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.

Combining Individual-Based Modeling and Food Microenvironment Descriptions To Predict the Growth of Listeria monocytogenes on Smear Soft Cheese

PubMed Central

Ferrier, Rachel; Hezard, Bernard; Lintz, Adrienne; Stahl, Valérie

2013-01-01

An individual-based modeling (IBM) approach was developed to describe the behavior of a few Listeria monocytogenes cells contaminating smear soft cheese surface. The IBM approach consisted of assessing the stochastic individual behaviors of cells on cheese surfaces and knowing the characteristics of their surrounding microenvironments. We used a microelectrode for pH measurements and micro-osmolality to assess the water activity of cheese microsamples. These measurements revealed a high variability of microscale pH compared to that of macroscale pH. A model describing the increase in pH from approximately 5.0 to more than 7.0 during ripening was developed. The spatial variability of the cheese surface characterized by an increasing pH with radius and higher pH on crests compared to that of hollows on cheese rind was also modeled. The microscale water activity ranged from approximately 0.96 to 0.98 and was stable during ripening. The spatial variability on cheese surfaces was low compared to between-cheese variability. Models describing the microscale variability of cheese characteristics were combined with the IBM approach to simulate the stochastic growth of L. monocytogenes on cheese, and these simulations were compared to bacterial counts obtained from irradiated cheeses artificially contaminated at different ripening stages. The simulated variability of L. monocytogenes counts with the IBM/microenvironmental approach was consistent with the observed one. Contrasting situations corresponding to no growth or highly contaminated foods could be deduced from these models. Moreover, the IBM approach was more effective than the traditional population/macroenvironmental approach to describe the actual bacterial behavior variability. PMID:23872572

Molecular binding mechanisms of aqueous cadmium and lead to siderophores, bacteria and mineral surfaces

NASA Astrophysics Data System (ADS)

Mishra, Bhoopesh

Recent studies have shown that diverse groups of bacteria adsorb metals to similar extents and uptake can be modeled using a universal adsorption model. In this study, XAFS has been used to resolve whether binding sites determined for single species systems are responsible for adsorption in more complex natural bacterial assemblages. Results obtained from a series of XAFS experiments on pure Gram positive and Gram negative bacterial strains and consortia of bacteria as a function of pH and Cd loading suggests that every bacterial strain has a complex physiology and they are all slightly different from each other. Nevertheless from the metal adsorption chemistry point of view, the main difference between them lies in the site ratio of three fundamental sites only - carboxyl, phosphoryl and sulfide. Two completely different consortia of bacteria (obtained from natural river water, and soil system with severe organic contamination) were successfully modeled in the pH range 3.4--7.8 using the EXAFS models developed for single species systems. Results thus obtained can potentially have very high impact on the modeling of the complex bacterial systems in realistic geological settings, leading to further refinement and development of robust remediation strategies for metal contamination at macroscopic level. In another study, solution speciation of Pb and Cd with DFO-B has been examined using a combination of techniques (ICP, TOC, thermodynamic modeling and XAFS). Results indicate that Pb does not complex with DFO-B at all until about pH 3.5, but forms a totally caged structure at pH 7.5. At intermediate pH conditions, mixture of species (one and two hydroxamate groups complexed) is formed. Cd on the other hand, does not complex until pH 5, forms intermediate complexes at pH 8 and is totally chelated at pH 9. Further studies were conducted for Pb sorption to mineral surface kaolinite with and without DFO-B. In the absence of DFO-B, results suggest outer sphere and inner sphere sorption of Pb on kaolinite surface at acidic and circumneutral pH conditions respectively. In the presence of DFO-B, bulk sorption studies indicated that Pb sorption is enhanced in the presence of DFO-B around pH 6 and inhibited above pH 6.5. This was confirmed by x-ray fluorescence measurements. Extended XAFS study clearly indicated unwrapping of DFO-B molecule at the surface. Our study has unambiguously recognized it as a "Type A" ternary complex ("Type A" complex means surface-metal-ligand type of interaction). Taken together, bulk adsorption measurements and XAFS experiments represent a powerful approach for determining and modeling metal speciation and adsorption.

Ultra-fast grain boundary diffusion and its contribution to surface segregation on a martensitic steel. Experiments and modeling

NASA Astrophysics Data System (ADS)

Christien, F.; Le Gall, R.

2011-09-01

Phosphorus surface segregation was measured by Auger Electron Spectroscopy on a 17-4 PH martensitic stainless steel at 450, 550 and 600 °C. Surface segregation was shown to be much faster than expected which was attributed to a high contribution of phosphorus diffusion along the former austenitic grain boundaries. A model of surface segregation was developed following the Darken-du Plessis approach and taking account of both bulk and grain boundary solute diffusion. The phosphorus grain boundary diffusion coefficient in 17-4 PH was estimated: DGB< = 6.2 10 4 exp(- 157 kJ mol - 1 /RT)cm 2 s - 1 . It is found to be more than three orders of magnitude higher in 17-4 PH steel than in α-iron.

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

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

Manzano, J. Sebastian; Singappuli-Arachchige, Dilini; Parikh, Bosky L.

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticlesmore » (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.« less

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

DOE PAGES

Manzano, J. Sebastian; Singappuli-Arachchige, Dilini; Parikh, Bosky L.; ...

2017-12-05

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticlesmore » (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.« less

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.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

Dolomite surface speciation and reactivity in aquatic systems

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques; Thomas, Fabien

1999-10-01

The surface charge of dolomite (CaMg(CO3)2) was measured as a function of pH (6.5-11.5), pCO2 (10-3.5, 0.01, and 0.96 atm) and ionic strength (0.01, 0.1, and 0.5 M NaCl) using potentiometric titrations in a limited residence time reactor. Dolomite zeta potential (ζ) was determined using streaming potential and electrophoresis techniques at pH 2 to 12 in solutions having ionic strengths from 0.001 to 0.1 M NaCl as a function of aqueous Ca2+, Mg2+, and CO32- concentrations. The point of zero charge (PZC) and isoelectric point (IEP) of dolomite are the same (pH ∼8 at pCO2 ∼10-3.5 atm) and very close to those of calcite and magnesite. On the basis of these results, a surface complexation model (SCM) is proposed that postulates the presence of three distinct primary hydration sites: >CO3H°, >CaOH°, and >MgOH°. The intrinsic stability constants of dolomite surface reactions were determined by fitting the pH dependence of the surface charge and taking into account the isoelectric points and ζ-potential values for a wide range of solution compositions. In most natural aquatic environments, dolomite surface speciation can be modeled using the following species: >CO3-, >CO3Me+, >MeOH2+, >MeHCO3o, and >MeCO3-, where Me = Ca, Mg. The speciation model presented in this study allows description of metal and ligand adsorption onto dolomite surface and provides new insights on the mechanisms that control dolomite dissolution/crystallization in aqueous solutions. In particular, it is shown that dolomite dissolution is controlled by the protonation of >CO3H° surface complexes at pH < 6 and by hydrolysis of >MeOH2+ groups at higher pH.

The Limitations of an Exclusively Colloidal View of Protein Solution Hydrodynamics and Rheology

PubMed Central

Sarangapani, Prasad S.; Hudson, Steven D.; Migler, Kalman B.; Pathak, Jai A.

2013-01-01

Proteins are complex macromolecules with dynamic conformations. They are charged like colloids, but unlike colloids, charge is heterogeneously distributed on their surfaces. Here we overturn entrenched doctrine that uncritically treats bovine serum albumin (BSA) as a colloidal hard sphere by elucidating the complex pH and surface hydration-dependence of solution viscosity. We measure the infinite shear viscosity of buffered BSA solutions in a parameter space chosen to tune competing long-range repulsions and short-range attractions (2 mg/mL ≤ [BSA] ≤ 500 mg/mL and 3.0 ≤ pH ≤ 7.4). We account for surface hydration through partial specific volume to define volume fraction and determine that the pH-dependent BSA intrinsic viscosity never equals the classical hard sphere result (2.5). We attempt to fit our data to the colloidal rheology models of Russel, Saville, and Schowalter (RSS) and Krieger-Dougherty (KD), which are each routinely and successfully applied to uniformly charged suspensions and to hard-sphere suspensions, respectively. We discover that the RSS model accurately describes our data at pH 3.0, 4.0, and 5.0, but fails at pH 6.0 and 7.4, due to steeply rising solution viscosity at high concentration. When we implement the KD model with the maximum packing volume fraction as the sole floating parameter while holding the intrinsic viscosity constant, we conclude that the model only succeeds at pH 6.0 and 7.4. These findings lead us to define a minimal framework for models of crowded protein solution viscosity wherein critical protein-specific attributes (namely, conformation, surface hydration, and surface charge distribution) are addressed. PMID:24268154

Analytical coupled-wave model for photonic crystal surface-emitting quantum cascade lasers.

PubMed

Wang, Zhixin; Liang, Yong; Yin, Xuefan; Peng, Chao; Hu, Weiwei; Faist, Jérôme

2017-05-15

An analytical coupled-wave model is developed for surface-emitting photonic-crystal quantum cascade lasers (PhC-QCLs). This model provides an accurate and efficient analysis of full three-dimensional device structure with large-area cavity size. Various laser properties of interest including the band structure, mode frequency, cavity loss, mode intensity profile, and far field pattern (FFP), as well as their dependence on PhC structures and cavity size, are investigated. Comparison with numerical simulations confirms the accuracy and validity of our model. The calculated FFP and polarization profile well explain the previously reported experimental results. In particular, we reveal the possibility of switching the lasing modes and generating single-lobed FFP by properly tuning PhC structures.

Surface complexation modeling

USDA-ARS?s Scientific Manuscript database

Adsorption-desorption reactions are important processes that affect the transport of contaminants in the environment. Surface complexation models are chemical models that can account for the effects of variable chemical conditions, such as pH, on adsorption reactions. These models define specific ...

Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

NASA Astrophysics Data System (ADS)

Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

2013-11-01

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Modeling the influence of variable pH on the transport of zinc in a contaminated aquifer using semiempirical surface complexation models

USGS Publications Warehouse

Kent, D.B.; Abrams, R.H.; Davis, J.A.; Coston, J.A.; LeBlanc, D.R.

2000-01-01

Land disposal of sewage effluent resulted in contamination of a sand and gravel aquifer (Cape Cod, Massachusetts) with zinc (Zn). The distribution of Zn was controlled by pH‐dependent adsorption; the Zn extended 15 m into the 30‐m‐thick sewage plume within approximately 100 m of the source but only 2–4 m into the plume between 100 and 400 m downgradient. A two‐dimensional vertical cross section model coupling groundwater flow with solute transport and equilibrium adsorption is used to simulate the influence of pH on Zn transport. Adsorption is described using semiempirical surface complexation models (SCM) by writing chemical reactions between dissolved Zn and mineral surface sites. SCM parameters were determined in independent laboratory experiments. A 59‐year simulation with a one‐site SCM describes the influence of pH on Zn transport well, with greater mobility at the low pH values near the upper sewage plume boundary than at the higher pH values deeper in the sewage‐contaminated zone. Simulation with a two‐site SCM describes both the sharpness and approximate location of the leading edge of the Zn‐contaminated region. Temporal variations in pH of incoming groundwater can result in large increases in Zn concentration and mobility. The influence of spatial and temporal variability in pH on adsorption and transport of Zn was accomplished much more easily with the semiempirical SCM approach than could be achieved with distribution coefficients or adsorption isotherms.

Hydroxy-Al and cell-surface negativity are responsible for the enhanced sensitivity of Rhodotorula taiwanensis to aluminum by increased medium pH.

