable material in the preconcentration of radionuclides from large volumes and the material can be used as backfill material in nuclear waste repository.     

Kinetic study on the sorption of dissolved natural organic matter onto different aquifer materials: the effects of hydrophobicity and functional groups

The subsurface sorption of Suwannee River fulvic acid (SRFA) and humic acid (SRHA) onto a synthetic aquifer material (iron-oxide-coated quartz) and two natural aquifer materials (Ringold sediment and Bemidji soils) was studied in both batch and column experiments. The hypothesis that hydrophobic effects followed by ligand exchange are the dominant mechanism contributing to the chemical sorption happening between dissolved natural organic matter (NOM) and the mineral surfaces is supported by observations of several phenomena: nonlinear isotherms, faster sorption rates versus slower desorption rates, phosphate competition, a solution pH increase during NOM sorption, and functional groups and aromaticity-related sorption. In addition, high-pressure size exclusion chromatography (HPSEC) and carboxylic acidity showed that lower molecular weight NOM components of SRHA are preferentially sorbed to iron oxide, a result in contrast to that for SRFA. Phosphate increased the desorption of sorbed NOM as well as soil organic matter. All of these trends support ligand exchange as the dominant reaction between NOM and the iron oxide surfaces; however, if the soil surface has been occupied by soil organic matter, then the sorption of NOM is more due to hydrophobic effect.     

Conformations, energies, and intramolecular hydrogen bonds in dicarboxylic acids: implications for the design of synthetic dicarboxylic acid receptors

The various conformers of the dicarboxylic acids HO2C--(CH2)n--CO2H, n = 1-4, were obtained using density functional methods (DFT), both in the gas phase and in the aqueous phase using a polarized continuum model (PCM). Several new conformers were identified, particularly for the two larger molecules glutaric (n = 3) and adipic acid (n =4). The PCM results show that the stability of most conformers were affected, many becoming unstable in the aqueous phase; and the energy ordering of conformers is also different. The results suggest that conformational preferences could be important in determining the design and stability of appropriate synthetic receptors for glutaric and adipic acid. Geometry changes between gas and aqueous phases were most marked in those conformers containing an intramolecular hydrogen bond. Additional calculations have probed the strength of intramolecular hydrogen bonds in these dicarboxylic acids. In the cases of glutaric and adipic acid, the strength of the intramolecular hydrogen bond were estimated to be around 28-29 kJ/mol, without any vibrational energy correction. The intramolecular hydrogen bond energies in malonic and succinic acid were also estimated from the calculated H-bond distances using an empirical relationship. Intramolecular H-bond redshifts of 170-250 cm(-1) have been estimated from the results of the harmonic frequency analyses.     

Removal of Co(II) from aqueous solution by using hydroxyapatite

Herein, hydroxyapatite (HAP) was prepared by aqueous precipitation technique and was characterized by using FT-IR and XRD to determine its chemical functional groups and micro-structure. The removal of cobalt from aqueous solution to HAP was studied by batch technique as a function of various environmental parameters such as contact time, pH, ionic strength, foreign ions, fulvic acid (FA), and temperature under ambient conditions. The results indicated that the sorption of Co(II) on HAP was strongly dependent on pH and ionic strength. The presence of FA enhanced the sorption of Co(II) on HAP at low pH, whereas reduced Co(II) sorption on HAP at high pH. The Langmuir, Freundlich and D-R models were used to simulate the sorption isotherms at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) calculated from the temperature dependent sorption isotherms indicated that the sorption process of Co(II) on HAP was spontaneous and endothermic. The sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange at low pH, whereas inner-sphere surface complexation or surface precipitation was the main sorption mechanism at high pH values. The results suggest that the HAP is a suitable material in the preconcentration and solidification of Co(II) from large volumes of aqueous solutions.     

Application of NKF-6 zeolite for the removal of U(VI) from aqueous solution

To better understand the application of NKF-6 zeolite as an adsorbent for the removal of U(VI) from radionuclides and heavy metal ions polluted water, herein, NKF-6 zeolite was employed to remove U(VI) at different experimental conditions. The influence of solid/liquid ratio, contact time, pH, ionic strength, humic substances and temperature on sorption of U(VI) to NKF-6 zeolite was investigated using batch technique under ambient conditions. The experimental results demonstrated that the sorption of U(VI) on NKF-6 zeolite was strongly dependent on pH. The sorption property of U(VI) was influenced by ionic strength at pH < 7.0, whereas was independent of ionic strength at pH > 7.0. The presence of fulvic acid or humic acid promoted the sorption of U(VI) on NKF-6 zeolite at low pH values while restrained the sorption at high pH values. The thermodynamic parameters (i.e., ΔS ⁰, ΔH ⁰, and ΔG ⁰) calculated from the temperature-dependent sorption isotherms demonstrated that the sorption process of U(VI) on NKF-6 zeolite was endothermic and spontaneous. At low pH values, the sorption of U(VI) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on NKF-6 zeolite surfaces, while inner-sphere surface complexation was the main sorption mechanism at high pH values. From the experimental results, one can conclude that NKF-6 zeolite can be used as a potential adsorbent for the preconcentration and solidification of U(VI) from large volumes of aqueous solutions.     