PubMed

Zhao, Xue Qiang; Bao, Xue Min; Wang, Chao; Xiao, Zuo Yi; Hu, Zhen Min; Zheng, Chun Li; Shen, Ren Fang

2017-10-01

Aluminum (Al) is ubiquitous and toxic to microbes. High Al 3+ concentration and low pH are two key factors responsible for Al toxicity, but our present results contradict this idea. Here, an Al-tolerant yeast strain Rhodotorula taiwanensis RS1 was incubated in glucose media containing Al with a continuous pH gradient from pH 3.1-4.2. The cells became more sensitive to Al and accumulated more Al when pH increased. Calculations using an electrostatic model Speciation Gouy Chapman Stern indicated that, the increased Al sensitivity of cells was associated with AlOH 2+ and Al(OH) 2 + rather than Al 3+ . The alcian blue (a positively charged dye) adsorption and zeta potential determination of cell surface indicated that, higher pH than 3.1 increased the negative charge and Al adsorption at the cell surface. Taken together, the enhanced sensitivity of R. taiwanensis RS1 to Al from pH 3.1-4.2 was associated with increased hydroxy-Al and cell-surface negativity.

The Importance of Protons in Reactive Transport Modeling

NASA Astrophysics Data System (ADS)

McNeece, C. J.; Hesse, M. A.

2014-12-01

The importance of pH in aqueous chemistry is evident; yet, its role in reactive transport is complex. Consider a column flow experiment through silica glass beads. Take the column to be saturated and flowing with solution of a distinct pH. An instantaneous change in the influent solution pH can yield a breakthrough curve with both a rarefaction and shock component (composite wave). This behavior is unique among aqueous ions in transport and is more complex than intuition would tell. Analysis of the hyperbolic limit of this physical system can explain these first order transport phenomenon. This analysis shows that transport behavior is heavily dependent on the shape of the adsorption isotherm. Hence it is clear that accurate surface chemistry models are important in reactive transport. The proton adsorption isotherm has nonconstant concavity due to the proton's ability to partition into hydroxide. An eigenvalue analysis shows that an inflection point in the adsorption isotherm allows the development of composite waves. We use electrostatic surface complexation models to calculate realistic proton adsorption isotherms. Surface characteristics such as specific surface area, and surface site density were determined experimentally. We validate the model by comparison against silica glass bead flow through experiments. When coupled to surface complexation models, the transport equation captures the timing and behavior of breakthrough curves markedly better than with commonly used Langmuir assumptions. Furthermore, we use the adsorption isotherm to predict, a priori, the transport behavior of protons across pH composition space. Expansion of the model to multicomponent systems shows that proton adsorption can force composite waves to develop in the breakthrough curves of ions that would not otherwise exhibit such behavior. Given the abundance of reactive surfaces in nature and the nonlinearity of chemical systems, we conclude that building a greater understanding of proton adsorption is of utmost importance to reactive transport modeling.

Protofit: A program for determining surface protonation constants from titration data

NASA Astrophysics Data System (ADS)

Turner, Benjamin F.; Fein, Jeremy B.

2006-11-01

Determining the surface protonation behavior of natural adsorbents is essential to understand how they interact with their environments. ProtoFit is a tool for analysis of acid-base titration data and optimization of surface protonation models. The program offers a number of useful features including: (1) enables visualization of adsorbent buffering behavior; (2) uses an optimization approach independent of starting titration conditions or initial surface charge; (3) does not require an initial surface charge to be defined or to be treated as an optimizable parameter; (4) includes an error analysis intrinsically as part of the computational methods; and (5) generates simulated titration curves for comparison with observation. ProtoFit will typically be run through ProtoFit-GUI, a graphical user interface providing user-friendly control of model optimization, simulation, and data visualization. ProtoFit calculates an adsorbent proton buffering value as a function of pH from raw titration data (including pH and volume of acid or base added). The data is reduced to a form where the protons required to change the pH of the solution are subtracted out, leaving protons exchanged between solution and surface per unit mass of adsorbent as a function of pH. The buffering intensity function Qads* is calculated as the instantaneous slope of this reduced titration curve. Parameters for a surface complexation model are obtained by minimizing the sum of squares between the modeled (i.e. simulated) buffering intensity curve and the experimental data. The variance in the slope estimate, intrinsically produced as part of the Qads* calculation, can be used to weight the sum of squares calculation between the measured buffering intensity and a simulated curve. Effects of analytical error on data visualization and model optimization are discussed. Examples are provided of using ProtoFit for data visualization, model optimization, and model evaluation.

Modeling the acid-base surface chemistry of montmorillonite.

PubMed

Bourg, Ian C; Sposito, Garrison; Bourg, Alain C M

2007-08-15

Proton uptake on montmorillonite edge surfaces can control pore water pH, solute adsorption, dissolution kinetics and clay colloid behavior in engineered clay barriers and natural weathering environments. Knowledge of proton uptake reactions, however, is currently limited by strong discrepancies between reported montmorillonite titration data sets and by conflicting estimates of edge structure, reactivity and electrostatics. In the present study, we show that the apparent discrepancy between titration data sets results in large part from the widespread use of an erroneous assumption of zero specific net proton surface charge at the onset of titration. Using a novel simulation scheme involving a surface chemistry model to simulate both pretreatment and titration, we find that montmorillonite edge surface chemistry models that account for the "spillover" of electrostatic potential from basal onto edge surfaces and for the stabilization of deprotonated Al-Si bridging sites through bond-length relaxation at the edge surface can reproduce key features of the best available experimental titration data (the influence of pretreatment conditions on experimental results, the absence of a point of zero salt effect, buffer capacity in the acidic pH range). However, no combination of current models of edge surface structure, reactivity and electrostatics can quantitatively predict, without fitted parameters, the experimental titration data over the entire range of pH (4.5 to 9) and ionic strength (0.001 to 0.5 mol dm(-3)) covered by available data.

Study of the adsorption of Cd and Zn onto an activated carbon: Influence of pH, cation concentration, and adsorbent concentration

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

Seco, A.; Marzal, P.; Gabaldon, C.

1999-06-01

The single adsorption of Cd and Zn from aqueous solutions has been investigated on Scharlau Ca 346 granular activated carbon in a wide range of experimental conditions: pH, metal concentration, and carbon concentration. The results showed the efficiency of the activated carbon as sorbent for both metals. Metal removals increase on raising the pH and carbon concentration, and decrease on raising the initial metal concentration. The adsorption processes have been modeled using the surface complex formation (SCF) Triple Layer Model (TLM). The adsorbent TLM parameters were determined. Modeling has been performed assuming a single surface bidentate species or an overallmore » surface species with fractional stoichiometry. The bidentate stoichiometry successfully predicted cadmium and zinc removals in all the experimental conditions. The Freundlich isotherm has been also checked.« less

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

USGS Publications Warehouse

Gao, S.; Goldberg, S.; Herbel, M.J.; Chalmers, A.T.; Fujii, R.; Tanji, K.K.

2006-01-01

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching in natural environments. ?? 2006 Elsevier B.V. All rights reserved.

Effect of equilibration time on Pu desorption from goethite

DOE PAGES

Wong, Jennifer C.; Zavarin, Mavrik; Begg, James D.; ...

2015-01-28

Strongly sorbing ions such as plutonium may become irreversibly bound to mineral surfaces over time implicates near- and far-field transport of Pu. Batch adsorption–desorption data were collected as a function of time and pH to study the surface stability of Pu on goethite. Pu(IV) was adsorbed to goethite over the pH range 4.2 to 6.6 for different periods of time (1, 6, 15, 34 and 116 d). Moreover, following adsorption, Pu was leached from the mineral surface with desferrioxamine B (DFOB), a complexant capable of effectively competing with the goethite surface for Pu. The amount of Pu desorbed from the goethitemore » was found to vary as a function of the adsorption equilibration time, with less Pu removed from the goethite following longer adsorption periods. This effect was most pronounced at low pH. Logarithmic desorption distribution ratios for each adsorption equilibration time were fit to a pH-dependent model. Model slopes decreased between 1 and 116 d adsorption time, indicating that overall Pu(IV) surface stability on goethite surfaces becomes less dependent on pH with greater adsorption equilibration time. The combination of adsorption and desorption kinetic data suggest that non-redox aging processes affect Pu sorption behavior on goethite.« less

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

PubMed

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S; Schott, Jacques

2010-08-03

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

The role of chemistry and pH of solid surfaces for specific adsorption of biomolecules in solution--accurate computational models and experiment.

PubMed

Heinz, Hendrik

2014-06-18

Adsorption of biomolecules and polymers to inorganic nanostructures plays a major role in the design of novel materials and therapeutics. The behavior of flexible molecules on solid surfaces at a scale of 1-1000 nm remains difficult and expensive to monitor using current laboratory techniques, while playing a critical role in energy conversion and composite materials as well as in understanding the origin of diseases. Approaches to implement key surface features and pH in molecular models of solids are explained, and distinct mechanisms of peptide recognition on metal nanostructures, silica and apatite surfaces in solution are described as illustrative examples. The influence of surface energies, specific surface features and protonation states on the structure of aqueous interfaces and selective biomolecular adsorption is found to be critical, comparable to the well-known influence of the charge state and pH of proteins and surfactants on their conformations and assembly. The representation of such details in molecular models according to experimental data and available chemical knowledge enables accurate simulations of unknown complex interfaces in atomic resolution in quantitative agreement with independent experimental measurements. In this context, the benefits of a uniform force field for all material classes and of a mineral surface structure database are discussed.

Surface complexation modeling of Cd(II) sorption to montmorillonite, bacteria, and their composite

NASA Astrophysics Data System (ADS)

Wang, Ning; Du, Huihui; Huang, Qiaoyun; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Chen, Wenli

2016-10-01

Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH < 5, where the values predicted by the model were lower than the experimental results. The Cd complexes of X2Cd, SOCd+, R-COOCd+, and R-POCd+ were the predominant species on the composite surface over the pH range of 3 to 8. The distribution ratio of the adsorbed Cd between montmorillonite and bacterial fractions in the composite as predicted by CA-SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

PubMed

Nie, Zhe; Finck, Nicolas; Heberling, Frank; Pruessmann, Tim; Liu, Chunli; Lützenkirchen, Johannes

2017-04-04

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

Surface-promoted hydrolysis of 2,4,6-trinitrotoluene and 2,4-dinitroanisole on pyrogenic carbonaceous matter.

PubMed

Ding, Kai; Byrnes, Cory; Bridge, Jarrod; Grannas, Amanda; Xu, Wenqing

2018-04-01

This study investigates the fate of sorbed nitroaromatics on the surface of pyrogenic carbonaceous matter (PCM) to assess the feasibility of a PCM-promoted hydrolysis. The degradation of two nitroaromatic compounds, 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole, was observed at pH 7 in the presence of graphite powder, a model PCM. By contrast, no decay occurred without graphite. Using TNT as a model compound, our results suggest that TNT decay demonstrated a strong pH dependence, with no reaction at pH 3-5 but rapid degradation at pH 6-10. Moreover, by fitting TNT decay at different pH conditions along with its sorption kinetics to the Langmuir Kinetic Model, our results suggest that the base-catalyzed hydrolysis was important. The activation energy for TNT decay was obtained by measuring reaction rates at different temperatures with or without graphite and no significant difference was observed. However, the addition of tetramethylammonium cation was able to promote TNT decay possibly due to its ability to attract more OH - from the aqueous solution, leading to an increase in the sorbed OH - concentrations. Nitrite and a Meisenheimer complex were identified as degradation products for TNT. Other PCM, such as biochar, also demonstrated a comparable ability in promoting TNT decay at pH 7. Furthermore, a rapid degradation of TNT at pH 7 was observed when biochar was used as a soil amendment (4% by weight). Our results suggest that PCM can facilitate TNT and 2,4-dinitroanisole decay via a surface-promoted hydrolysis at neutral pH conditions, suggesting a promising alternative for in situ soil remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Development of a model to predict the adsorption of lead from solution on a natural streambed sediment

USGS Publications Warehouse

Brown, David Wayne; Hem, John David

1984-01-01

Adsorption of solutes by solid mineral surfaces commonly influences the dissolved ionic composition of natural waters. A model based on electrical double-layer theory has been developed which appears to be capable of characterizing the surface chemical behavior of a natural fine-grained sediment containing mostly quartz and feldspar. This variable surface charge-variable surface potential (VSC-VSP) model differs from others in being capable of evaluating more closely the effect of total metal ion activity on the pH-dependent change in electrical potential at the solid surface. The model was tested using 10-4 molar solutions of lead and a silt-size fraction of sediment from the bed of Colma Creek, a small stream in urban northern San Mateo County, California. The average deviation of measured percent adsorption and values calculated from the model was 6.6 adsorption percent from pH 2.0 to pH 7.0.

Modeling the acid-base properties of bacterial surfaces: A combined spectroscopic and potentiometric study of the gram-positive bacterium Bacillus subtilis.

PubMed

Leone, Laura; Ferri, Diego; Manfredi, Carla; Persson, Per; Shchukarev, Andrei; Sjöberg, Staffan; Loring, John

2007-09-15

In this study, macroscopic and spectroscopic data were combined to develop a surface complexation model that describes the acid-base properties of Bacillus subtilis. The bacteria were freeze-dried and then resuspended in 0.1 M NaCl ionic medium. Macroscopic measurements included potentiometric acid-base titrations and electrophoretic mobility measurements. In addition, ATR-FTIR spectra of wet pastes from suspensions of Bacillus subtilis at different pH values were collected. The least-squares program MAGPIE was used to generate a surface complexation model that takes into account the presence of three acid-base sites on the surface: tripple bond COOH, tripple bond NH+, and tripple bond PO-, which were identified previously by XPS measurements. Both potentiometric titration data and ATR-FTIR spectra were used quantitatively, and electrostatic effects at the charged bacterial surface were accounted for using the constant capacitance model. The model was calculated using two different approaches: in the first one XPS data were used to constrain the ratio of the total concentrations of all three surface sites. The capacitance of the double layer, the total buffer capacity, and the deprotonation constants of the tripple bond NH+, tripple bond POH, and tripple bond COOH species were determined in the fit. A second approach is presented in which the ratio determined by XPS of the total concentrations of tripple bond NH+ to tripple bond PO- sites is relaxed. The total concentration of tripple bond PO- sites was determined in the fit, while the deprotonation constant for tripple bond POH was manually varied until the minimization led to a model which predicted an isoelectric point that resulted in consistency with electrophoretic mobility data. The model explains well the buffering capacity of Bacillus subtilis suspensions in a wide pH range (between pH=3 and pH=9) which is of considerable environmental interest. In particular, a similar quantitative use of the IR data opens up possibilities to model other bacterial surfaces at the laboratory scale and help estimate the buffering capacity of carboxylate-containing compounds in natural samples.

The Probable Explanation for the Low Friction of Natural Joints.

PubMed

Pawlak, Zenon; Urbaniak, Wieslaw; Hagner-Derengowska, Magdalena; Hagner, Wojciech

2015-04-01

The surface of an articular cartilage, coated with phospholipid (PL) bilayers, plays an important role in its lubrication and movement. Intact (normal) and depleted surfaces of the joint were modelled and the pH influence on the surface interfacial energy, wettability and friction were investigated. In the experiments, the deterioration of the PL bilayer was controlled by its wettability and the applied friction. The surrounding fluid of an undamaged articular cartilage, the synovial fluid, has a pH value of approximately 7.4. Buffer solutions were formulated to represent the synovial fluid with various pH values. It was found that the surface interfacial energy was stabilised at its lowest values when the pH varied between 6.5 and 9.5. These results suggested that as the PL bilayers deteriorated, the hydration repulsion mechanism became less effective as friction increased. The decreased number of bilayers changed the wettability and lowered PL lubricant properties.

Vibrational spectroscopic study of pH dependent solvation at a Ge(100)-water interface during an electrode potential triggered surface termination transition

NASA Astrophysics Data System (ADS)

Niu, Fang; Rabe, Martin; Nayak, Simantini; Erbe, Andreas

2018-06-01

The charge-dependent structure of interfacial water at the n-Ge(100)-aqueous perchlorate interface was studied by controlling the electrode potential. Specifically, a joint attenuated total reflection infrared spectroscopy and electrochemical experiment was used in 0.1M NaClO4 at pH ≈ 1-10. The germanium surface transformation to an H-terminated surface followed the thermodynamic Nernstian pH dependence and was observed throughout the entire pH range. A singular value decomposition-based spectra deconvolution technique coupled to a sigmoidal transition model for the potential dependence of the main components in the spectra shows the surface transformation to be a two-stage process. The first stage was observed together with the first appearance of Ge-H stretching modes in the spectra and is attributed to the formation of a mixed surface termination. This transition was reversible. The second stage occurs at potentials ≈0.1-0.3 V negative of the first one, shows a hysteresis in potential, and is attributed to the formation of a surface with maximum Ge-H coverage. During the surface transformation, the surface becomes hydrophobic, and an effective desolvation layer, a "hydrophobic gap," developed with a thickness ≈1-3 Å. The largest thickness was observed near neutral pH. Interfacial water IR spectra show a loss of strongly hydrogen-bound water molecules compared to bulk water after the surface transformation, and the appearance of "free," non-hydrogen bound OH groups, throughout the entire pH range. Near neutral pH at negative electrode potentials, large changes at wavenumbers below 1000 cm-1 were observed. Librational modes of water contribute to the observed changes, indicating large changes in the water structure.

Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

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

Hassett, J.M.

1988-01-01

Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, andmore » 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.« less

Methotrexate loading in chitosan nanoparticles at a novel pH: Response surface modeling, optimization and characterization.

PubMed

Hashad, Rania A; Ishak, Rania A H; Geneidi, Ahmed S; Mansour, Samar

2016-10-01

The aim of this study was to assess the feasibility of employing a novel but critical formulation pH (6.2) to encapsulate an anionic model drug (methotrexate, MTX) into chitosan(Cs)-tripolyphosphate nanoparticles(NPs). A response surface methodology using a three-level full factorial design was applied studying the effects of two independent variables namely; Cs concentration and MTX concentration. The responses investigated were the entrapment efficiency (EE%), mean hydrodynamic particle size (PS), polydispersity index (PDI) and zeta potential (ZP). In order to simultaneously optimize the series of models obtained, the desirability function approach was applied with a goal to produce high percent of MTX encapsulated into highly charged Cs-TPP NPs of homogenous optimum PS. MTX-loaded CsNPs were successfully prepared at the novel pH applied. The suggested significant models were found quadratic for EE, PS and ZP responses, while 2-factor interaction model for PDI. The optimization overlay graph showed that the maximum global desirability, D=0.856, was reached when the conditions were set at high Cs and MTX concentration. Thus, the use of such optimized conditions, at this novel pH, achieved a maximum drug EE% (73.38%) into NPs characterized by optimum PS (232.6nm), small PDI value (0.195) and highly surface charged (+18.4mV). Copyright © 2016 Elsevier B.V. All rights reserved.

Protein adsorption at charged surfaces: the role of electrostatic interactions and interfacial charge regulation.

PubMed

Hartvig, Rune A; van de Weert, Marco; Østergaard, Jesper; Jorgensen, Lene; Jensen, Henrik

2011-03-15

The understanding of protein adsorption at charged surfaces is important for a wide range of scientific disciplines including surface engineering, separation sciences and pharmaceutical sciences. Compared to chemical entities having a permanent charge, the adsorption of small ampholytes and proteins is more complicated as the pH near a charged surface can be significantly different from the value in bulk solution. In this work, we have developed a phenomenological adsorption model which takes into account the combined role of interfacial ion distribution, interfacial charge regulation of amino acids in the proximity of the surface, electroneutrality, and mass balance. The model is straightforward to apply to a given set of experimental conditions as most model parameters are obtained from bulk properties and therefore easy to estimate or are directly measurable. The model provides a detailed understanding of the importance of surface charge on adsorption and in particular of how changes in surface charge, concentration, and surface area may affect adsorption behavior. The model is successfully used to explain the experimental adsorption behavior of the two model proteins lysozyme and α-lactalbumin. It is demonstrated that it is possible to predict the pH and surface charge dependent adsorption behavior from experimental or theoretical estimates of a preferred orientation of a protein at a solid charged interface.

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

PubMed

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2)-BET specific surface area, SSA(BET) (thus, total edge site concentrations). The specific surface area should be at least 80-100m(2)/g for smectite clays in order to reach convergence during the modeling. The range of 10-20% SSA(BET) was used to estimate the values of edge site surfaces that led to the convergence during modeling. An agreement between the experimental data and model predictions is found reasonable when 15% SSA(BET) was used as edge site surface. However, the predicted U (VI) adsorption underestimated and overestimated the experimental observations at the 10 and 20% of the measured SSA(BET), respectively. The dependence of uranium sorption modeling results on specific surface area and edge site surface is useful to describe and predict U (VI) retardation as a function of chemical conditions in the field-scale reactive transport simulations. Therefore this approach can be used in the environmental quality assessment.

Defining reactive sites on hydrated mineral surfaces: Rhombohedral carbonate minerals

NASA Astrophysics Data System (ADS)

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

Despite the success of surface complexation models (SCMs) to interpret the adsorptive properties of mineral surfaces, their construct is sometimes incompatible with fundamental chemical and/or physical constraints, and thus, casts doubts on the physical-chemical significance of the derived model parameters. In this paper, we address the definition of primary surface sites (i.e., adsorption units) at hydrated carbonate mineral surfaces and discuss its implications to the formulation and calibration of surface equilibria for these minerals. Given the abundance of experimental and theoretical information on the structural properties of the hydrated (10.4) cleavage calcite surface, this mineral was chosen for a detailed theoretical analysis of critical issues relevant to the definition of primary surface sites. Accordingly, a single, generic charge-neutral surface site ( tbnd CaCO 3·H 2O 0) is defined for this mineral whereupon mass-action expressions describing adsorption equilibria were formulated. The one-site scheme, analogous to previously postulated descriptions of metal oxide surfaces, allows for a simple, yet realistic, molecular representation of surface reactions and provides a generalized reference state suitable for the calculation of sorption equilibria for rhombohedral carbonate minerals via Law of Mass Action (LMA) and Gibbs Energy Minimization (GEM) approaches. The one-site scheme is extended to other rhombohedral carbonate minerals and tested against published experimental data for magnesite and dolomite in aqueous solutions. A simplified SCM based on this scheme can successfully reproduce surface charge, reasonably simulate the electrokinetic behavior of these minerals, and predict surface speciation agreeing with available spectroscopic data. According to this model, a truly amphoteric behavior is displayed by these surfaces across the pH scale but at circum-neutral pH (5.8-8.2) and relatively high ΣCO 2 (⩾1 mM), proton/bicarbonate co-adsorption becomes important and leads to the formation of a charge-neutral H 2CO 3-like surface species which may largely account for the surface charge-buffering behavior and the relatively wide range of pH values of isoelectric points (pH iep) reported in the literature for these minerals.

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.

Quantification of surface charge density and its effect on boundary slip.