Impact of environmental conditions on the removal of Ni(II) from aqueous solution to bentonite/iron oxide magnetic composites

The sorption of radionuclide ⁶³Ni(II) on bentonite/iron oxide magnetic composites was investigated by batch technique under ambient conditions. The effect of contact time, solid content, pH, coexistent electrolyte ions, fulvic acid, and temperature on Ni(II) sorption to bentonite/iron oxide magnetic composites was examined. The results demonstrated that the sorption of Ni(II) was strongly dependent on pH and ionic strength at pH <8.0, and was independent of pH and ionic strength at high pH values. The sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange at low pH, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The experimental data were well fitted by Langmuir model. The thermodynamic parameters (∆G°, ∆S°, ∆H°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Ni(II) on bentonite/iron oxide magnetic composites was an endothermic and spontaneous processes. The results show that bentonite/iron oxide magnetic composites are promising magnetic materials for the preconcentration and separation of radionickel from aqueous solutions in environmental pollution.     

Pressure-driven flow in open fluidic channels

Arsenic is an element that exists naturally in many rocks and minerals around the world. It also accumulates in petroleum, shale, oil sands, and coal deposits as a result of biogeochemical processes, and it has been found in fly ash from the combustion of solid biofuels. Arsenic compounds in their organic and inorganic forms pose both a health and an environmental risk, and continue to be a challenge to the energy industry. The environmental fate and removal technologies of arsenic compounds are controlled to a large extent by their surface interactions with inorganic and organic adsorbents. We report thermodynamic binding constants, K(binding), from applying the triple-layer surface complexation model to adsorption isotherm and pH envelope data for dimethylarsinic acid (DMA) and p-arsanilic acid (p-AsA) on hematite and goethite. Ligand exchange reactions were constructed based on the interpretation of ATR-FTIR spectra of DMA and p-AsA surface complexes. Surface coverage of adsorbates was quantified in situ from the spectral component at 840 cm(-1). The best fit to the DMA adsorption data was obtained using outer-sphere complex formation, whereas for p-AsA, the best fit was obtained using two monodentate inner-sphere surface complexes. The significance of the results is discussed in relation to improving modeling tools used by environmental regulators and the energy sector for optimum control of arsenic content in fuels.     

Study of <Superscript>63</Superscript>Ni(II) sorption on CMC-bound bentonite from aqueous solutions

Bentonite was investigated to remove Ni(II) from aqueous solutions because of its strong sorption ability. Herein, bentonite was modified with sodium carboxymethylcellulose (CMC) and used as an adsorbent to remove Ni(II) from aqueous solutions. The results indicated that CMC-bentonite had higher sorption capacity than bare bentonite in the sorption of Ni(II) from aqueous solutions. Sorption of Ni(II) on CMC-bentonite was mainly dominated by ion exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation or surface precipitation at high pH values. The thermodynamic data calculated from temperature dependent sorption isotherms indicated that the sorption of Ni(II) to CMC-bentonite hybrids was an spontaneous process and enhanced with increasing temperature.     

Effect of pH,ionic strength,foreign ions,humic acid and temperature on sorption of radionuclide <Superscript>60</Superscript>Co(II) on illite

In this article, a series of batch experiments were carried out to investigate the effect of various environmental factors such as contact time, solid content, pH, ionic strength, foreign ions, temperature and coexisting humic acid on the sorption behavior radionuclide ⁶⁰Co(II) on illite. The results indicated that the sorption of Co(II) was strongly dependent on pH, ionic strength and temperature. At low pH, the sorption was dominated by outer-sphere surface complexation and ion exchange on illite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were used to simulate the sorption isotherms at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic data (∆G ⁰, ∆S ⁰, ∆H ⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Co(II) on illite was an endothermic and spontaneous process. The sorption test revealed that the illite can be as a cost-effective adsorbent suitable for pre-concentration of Co(II) from large volumes of aqueous solutions.