PubMed

Jing, Dalei; Bhushan, Bharat

2013-06-11

Reduction of fluid drag is important in the micro-/nanofluidic systems. Surface charge and boundary slip can affect the fluid drag, and surface charge is also believed to affect boundary slip. The quantification of surface charge and boundary slip at a solid-liquid interface has been widely studied, but there is a lack of understanding of the effect of surface charge on boundary slip. In this paper, the surface charge density of borosilicate glass and octadecyltrichlorosilane (OTS) surfaces immersed in saline solutions with two ionic concentrations and deionized (DI) water with different pH values and electric field values is quantified by fitting experimental atomic force microscopy (AFM) electrostatic force data using a theoretical model relating the surface charge density and electrostatic force. Results show that pH and electric field can affect the surface charge density of glass and OTS surfaces immersed in saline solutions and DI water. The mechanisms of the effect of pH and electric field on the surface charge density are discussed. The slip length of the OTS surface immersed in saline solutions with two ionic concentrations and DI water with different pH values and electric field values is measured, and their effects on the slip length are analyzed from the point of surface charge. Results show that a larger absolute value of surface charge density leads to a smaller slip length for the OTS surface.

The effects of smoothies on enamel erosion: an in situ study.

PubMed

Ali, Hanein; Tahmassebi, Jinous F

2014-05-01

To measure, in vitro, the pH and titratable acidity (TA) of various soft drinks and to assess the erosive effect of smoothies using an in situ model. The in vitro phase of this study included measuring the inherent pH of six different commercially available smoothies, diet coke, and citric acid 0.3% (positive control) using a pH meter. The TA was determined by titration with NaOH. In the second part of the study, an in situ model was used. An upper removable appliance capable of retaining two enamel slabs was constructed and worn by 14 volunteers. The drinks under test were Innocent(®) strawberries and banana smoothie and citric acid. Volunteers were instructed to dip the appliance in the test solutions extra-orally five times daily for 2 min each time for 21 days. Measurements of enamel loss were made by surface profilometry and microhardness. Diet Coke was found to be the most acidic drink (pH 2.61), whereas Innocent(®) mangoes and passion fruit smoothie showed to be the least (pH 3.9). With regard to TA, Innocent(®) blackberries, strawberries, and blackcurrant smoothie had the highest TA requiring 10.8 mol of NaOH to reach pH 7.0, whereas citric acid required only 3.1 mol of NaOH to reach the same pH value. Surface profilometry and microhardness testing revealed that citric acid caused a statistically significantly greater tooth surface loss compared with smoothie after 21-day pH cycling protocol. Smoothies are acidic and have high TA levels. Innocent(®) strawberries and banana smoothie had an erosive potential to the teeth. However, its erosive effect was significantly less compared with citric acid after 21-day pH cycling protocol using an in situ model. © 2013 BSPD, IAPD and John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

The titration of carboxyl-terminated monolayers revisited: in situ calibrated fourier transform infrared study of well-defined monolayers on silicon.

PubMed

Aureau, D; Ozanam, F; Allongue, P; Chazalviel, J-N

2008-09-02

The acid-base equilibrium at the surface of well-defined mixed carboxyl-terminated/methyl-terminated monolayers grafted on silicon (111) has been investigated using in situ calibrated infrared spectroscopy (attenuated total reflectance (ATR)) in the range of 900-4000 cm (-1). Spectra of surfaces in contact with electrolytes of various pH provide a direct observation of the COOH <--> COO (-) conversion process. Quantitative analysis of the spectra shows that ionization of the carboxyl groups starts around pH 6 and extends over more than 6 pH units: approximately 85% ionization is measured at pH 11 (at higher pH, the layers become damaged). Observations are consistently accounted for by a single acid-base equilibrium and discussed in terms of change in ion solvation at the surface and electrostatic interactions between surface charges. The latter effect, which appears to be the main limitation, is qualitatively accounted for by a simple model taking into account the change in the Helmholtz potential associated with the surface charge. Furthermore, comparison of calculated curves with experimental titration curves of mixed monolayers suggests that acid and alkyl chains are segregated in the monolayer.

Response surface model for predicting chronic toxicity of cadmium to Paronychiurus kimi (Collembola), with a special emphasis on the importance of soil characteristics in the reproduction test.

PubMed

Son, Jino; Shin, Key-il; Cho, Kijong

2009-11-01

A central composite design (CCD) was employed to investigate the effects of organic matter (OM) content and soil pH on the reproduction, and chronic toxicity (28-d EC(50-reproduction)) of cadmium for Paronychiurus kimi after 28days exposure in a standard artificial soil. Two statistical models were developed, one describing reproduction in control artificial soils as a function of OM content and pH, and the other describing cadmium toxicity to the same soil parameters. In the reproduction model, pH was the most important factor, followed by two quadratic factors of OM(2) and pH(2). The parameter pH alone could explain 75.5% of the response variation. The reproduction model will allow us to predict a mean reproduction in the non-treated control soils that contain various combinations of OM content and different pH values. In the chronic toxicity model, only the linear factor of the OM content and pH significantly (p<0.05) affect cadmium toxicity, which explains the 78.9% and 14.9% of total response variance, respectively. Therefore, the final polynomial regression describing the chronic toxicity of cadmium to P. kimi is as follows: predicted 28-d EC(50) of cadmium (mgkg(-1))=-21.231+2.794 x OM+4.874 x pH. The present study show that soil characteristics, which can alter the toxicity of cadmium, can also act as stressors themselves in regards to the reproduction of P. kimi. Based on the physico-chemical characteristics of the test media, the response surface model developed in this study can be used to provide initial toxicity information for cadmium within a region of interest in terms of OM content and pH, and may lead to more scientific based risk assessment for metals.

The interplay between pH sensitivity and label-free protein detection in immunologically modified nano-scaled field-effect transistor.

PubMed

Shalev, Gil; Rosenwaks, Yossi; Levy, Ilan

2012-01-15

We present experimental results in order to establish a correlation between pH sensitivity of immunologically modified nano-scaled field-effect transistor (NS-ImmunoFET) with their sensing capacity for label-free detection. The NS-ImmunoFETs are fabricated from silicon-on-insulator (SOI) wafers and are fully-depleted with thickness of ~20 nm. The data shows that higher sensitivity to pH entails enhanced sensitivity to analyte detection. This suggests that the mechanism of analyte detection as pure electrostatic perturbation induced by antibody-analyte interaction is over simplified. The fundamental assumption, in existing models for field-effect sensing mechanism assumes that the analyte molecules do not directly interact with the surface but rather stand 'deep' in the solution and away from the dielectric surface. Recent studies clearly provide contradicting evidence demonstrating that antibodies lie down flat on the surface. These observations led us to propose that the proteins that cover the gate area intimately interact with active sites on the surface thus forming a network of interacting sites. Since sensitivity to pH is directly correlated with the amount of amphoteric sites, we witness a direct correlation between sensitivity to pH and analyte detection. The highest and lowest threshold voltage shift for a label-free and specific detection of 6.5 nM IgG were 40 mV and 2.3 mV for NS-ImmunoFETs with pH sensitivity of 35 mV/decade and 15 mV/decade, respectively. Finally, physical modeling of the NS-ImmunoFET is presented and charge of a single IgG protein at pH 6 is calculated. The obtained value is consistent with charge of IgG protein cited in literature. Copyright © 2011 Elsevier B.V. All rights reserved.

Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Formulation design space for stable, pH sensitive crystalline nifedipine nanoparticles.

PubMed

Jog, Rajan; Unachukwu, Kenechi; Burgess, Diane J

2016-11-30

Enteric coated formulations protect drugs from degrading in the harsh environment of the stomach (acidic pH and enzymes), and promotes drug delivery to and absorption into the duodenum and/or later parts of the intestine. Four DoE models were applied to optimize formulation parameters for the preparation of pH sensitive nifedipine nanoparticles. Stability studies were performed on the optimized formulations to monitor any possible variation in particle size distribution, homogeneity index, surface charge and drug release (pH 1.2 and pH 6.8). Stability studies were performed for 3 months at 4°C, 25°C and 40°C. A combination of Eudragit ® L 100-55 and polyvinyl alcohol was determined to be the most effective in stabilizing the nanoparticle suspension. The average particle size distribution, polydispersity index and surface charge of the optimized pH sensitive nifedipine nanoparticles were determined to be 131.86±8.21nm, 0.135±0.008 and -7.631±0.146mV, respectively. Following three months storage, it was observed that the formulations stored at 4°C were stable in terms of particle size distribution, polydispersity index, surface charge, drug loading and drug release, whereas those stored at 25°C and 40°C were relatively unstable. A predictive model to prepare stable pH sensitive nifedipine nanoparticles, was successfully developed using multiple linear regression analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model

NASA Astrophysics Data System (ADS)

Salazar-Camacho, Carlos; Villalobos, Mario

2010-04-01

We developed a model that describes quantitatively the arsenate adsorption behavior for any goethite preparation as a function of pH and ionic strength, by using one basic surface arsenate stoichiometry, with two affinity constants. The model combines a face distribution-crystallographic site density model for goethite with tenets of the Triple Layer and CD-MUSIC surface complexation models, and is self-consistent with its adsorption behavior towards protons, electrolytes, and other ions investigated previously. Five different systems of published arsenate adsorption data were used to calibrate the model spanning a wide range of chemical conditions, which included adsorption isotherms at different pH values, and adsorption pH-edges at different As(V) loadings, both at different ionic strengths and background electrolytes. Four additional goethite-arsenate systems reported with limited characterization and adsorption data were accurately described by the model developed. The adsorption reaction proposed is: lbond2 FeOH +lbond2 SOH +AsO43-+H→lbond2 FeOAsO3[2-]…SOH+HO where lbond2 SOH is an adjacent surface site to lbond2 FeOH; with log K = 21.6 ± 0.7 when lbond2 SOH is another lbond2 FeOH, and log K = 18.75 ± 0.9, when lbond2 SOH is lbond2 Fe 2OH. An additional small contribution of a protonated complex was required to describe data at low pH and very high arsenate loadings. The model considered goethites above 80 m 2/g as ideally composed of 70% face (1 0 1) and 30% face (0 0 1), resulting in a site density for lbond2 FeOH and for lbond2 Fe 3OH of 3.125/nm 2 each. Below 80 m 2/g surface capacity increases progressively with decreasing area, which was modeled by considering a progressively increasing proportion of faces (0 1 0)/(1 0 1), because face (0 1 0) shows a much higher site density of lbond2 FeOH groups. Computation of the specific proportion of faces, and thus of the site densities for the three types of crystallographic surface groups present in goethite, may be performed for each preparation either by experimental determination of site saturation by an index ion (e.g., chromate), or by achieving congruency of proton adsorption data with those of ideal goethites when plotted as percentage of proton-reactive ( lbond2 FeOH + lbond2 Fe 3OH) sites occupied. The surface arsenate complexes proposed additionally explained: (1) the higher affinity of goethite for As(V) than for Cr(VI) at high pH, and thus the gentle slope of the arsenate pH adsorption edges; and (2) the lower adsorption capacity for As(V) than for Cr(VI) at low pH on low-surface area goethites, through incomplete lbond2 FeOH site occupancy of As(V). The model is very promising as a practical means of predicting the adsorption behavior of arsenate on any goethite preparation, and may extend to predictive capabilities for adsorption behavior of many other relevant oxyanions, as well as for explaining differences in ligand-promoted surface transformation processes on goethite as a function of particle size.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

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.

Unfolding of a model protein on ion exchange and mixed mode chromatography surfaces.

PubMed

Gospodarek, Adrian M; Hiser, Diana E; O'Connell, John P; Fernandez, Erik J

2014-08-15

Recent studies with proteins indicate that conformational changes and aggregation can occur during ion exchange chromatography (IEC). Such behavior is not usually expected, but could lead to decreased yield and product degradation from both IEC and multi mode chromatography (MMC) that has ligands of both hydrophobic and charged functionalities. In this study, we used hydrogen exchange mass spectrometry to investigate unfolding of the model protein BSA on IEC and MMC surfaces under different solution conditions at 25°C. Increased solvent exposure, indicating greater unfolding relative to that in solution, was found for protein adsorbed on cationic IEC and MMC surfaces in the pH range of 3.0 to 4.5, where BSA has decreased stability in solution. There was no effect of anionic surfaces at pH values in the range from 6.0 to 9.0. Differences of solvent exposure of whole molecules when adsorbed and in solution suggest that adsorbed BSA unfolds at lower pH values and may show aggregation, depending upon pH and the surface type. Measurements on digested peptides showed that classifications of stability can be made for various regions; these are generally retained as pH is changed. When salt was added to MMC systems, where electrostatic interactions would be minimized, less solvent exposure was seen, implying that it is the cationic moieties, rather than the hydrophobic ligands, which cause greater surface unfolding at low salt concentrations. These results suggest that proteins of lower stability may exhibit unfolding and aggregation during IEC and MMC separations, as they can with hydrophobic interaction chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

Modeling CO2 degassing and pH in a stream-aquifer system

USGS Publications Warehouse

Choi, J.; Hulseapple, S.M.; Conklin, M.H.; Harvey, J.W.

1998-01-01

Pinal Creek, Arizona receives an inflow of ground water with high dissolved inorganic carbon (57-75 mg/l) and low pH (5.8-6.3). There is an observed increase of in-stream pH from approximately 6.0-7.8 over the 3 km downstream of the point of groundwater inflow. We hypothesized that CO2 gas-exchange was the most important factor causing the pH increase in this stream-aquifer system. An existing transport model, for coupled ground water-surface water systems (OTIS), was modified to include carbonate equilibria and CO2 degassing, used to simulate alkalinity, total dissolved inorganic carbon (C(T)), and pH in Pinal Creek. Because of the non-linear relation between pH and C(T), the modified transport model used the numerical iteration method to solve the non-linearity. The transport model parameters were determined by the injection of two tracers, bromide and propane. The resulting simulations of alkalinity, C(T) and pH reproduced, without fitting, the overall trends in downstream concentrations. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that C(T) and pH in stream water were controlled by the mixing of ground water with stream water and CO2 degassing. The relative importance of these two processes varied spatially depending on the hydrologic conditions, such as stream flow velocity and whether a reach gained or lost stream water caused by the interaction with the ground water. The coupled transport model with CO2 degassing and generalized sensitivity analysis presented in this study can be applied to evaluate carbon transport and pH in other coupled stream-ground water systems.An existing transport model for coupled groundwater-surface water systems was modified to include carbonate equilibria and CO2 degassing. The modified model was used to simulate alkalinity, total dissolved inorganic carbon (CT) and pH in Pinal Creek. The model used the numerical iteration method to solve the nonlinear relation between pH and CT. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that CT and pH in the stream water were controlled by the mixing of groundwater with stream water and CO2 degassing.

pH variation and influence in an autotrophic nitrogen removing biofilm system using an efficient numerical solution strategy.

PubMed

Vangsgaard, Anna Katrine; Mauricio-Iglesias, Miguel; Valverde-Pérez, Borja; Gernaey, Krist V; Sin, Gürkan

2013-01-01

A pH simulator consisting of an efficient numerical solver of a system of nine nonlinear equations was constructed and implemented in the modeling software MATLAB. The pH simulator was integrated in a granular biofilm model and used to simulate the pH profiles within granules performing the nitritation-anammox process for a range of operating points. The simulation results showed that pH profiles were consistently increasing with increasing depth into the granule, since the proton-producing aerobic ammonium-oxidizing bacteria (AOB) were located close to the granule surface. Despite this pH profile, more NH3 was available for AOB than for anaerobic ammonium oxidizers, located in the center of the granules. However, operating at a higher oxygen loading resulted in steeper changes in pH over the depth of the granule and caused the NH3 concentration profile to increase from the granule surface towards the center. The initial value of the background charge and influent bicarbonate concentration were found to greatly influence the simulation result and should be accurately measured. Since the change in pH over the depth of the biofilm was relatively small, the activity potential of the microbial groups affected by the pH did not change more than 5% over the depth of the granules.

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.

An Investigation of the Adsorption Characteristics of 5'ATP and 5'AMP onto the Surface of Caso4 x 2H2O

NASA Technical Reports Server (NTRS)

Calderon, J.; Sweeney, M. A.

1984-01-01

A model has been proposed in which solid surfaces can act as a site for cataletic activity of condensation reactions for certain biomolecules. From this model, the adsorption characteristics of 5'ATP and 5'AMP onto the surface of CaSO4.2H2O was chosen for study. It has been proven that 5'ATP and 5'AMP do adsorb onto the surface of CaSO4. Studies were then made to determine the dependence of absorption versus time, concentration, ionic strength and pH. It was found that the adsorption of the nucleotides is highly pH dependent, primarily determined by the phosphate acid groups of the nucleic acid molecule. From this investigation, the data obtained is discussed in relation to the model for the prebiotic earth.

An investigation of the adsorption characteristics of 5 prime ATP and 5 prime AMP onto the surface of CaSO sub 4 x 2H sub 2 O

NASA Technical Reports Server (NTRS)

Calderon, J.; Sweeney, M. A.

1986-01-01

A model has been proposed (Lahev and Chans, 1982) in which solid surfaces can act as a site for catalytic activity of condensation reactions for certain biomolecules. From this model, the adsorption characteristics of 5'ATP and 5'AMP onto the surface of CaSO4 2H2O was chosen for study. It has been proven that 5'ATP and 5'AMP do adsorb onto the surface of CaSO4. Studies were then made to determine the dependence of adsorption versus time, concentration, ionic strength and pH. It was found that the adsorption of the nucleotides is highly pH dependent, primarily determined by the phosphate acid groups of the nucleic acid molecule. From this investigation, the data obtained are discussed in relation to the model for the prebiotic earth.

Comparison of the surface ion density of silica gel evaluated via spectral induced polarization versus acid-base titration

NASA Astrophysics Data System (ADS)

Hao, Na; Moysey, Stephen M. J.; Powell, Brian A.; Ntarlagiannis, Dimitrios

2016-12-01

Surface complexation models are widely used with batch adsorption experiments to characterize and predict surface geochemical processes in porous media. In contrast, the spectral induced polarization (SIP) method has recently been used to non-invasively monitor in situ subsurface chemical reactions in porous media, such as ion adsorption processes on mineral surfaces. Here we compare these tools for investigating surface site density changes during pH-dependent sodium adsorption on a silica gel. Continuous SIP measurements were conducted using a lab scale column packed with silica gel. A constant inflow of 0.05 M NaCl solution was introduced to the column while the influent pH was changed from 7.0 to 10.0 over the course of the experiment. The SIP measurements indicate that the pH change caused a 38.49 ± 0.30 μS cm- 1 increase in the imaginary conductivity of the silica gel. This increase is thought to result from deprotonation of silanol groups on the silica gel surface caused by the rise in pH, followed by sorption of Na+ cations. Fitting the SIP data using the mechanistic model of Leroy et al. (Leroyet al., 2008), which is based on the triple layer model of a mineral surface, we estimated an increase in the silica gel surface site density of 26.9 × 1016 sites m- 2. We independently used a potentiometric acid-base titration data for the silica gel to calibrate the triple layer model using the software FITEQL and observed a total increase in the surface site density for sodium sorption of 11.2 × 1016 sites m- 2, which is approximately 2.4 times smaller than the value estimated using the SIP model. By simulating the SIP response based on the calibrated surface complexation model, we found a moderate association between the measured and estimated imaginary conductivity (R2 = 0.65). These results suggest that the surface complexation model used here does not capture all mechanisms contributing to polarization of the silica gel captured by the SIP data.

The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

USGS Publications Warehouse

Plummer, Niel; Wigley, T.M.L.

1976-01-01

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

Surface functional groups in capacitive deionization with porous carbon electrodes

NASA Astrophysics Data System (ADS)

Hemmatifar, Ali; Oyarzun, Diego I.; Palko, James W.; Hawks, Steven A.; Stadermann, Michael; Santiago, Juan G.; Stanford Microfluidics Lab Team; Lawrence Livermore National Lab Team

2017-11-01

Capacitive deionization (CDI) is a promising technology for removal of toxic ions and salt from water. In CDI, an applied potential of about 1 V to pairs of porous electrodes (e.g. activated carbon) induces ion electromigration and electrostatic adsorption at electrode surfaces. Immobile surface functional groups play a critical role in the type and capacity of ion adsorption, and this can dramatically change desalination performance. We here use models and experiments to study weak electrolyte surface groups which protonate and/or depropotante based on their acid/base dissociation constants and local pore pH. Net chemical surface charge and differential capacitance can thus vary during CDI operation. In this work, we present a CDI model based on weak electrolyte acid/base equilibria theory. Our model incorporates preferential cation (anion) adsorption for activated carbon with acidic (basic) surface groups. We validated our model with experiments on custom built CDI cells with a variety of functionalizations. To this end, we varied electrolyte pH and measured adsorption of individual anionic and cationic ions using inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) techniques. Our model shows good agreement with experiments and provides a framework useful in the design of CDI control schemes.

An extended model based on the modified Nernst-Planck equation for describing transdermal iontophoresis of weak electrolytes.

PubMed

Imanidis, Georgios; Luetolf, Peter

2006-07-01

An extended model for iontophoretic enhancement of transdermal drug permeation under constant voltage is described based on the previously modified Nernst-Planck equation, which included the effect of convective solvent flow. This model resulted in an analytical expression for the enhancement factor as a function of applied voltage, convective flow velocity due to electroosmosis, ratio of lipid to aqueous pathway passive permeability, and weighted average net ionic valence of the permeant in the aqueous epidermis domain. The shift of pH in the epidermis compared to bulk caused by the electrical double layer at the lipid-aqueous domain interface was evaluated using the Poisson-Boltzmann equation. This was solved numerically for representative surface charge densities and yielded pH differences between bulk and epidermal aqueous domain between 0.05 and 0.4 pH units. The developed model was used to analyze the experimental enhancement of an amphoteric weak electrolyte measured in vitro using human cadaver epidermis and a voltage of 250 mV at different pH values. Parameter values characterizing the involved factors were determined that yielded the experimental enhancement factors and passive permeability coefficients at all pH values. The model provided a very good agreement between experimental and calculated enhancement and passive permeability. The deduced parameters showed (i) that the pH shift in the aqueous permeation pathway had a notable effect on the ionic valence and the partitioning of the drug in this domain for a high surface charge density and depending on the pK(a) and pI of the drug in relation to the bulk pH; (ii) the magnitude and the direction of convective transport due to electroosmosis typically reflected the density and sign, respectively, of surface charge of the tissue and its effect on enhancement was substantial for bulk pH values differing from the pI of epidermal tissue; (iii) the aqueous pathway predominantly determined passive permeability of the studied compound despite its measurable lipophilicity and therefore the lipid pathway did not notably affect enhancement. Hence, the proposed model can provide a good quantitative insight into the interplay between different phenomena and permeant properties influencing iontophoresis and can potentially be used as a predictive tool of the process.

Ionic strength effects on silicic acid (H4SiO4) sorption and oligomerization on an iron oxide surface: an interesting interplay between electrostatic and chemical forces.

PubMed

Hamid, Rossuriati Dol; Swedlund, Peter J; Song, Yantao; Miskelly, Gordon M

2011-11-01

The effect of ionic strength on reactions at aqueous interfaces can provide insights into the nature of the chemistry involved. The adsorption of H(4)SiO(4) on iron oxides at low surface silicate concentration (Γ(Si)) forms monomeric silicate complexes with Fe-O-Si linkages, but as Γ(Si) increases silicate oligomers with Si-O-Si linkages become increasingly prevalent. In this paper, the effect of ionic strength (I) on both Γ(Si) and the extent of silicate oligomerization on the ferrihydrite surface is determined at pH 4, 7, and 10, where the surface is, respectively, positive, nearly neutral, and negatively charged. At pH 4, an increase in ionic strength causes Γ(Si) to decrease at a given H(4)SiO(4) solution concentration, while the proportion of oligomers on the surface at a given Γ(Si) increases. At pH 10, the opposite is observed; Γ(Si) increases as I increases, while the proportion of surface oligomers at a given Γ(Si) decreases. Ionic strength has only a small effect on the surface chemistry of H(4)SiO(4) at pH 7, but at low Γ(Si) this effect is in the direction observed at pH 4 while at high Γ(Si) the effect is in the direction observed at pH 10. The pH where the surface has zero charge decreases from ≈8 to 6 as Γ(Si) increases so that the surface potential (Ψ) is positive at pH 4 for all Γ(Si) and at pH 7 with low Γ(Si). Likewise, Ψ < 0 at pH 10 for all Γ(Si) and at pH 7 with high Γ(Si). The diffuse layer model is used to unravel the complex and subtle interactions between surface potential (Ψ) and chemical parameters that influence interfacial silicate chemistry. This analysis reveals that the decrease in the absolute value of Ψ as I increases causes Γ(Si) to decrease or increase where Ψ is, respectively, positive or negative. Therefore, at a given Γ(Si), the solution H(4)SiO(4) concentration changes with I, and because oligomerization has a higher H(4)SiO(4) stoichiometry coefficient than monomer adsorption, this results in the observed dependence of the extent of silicate oligomerization on I.

Organosilane functionalization of halloysite nanotubes for enhanced loading and controlled release.

PubMed

Yuan, Peng; Southon, Peter D; Liu, Zongwen; Kepert, Cameron J

2012-09-21

The surfaces of naturally occurring halloysite nanotubes were functionalized with γ-aminopropyltriethoxysilane (APTES), which was found to have a substantial effect on the loading and subsequent release of a model dye molecule. APTES was mostly anchored at the internal lumen surface of halloysite through covalent grafting, forming a functionalized surface covered by aminopropyl groups. The dye loading of the functionalized halloysite was 32% greater than that of the unmodified sample, and the release from the functionalized halloysite was dramatically prolonged as compared to that from the unmodified one. Dye release was prolonged at low pH and the release at pH 3.5 was approximately three times slower than that at pH 10.0. These results demonstrate that organosilane functionalization makes pH an external trigger for controlling the loading of guest on halloysite and the subsequent controlled release.

How Helicobacter pylori urease may affect external pH and influence growth and motility in the mucus environment: evidence from in-vitro studies.

PubMed

Sidebotham, Ramon L; Worku, Mulugeta L; Karim, Q Najma; Dhir, Nirmal K; Baron, J Hugh

2003-04-01

Survival of Helicobacter pylori is dependent upon urease in the cytoplasm and at the bacterial surface. We have sought to clarify how alkaline ammonium salts, released from urea by this enzyme, might alter mucus pH and so affect growth and motility of the bacterium in the gastric mucus environment. Experiments were conducted in vitro to determine how the growth and motility of H. pylori are affected by changes in external pH, and how the bacterium, by hydrolysing urea, alters the pH of the bicarbonate buffer that occurs at the gastric mucosal surface. These data were fitted into experimental models that describe how pH varies within the mucus layer in the acid-secreting stomach. H. pylori was motile between pH 5 and 8, with optimal motility at pH 5. It grew between pH 6 and 8, with optimal growth at pH 6. The bacterium had urease activity between pH 2.7 and 7.4, as evidenced by pH rises in bicarbonate-buffered solutions of urea. Changes in buffer pH were dependent upon initial pH and urea concentration, with the greatest rate of pH change occurring at pH 3. Modelling experiments utilizing these data indicated that (1) in the absence of urease, H. pylori growth and motility in the mucus layer would be restricted severely by low mucus pH in the acid-secreting stomach, and (2) urease will sometimes inhibit H. pylori growth and motility in the mucus layer by elevating the pH of the mucus environment above pH 8. Urease is essential to the growth and motility of H. pylori in the mucus layer in the acid-secreting stomach, but, paradoxically, sometimes it might suppress colonization by raising the mucus pH above 8. This latter effect may protect the bacteria from the adverse consequences of overpopulation.

Removal of aniline and phenol from water using raw and aluminum hydroxide-modified diatomite.

PubMed

Wu, C D; Zhang, J Y; Wang, L; He, M H

2013-01-01

The feasibility of using raw diatomite and aluminum hydroxide-modified diatomite (Al-diatomite) for removal of aniline and phenol from water was investigated. Their physicochemical characteristics such as pHsolution, point of zero charge (pHPZC), surface area, Fourier transform infrared (FT-IR) and scanning electron microscopy was determined. After the raw diatomite was modified, the surface area of Al-diatomite increases from 26.67 to 82.65 m(2) g(-1). The pHPZC and pHsolution (10%) occurred around pH 5.2 and pH 8.6, respectively. The removal rates of aniline and phenol on diatomite and Al-diatomite decreased with increasing solution pH, while surface charge density decreased. The adsorption of aniline and phenol on diatomite presented a good fit to the Langmuir and Freundlich models, but the models are not fit to forecast the adsorption of aniline and phenol on Al-diatomite. The study indicated that electrostatic interaction was a dominating mechanism of aniline and phenol sorption onto Al-diatomite.

Migration of the guinea pig sperm membrane protein PH-20 from one localized surface domain to another does not occur by a simple diffusion-trapping mechanism.

PubMed

Cowan, A E; Myles, D G; Koppel, D E

1991-03-01

The redistribution of membrane proteins on the surface of cells is a prevalent feature of differentiation in a variety of cells. In most cases the mechanism responsible for such redistribution is poorly understood. Two potential mechanisms for the redistribution of surface proteins are: (1) passive diffusion coupled with trapping, and (2) active translocation. We have studied the process of membrane protein redistribution for the PH-20 protein of guinea pig sperm, a surface protein required for sperm binding to the egg zona pellucida (P. Primakoff, H. Hyatt, and D. G. Myles (1985). J. Cell Biol. 101, 2239-2244). PH-20 protein is localized to the posterior head plasma menbrane of the mature sperm cell. Following the exocytotic acrosome reaction, PH-20 protein moves into the newly incorporated inner acrosomal membrane (IAM), placing it in a position favorable for a role in binding sperm to the egg zona pellucida (D. G. Myles, and P. Primakoff (1984), J. Cell Biol. 99, 1634-1641). To analyze the mechanistic basis for this protein migration, we have used fluorescence microscopy and digital image processing to characterize PH-20 protein migration in individual cells. PH-20 protein was observed to move against a concentration gradient in the posterior head plasma membrane. This result argues strongly against a model of passive diffusion followed by trapping in the IAM, and instead suggests that an active process serves to concentrate PH-20 protein toward the boundary separating the posterior head and IAM regions. A transient gradient of PH-20 concentration observed in the IAM suggests that once PH-20 protein reaches the IAM, it is freely diffusing. Additionally, we observed that migration of PH-20 protein was calcium dependent.

Silicic acid competes for dimethylarsinic acid (DMA) immobilization by the iron hydroxide plaque mineral goethite.

PubMed

Kersten, Michael; Daus, Birgit

2015-03-01

A surface complexation modeling approach was used to extend the knowledge about processes that affect the availability of dimethylarsinic acid (DMA) in the soil rhizosphere in presence of a strong sorbent, e.g., Fe plaques on rice roots. Published spectroscopic and molecular modeling information suggest for the organoarsenical agent to form bidentate-binuclear inner-sphere surface complexes with Fe hydroxides similar to the inorganic As oxyanions. However, since also the ubiquitous silicic acid oxyanion form the same bidentate binuclear surface complexes, our hypothesis was that it may have an effect on the adsorption of DMA by Fe hydroxides in soil. Our experimental batch equilibrium data show that DMA is strongly adsorbed in the acidic pH range, with a steep adsorption edge in the circumneutral pH region between the DMA acidity constant (pKa=6.3) and the point of zero charge value of the goethite adsorbent (pHpzc=8.6). A 1-pK CD-MUSIC surface complexation model was chosen to fit the experimental adsorption vs. pH data. The same was done for silicic acid batch equilibrium data with our goethite adsorbent. Both model parameters for individual DMA and silicic acid adsorption were then merged into one CD-MUSIC model to predict the binary DMA+Si adsorption behavior. Silicic acid (500 μM) was thus predicted by the model to strongly compete for DMA with up to 60% mobilization of the latter at a pH6. This model result could be verified subsequently by experimental batch equilibrium data with zero adjustable parameters. The thus quantified antagonistic relation between DMA and silicic acid is discussed as one of factors to explain the increase of the DMA proportion in rice grains as observed upon silica fertilization of rice fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of Acidified Sorbate Solutions on the Lag-Phase Durations and Growth Rates of Listeria monocytogenes on Meat Surfaces.

PubMed

Hwang, Cheng-An; Huang, Lihan; Juneja, Vijay

2015-06-01

The surfaces of ready-to-eat meats are susceptible to postprocessing contamination by Listeria monocytogenes. This study quantified the lag-phase durations (LPD) and growth rates (GR) of L. monocytogenes on the surfaces of cooked ham as affected by sorbate solutions of different concentrations and pH levels. Slices of cooked ham inoculated with a four-strain mixture of L. monocytogenes (ca. 10(3) CFU/g) were surface treated with sorbate solutions of 0 to 4% (wt/vol) at pH 4.0 to 6.5, vacuum packaged, and stored at 4 to 12 °C for up to 45 days. The LPD and GR of L. monocytogenes were used to develop response surface models. The models estimated that the LPD of L. monocytogenes in samples treated with solutions of pH 4.0 to 5.5 (no sorbate) were 0 to 11 days and the GR were 0.25 to 0.36 log CFU/day, respectively, at 4 °C. With the treatments of 2 and 4% (wt/vol) sorbate solutions, the LPD were estimated to be extended to 2 to 26 days and 34 to >45 days, and the GR were reduced to 0.15 to 0.30 and 0 to 0.19 log CFU/day, respectively. At 4 °C, increasing sorbate concentrations by 1% (wt/vol) to 2, 3, and 4% (wt/vol) at pH 5.5 to 4.0 led to an extension of LPD by 2 to 11, 10 to 19, and 18 to 27 days, whereas the GR were reduced by 0.037 to 0.055, 0.048 to 0.066, and 0.060 to 0.078 log CFU/day, respectively. Sorbate also extended the LPD and reduced the GR of L. monocytogenes at 8 and 12 °C. Results indicated that sorbate concentration and pH level were significant factors affecting the LPD and GR of L. monocytogenes and that the combination of sorbate and low pH has potential for use as a surface treatment to control L. monocytogenes on meat surfaces.

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and on pH, electrostatic interactions, hydrogen bonding, and ternary surface complexation contribute in varying degrees to the adsorption process. Linear distribution coefficients K d between 8.7 and 60.5 L kg -1 (1 mmol L -1 initial PHCA concentration) indicate a considerable mineral surface affinity at very high pH, thus lowering the PHCA fraction available for the complexation of metal ions including radionuclides in solution and their subsequent mobilization.

Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.

PubMed

Sjöstedt, Carin S; Gustafsson, Jon Petter; Köhler, Stephan J

2010-11-15

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

PubMed

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level < 2 ppmv. Tin redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

Cotton growth modeling and assessment using unmanned aircraft system visual-band imagery

NASA Astrophysics Data System (ADS)

Chu, Tianxing; Chen, Ruizhi; Landivar, Juan A.; Maeda, Murilo M.; Yang, Chenghai; Starek, Michael J.

2016-07-01

This paper explores the potential of using unmanned aircraft system (UAS)-based visible-band images to assess cotton growth. By applying the structure-from-motion algorithm, the cotton plant height (ph) and canopy cover (cc) information were retrieved from the point cloud-based digital surface models (DSMs) and orthomosaic images. Both UAS-based ph and cc follow a sigmoid growth pattern as confirmed by ground-based studies. By applying an empirical model that converts the cotton ph to cc, the estimated cc shows strong correlation (R2=0.990) with the observed cc. An attempt for modeling cotton yield was carried out using the ph and cc information obtained on June 26, 2015, the date when sigmoid growth curves for both ph and cc tended to decline in slope. In a cross-validation test, the correlation between the ground-measured yield and the estimated equivalent derived from the ph and/or cc was compared. Generally, combining ph and cc, the performance of the yield estimation is most comparable against the observed yield. On the other hand, the observed yield and cc-based estimation produce the second strongest correlation, regardless of the complexity of the models.

Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) surfaces at 10-50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

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.

Effect of pH and pulsed electric field process parameters on the aflatoxin reduction in model system using response surface methodology: Effect of pH and PEF on Aflatoxin Reduction.

PubMed

Vijayalakshmi, Subramanian; Nadanasabhapathi, Shanmugam; Kumar, Ranganathan; Sunny Kumar, S

2018-03-01

The presence of aflatoxin, a carcinogenic and toxigenic secondary metabolite produced by Aspergillus species, in food matrix has been a major worldwide problem for years now. Food processing methods such as roasting, extrusion, etc. have been employed for effective destruction of aflatoxins, which are known for their thermo-stable nature. The high temperature treatment, adversely affects the nutritive and other quality attributes of the food, leading to the necessity of application of non-thermal processing techniques such as ultrasonication, gamma irradiation, high pressure processing, pulsed electric field (PEF), etc. The present study was focused on analysing the efficacy of the PEF process in the reduction of the toxin content, which was subsequently quantified using HPLC. The process parameters of different pH model system (potato dextrose agar) artificially spiked with aflatoxin mix standard was optimized using the response surface methodology. The optimization of PEF process effects on the responses aflatoxin B1 and total aflatoxin reduction (%) by pH (4-10), pulse width (10-26 µs) and output voltage (20-65%), fitted 2FI model and quadratic model respectively. The response surface plots obtained for the processes were of saddle point type, with the absence of minimum or maximum response at the centre point. The implemented numerical optimization showed that the predicted and actual values were similar, proving the adequacy of the fitted models and also proved the possible application of PEF in toxin reduction.

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

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

Cances, Benjamin; Benedetti, Marc; Farges, Francois

2007-02-02

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands atmore » pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

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

Cances, Benjamin; /Marne La Vallee U.; Benedetti, Marc

2006-12-13

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OHmore » ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

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.

Gallium(III) adsorption on carbonates and oxides: X-ray absorption fine structure spectroscopy study and surface complexation modeling.

PubMed

Pokrovsky, O S; Pokrovski, G S; Schott, J

2004-11-15

Adsorption of Ga on calcite, magnesite, amorphous silica, and manganese oxide as a function of pH and gallium concentration in solution was studied using a batch adsorption technique. Adsorbed complexes of Ga on calcite, magnesite, and delta-MnO2 were further characterized using XAFS spectroscopy. At high surface loadings from supersaturated solutions, Ga is likely to form a polymeric network at the surface (edge- and corner-sharing octahedra). At low surface loadings, Ga presents as isolated octahedra, probably attached to the Me-O sites on the surface, and coordinated by water molecules and hydroxide groups at 1.90-1.94 A. At pH>6, Ga therefore changes its coordination from 4 to 6 when adsorbing from solution (Ga(OH)(-)4(aq)) onto metal surface sites (MeOGa(OH)n(H2O)2-n(5-n), Me = Ca, Mg, or Mn, and n=1 and 2 for carbonate minerals and MnO2, respectively). Because the EXAFS is not capable of seeing hydrogen atoms, the protonation of surface complexes was determined by fitting the experimental pH-dependent Ga adsorption edge. A surface complexation model which assumes the constant capacitance of the electric double layer (CCM) and postulates the formation of positively charged, neutral and negatively charged surface complexes for carbonates, manganese oxide and silica, respectively, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Ga concentration.

Phosphate adsorption on hematite, kaolinite, and kaolinite-hematite (k-h) systems as described by a constant capacitance model

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

Ioannou, A.; Dimirkou, A.

1997-08-01

The constant capacitance model was used to describe phosphate adsorption on hematite, kaolinite, and a kaolinite-hematite system (k-h). The model assumes a ligand exchange mechanism and considers the charge on both adsorbate and adsorbent. The model is shown to provide a quantitative description of phosphate adsorption on these, including the effect of varying pH values. The computer program Ma-Za 2, a program that fits equilibrium constants to experimental data using an optimization technique, was used to obtain optimal values for the anion surface complexation constants on hematite, kaolinite, and a kaolinite-hematite system, while the PC program Ma-Za 1 in Q-Basicmore » language was used for the application of the constant capacitance model. The model represented adsorption of phosphate anions well over the entire pH range studied (3.8--9.0). The main advantage of the model is its ability to represent changes in anion adsorption occurring with changes in pH. Extension of the model to describe phosphate adsorption in a mixed system, such as the kaolinite-hematite system, using the surface protonation-dissociation constant of hematite was qualitatively successful. In mixed system the model reproduced the shape of the adsorption isotherms well over the pH range 3.8--9.0. However, phosphate adsorption was overestimated. The hematite and the kaolinite-hematite system were synthesized and identified by X-ray, NMR, and FT-IR spectroscopy.« less

Modeling the growth of Listeria monocytogenes on the surface of smear- or mold-ripened cheese.

PubMed

Schvartzman, M Sol; Gonzalez-Barron, Ursula; Butler, Francis; Jordan, Kieran

2014-01-01

Surface-ripened cheeses are matured by means of manual or mechanical technologies posing a risk of cross-contamination, if any cheeses are contaminated with Listeria monocytogenes. In predictive microbiology, primary models are used to describe microbial responses, such as growth rate over time and secondary models explain how those responses change with environmental factors. In this way, primary models were used to assess the growth rate of L. monocytogenes during ripening of the cheeses and the secondary models to test how much the growth rate was affected by either the pH and/or the water activity (aw) of the cheeses. The two models combined can be used to predict outcomes. The purpose of these experiments was to test three primary (the modified Gompertz equation, the Baranyi and Roberts model, and the Logistic model) and three secondary (the Cardinal model, the Ratowski model, and the Presser model) mathematical models in order to define which combination of models would best predict the growth of L. monocytogenes on the surface of artificially contaminated surface-ripened cheeses. Growth on the surface of the cheese was assessed and modeled. The primary models were firstly fitted to the data and the effects of pH and aw on the growth rate (μmax) were incorporated and assessed one by one with the secondary models. The Logistic primary model by itself did not show a better fit of the data among the other primary models tested, but the inclusion of the Cardinal secondary model improved the final fit. The aw was not related to the growth of Listeria. This study suggests that surface-ripened cheese should be separately regulated within EU microbiological food legislation and results expressed as counts per surface area rather than per gram.

On-chip surface modified nanostructured ZnO as functional pH sensors

NASA Astrophysics Data System (ADS)

Zhang, Qing; Liu, Wenpeng; Sun, Chongling; Zhang, Hao; Pang, Wei; Zhang, Daihua; Duan, Xuexin

2015-09-01

Zinc oxide (ZnO) nanostructures are promising candidates as electronic components for biological and chemical applications. In this study, ZnO ultra-fine nanowire (NW) and nanoflake (NF) hybrid structures have been prepared by Au-assisted chemical vapor deposition (CVD) under ambient pressure. Their surface morphology, lattice structures, and crystal orientation were investigated by scanning electron microscopy (SEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM). Two types of ZnO nanostructures were successfully integrated as gate electrodes in extended-gate field-effect transistors (EGFETs). Due to the amphoteric properties of ZnO, such devices function as pH sensors. We found that the ultra-fine NWs, which were more than 50 μm in length and less than 100 nm in diameter, performed better in the pH sensing process than NW-NF hybrid structures because of their higher surface-to-volume ratio, considering the Nernst equation and the Gouy-Chapman-Stern model. Furthermore, the surface coating of (3-Aminopropyl)triethoxysilane (APTES) protects ZnO nanostructures in both acidic and alkaline environments, thus enhancing the device stability and extending its pH sensing dynamic range.

Macroion induced dehydration of weak polyelectrolyte brushes

NASA Astrophysics Data System (ADS)

Zheng, Zhongli; Zhu, Y. Elaine

2014-03-01

The interaction of macroions, including polyelectrolytes, DNAs, and proteins, with polymer and cellular surfaces is critically related to many biomolecular activities, such as protein adsorption and DNA hybridization at probe surfaces. In an experimental approach to examine the macroion electrostatic interaction with a polymer surface while minimizing the long-debated hydrophobic interaction, we study the interaction of molybdenum-based inorganic polyoxometalate (POM) nanoclusters carrying 42 negative charges as model hydrophilic macroions with surface-tethered poly-2-vinylpyridine (P2VP) brushes immersed in aqueous solutions. By AFM, QCM, and contact goniometer, we have observed the collapse of P2VP chains by adding POM macroions at a constant pH. Surprisingly, added POM macroions can cause the shift of swollen-to-collapse transition pH to a lower value, in contrast to the shift to high pH value by adding simple monovalent salts. At sufficiently high POM concentration, a stable POM-P2VP composite layer, showing little dependence on solution pH and additional salts, can be formed, suggesting a simple route to construct meso-porous polymer membranes.

Anomalous pH-Dependent Nanofluidic Salinity Gradient Power.

PubMed

Yeh, Li-Hsien; Chen, Fu; Chiou, Yu-Ting; Su, Yen-Shao

2017-12-01

Previous studies on nanofluidic salinity gradient power (NSGP), where energy associated with the salinity gradient can be harvested with ion-selective nanopores, all suggest that nanofluidic devices having higher surface charge density should have higher performance, including osmotic power and conversion efficiency. In this manuscript, this viewpoint is challenged and anomalous counterintuitive pH-dependent NSGP behaviors are reported. For example, with equal pH deviation from its isoelectric point (IEP), the nanopore at pH < IEP is shown to have smaller surface charge density but remarkably higher NSGP performance than that at pH > IEP. Moreover, for sufficiently low pH, the NSGP performance decreases with lowering pH (increasing nanopore charge density). As a result, a maximum osmotic power density as high as 5.85 kW m -2 can be generated along with a conversion efficiency of 26.3% achieved for a single alumina nanopore at pH 3.5 under a 1000-fold concentration ratio. Using the rigorous model with considering the surface equilibrium reactions on the pore wall, it is proved that these counterintuitive surface-charge-dependent NSGP behaviors result from the pH-dependent ion concentration polarization effect, which yields the degradation in effective concentration ratio across the nanopore. These findings provide significant insight for the design of next-generation, high-performance NSGP devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Photooxidative Removal of Phenazopyridine from Water

NASA Astrophysics Data System (ADS)

Saeid, Soudabeh; Behnajady, Mohammad A.; Tolvanen, Pasi; Salmi, Tapio

2018-05-01

The photooxidative removal of analgesic pharmaceutical compound phenazopyridine (PhP) from aqueous solutions by UV/H2O2 system with a re-circulated photoreactor was investigated. Response surface methodology (RSM) was employed to optimize the effect of operational parameters on the photooxidative removal efficiency. The investigated variables were: the initial PhP and H2O2 concentrations, irradiation time, volume of solution and pH. The analysis of variance (ANOVA) of quadratic model demonstrated that the described model was highly significant. The predicted values of the photooxidative removal efficiency were found to be in a fair agreement with experimental values ( R 2 = 0.9832, adjusted R 2 = 0.9716). The model predicted that the optimal reaction conditions for a maximum removal of PhP (>98%) were: initial PhP concentration less than 23 mg L-1, initial concentration of H2O2 higher than 470 mg L-1, solution volume less than 500 mL, pH close to 2 and irradiation time longer than 6 min.

Development and characterization of a voltammetric carbon-fiber microelectrode pH sensor.

PubMed

Makos, Monique A; Omiatek, Donna M; Ewing, Andrew G; Heien, Michael L

2010-06-15

This work describes the development and characterization of a modified carbon-fiber microelectrode sensor capable of measuring real-time physiological pH changes in biological microenvironments. The reagentless sensor was fabricated under ambient conditions from voltammetric reduction of the diazonium salt Fast Blue RR onto a carbon-fiber surface in aprotic media. Fast-scan cyclic voltammetry was used to probe redox activity of the p-quinone moiety of the surface-bound molecule as a function of pH. In vitro calibration of the sensor in solutions ranging from pH 6.5 to 8.0 resulted in a pH-dependent anodic peak potential response. Flow-injection analysis was used to characterize the modified microelectrode, revealing sensitivity to acidic and basic changes discernible to 0.005 pH units. Furthermore, the modified electrode was used to measure dynamic in vivo pH changes evoked during neurotransmitter release in the central nervous system of the microanalytical model organism Drosophila melanogaster.

Development and Characterization of a Voltammetric Carbon-fiber Microelectrode pH Sensor

PubMed Central

Makos, Monique A.; Omiatek, Donna M.; Ewing, Andrew G.; Heien, Michael L.

2010-01-01

This work describes the development and characterization of a modified carbon-fiber microelectrode sensor capable of measuring real-time physiological pH changes in biological microenvironments. The reagentless sensor was fabricated under ambient conditions from voltammetric reduction of the diazonium salt Fast Blue RR onto a carbon-fiber surface in aprotic media. Fast-scan cyclic voltammetry was used to probe redox activity of the p-quinone moiety of the surface-bound molecule as a function of pH. In vitro calibration of the sensor in solutions ranging from pH 6.5 to 8.0 resulted in a pH-dependent anodic peak potential response. Flow-injection analysis was used to characterize the modified microelectrode, revealing sensitivity to acidic and basic changes discernable to 0.005 pH units. Furthermore, the modified electrode was used to measure dynamic in vivo pH changes evoked during neurotransmitter release in the central nervous system of the microanalytical model organism Drosophila melanogaster. PMID:20380393

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).

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.

Adsorption behavior of a human monoclonal antibody at hydrophilic and hydrophobic surfaces

PubMed Central

Couston, Ruairidh G.; Skoda, Maximilian W.; Uddin, Shahid; van der Walle, Christopher F.

2013-01-01

One aspiration for the formulation of human monoclonal antibodies (mAb) is to reach high solution concentrations without compromising stability. Protein surface activity leading to instability is well known, but our understanding of mAb adsorption to the solid-liquid interface in relevant pH and surfactant conditions is incomplete. To investigate these conditions, we used total internal reflection fluorescence (TIRF) and neutron reflectometry (NR). The mAb tested (“mAb-1”) showed highest surface loading to silica at pH 7.4 (~12 mg/m2), with lower surface loading at pH 5.5 (~5.5 mg/m2, further from its pI of 8.99) and to hydrophobized silica (~2 mg/m2). The extent of desorption of mAb-1 from silica or hydrophobized silica was related to the relative affinity of polysorbate 20 or 80 for the same surface. mAb-1 adsorbed to silica on co-injection with polysorbate (above its critical micelle concentration) and also to silica pre-coated with polysorbate. A bilayer model was developed from NR data for mAb-1 at concentrations of 50–5000 mg/L, pH 5.5, and 50–2000 mg/L, pH 7.4. The inner mAb-1 layer was adsorbed to the SiO2 surface at near saturation with an end-on” orientation, while the outer mAb-1 layer was sparse and molecules had a “side-on” orientation. A non-uniform triple layer was observed at 5000 mg/L, pH 7.4, suggesting mAb-1 adsorbed to the SiO2 surface as oligomers at this concentration and pH. mAb-1 adsorbed as a sparse monolayer to hydrophobized silica, with a layer thickness increasing with bulk concentration - suggesting a near end-on orientation without observable relaxation-unfolding. PMID:23196810

Optimal Semi-Adaptive Search With False Targets

DTIC Science & Technology

2017-12-01

we do not execute a full experimental design to attempt to build a response surface for the performance of these model under various combinations of...the degree of MASTER OF SCIENCE IN OPERATIONS RESEARCH from the NAVAL POSTGRADUATE SCHOOL December 2017 Approved by: Johannes O. Royset, Ph.D. Thesis...Advisor Dashi I. Singham, Ph.D. Second Reader Patricia A. Jacobs, Ph.D. Chair, Department of Operations Research iii THIS PAGE INTENTIONALLY LEFT

Modeling the Effect of pH and Temperature for Cellulases Immobilized on Enzymogel Nanoparticles.

PubMed

Samaratunga, Ashani; Kudina, Olena; Nahar, Nurun; Zakharchenko, Andrey; Minko, Sergiy; Voronov, Andriy; Pryor, Scott W

2015-06-01

Production costs of cellulosic biofuels can be lowered if cellulases are recovered and reused using particulate carriers that can be extracted after biomass hydrolysis. Such enzyme recovery was recently demonstrated using enzymogel nanoparticles with grafted polymer brushes loaded with cellulases. In this work, cellulase (NS50013) and β-glucosidase (Novozyme 188) were immobilized on enzymogels made of poly(acrylic acid) polymer brushes grafted to the surface of silica nanoparticles. Response surface methodology was used to model effects of pH and temperature on hydrolysis and recovery of free and attached enzymes. Hydrolysis yields using both enzymogels and free cellulase and β-glucosidase were highest at the maximum temperature tested, 50 °C. The optimal pH for cellulase enzymogels and free enzyme was 5.0 and 4.4, respectively, while both free β-glucosidase and enzymogels had an optimal pH near 4.4. Highest hydrolysis sugar concentrations with cellulase and β-glucosidase enzymogels were 69 and 53 % of those with free enzymes, respectively. Enzyme recovery using enzymogels decreased with increasing pH, but cellulase recovery remained greater than 88 % throughout the operating range of pH values less than 5.0 and was greater than 95 % at pH values below 4.3. Recovery of β-glucosidase enzymogels was not affected by temperature and had little impact on cellulase recovery.

pH dependent silver nanoparticles releasing titanium implant: A novel therapeutic approach to control peri-implant infection.

PubMed

Dong, Yiwen; Ye, Hui; Liu, Yi; Xu, Lihua; Wu, Zuosu; Hu, Xiaohui; Ma, Jianfeng; Pathak, Janak L; Liu, Jinsong; Wu, Gang

2017-10-01

Peri-implant infection control is crucial for implant fixation and durability. Antimicrobial administration approaches to control peri-implant infection are far from satisfactory. During bacterial infection, pH level around the peri-implant surface decreases as low as pH 5.5. This change of pH can be used as a switch to control antimicrobial drug release from the implant surface. Silver nanoparticles (AgNPs) have broad-spectrum antimicrobial properties. In this study, we aimed to design a pH-dependent AgNPs releasing titania nanotube arrays (TNT) implant for peri-implant infection control. The nanotube arrays were fabricated on the surface of titanium implant as containers; AgNPs were grafted on TNT implant surface via a low pH-sensitive acetal linker (TNT-AL-AgNPs). SEM, TEM, AFM, FTIR as well as XPS data showed that AgNPs have been successfully linked to TNT via acetal linker without affecting the physicochemical characteristics of TNT. The pH 5.5 enhanced AgNPs release from TNT-AL-AgNPs implant compared with pH 7.4. AgNPs released at pH 5.5 robustly increased antimicrobial activities against gram-positive and gram-negative bacteria compared with AgNPs released at pH 7.4. TNT-AL-AgNPs implant enhanced osteoblast proliferation, differentiation, and did not affect osteoblast morphology in vitro. In conclusion, incorporation of AgNPs in TNT via acetal linker maintained the surface characteristics of TNT. TNT-AL-AgNPs implant was biocompatible to osteoblasts and showed osteoinductive properties. AgNPs were released from TNT-AL-AgNPs implant in high dose at pH 5.5, and this release showed strong antimicrobial properties in vitro. Therefore, this novel design of low pH-triggered AgNPs releasing TNT-AL-AgNPs could be an infection-triggered antimicrobial releasing implant model to control peri-implant infection. Copyright © 2017 Elsevier B.V. All rights reserved.

Uranium Adsorption on Ferrihydrite - Effects of Phosphate and Humic Acid

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Waite, T.D.

1996-01-01

Uranium adsorption on ferrihydrite was studied as a function of pH in systems equilibrated with air, in the presence and absence of added phosphate and humic acid (HA). The objective was to determine the influence of PO43- and HA on uranium uptake. Below pH 7, the sorption of UO22+ typically increases with increasing pH (the 'low pH sorption edge'), with a sharp decrease in sorption above this pH value (the 'high pH edge'). The presence of ??PO43- of 10-4 mol/L moved the low pH edge to the left by approximately 0.8 pH units. The PO43- was strongly bound by the ferrihydrite surface, and the increased uptake of U was attributed to the formation of ternary surface complexes involving both UO22+ and PO43-. The addition of HA (9 mg/L) increased U uptake at pH values below 7, with little effect at higher pH values. The positions of the pH edges were also affected by the ionic strength and total U content. These experiments show that sorption interactions involving PO43 and HA must be considered in order to model the behavior of U in natural systems, in which these components are often present.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

USGS Publications Warehouse

Arai, Yuji; Fuller, C.C.

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

PubMed

Arai, Yuji; Fuller, C C

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

Adsorption of 6-mercaptopurine and 6-mercaptopurine riboside on silver colloid: a pH dependent surface enhanced Raman spectroscopy and density functional theory study. Part I. 6-Mercaptopurine

NASA Astrophysics Data System (ADS)

Szeghalmi, A. V.; Leopold, L.; Pînzaru, S.; Chis, V.; Silaghi-Dumitrescu, I.; Schmitt, M.; Popp, J.; Kiefer, W.

2005-02-01

Surface enhanced Raman spectroscopy (SERS) on silver colloid has been applied to characterize the interaction of 6-mercaptopurine (6MP), an active drug used in chemotherapy of acute lymphoblastic leukemia, with a model biological substrate at therapeutical concentrations and as function of the pH value. The adsorption active sites and molecular orientation on the metal surface have been determined on the basis of SERS 'surface selection rules' subsequent to a detailed vibrational analysis of the 6MP tautomeric forms. Therefore, DFT calculations (vibrational wavenumbers, Raman scattering activities, partial atomic charges) of the optimized tautomers and potential energy distribution calculations have been performed. Around neutral pH value reorientation of the molecule has been observed. Under basic conditions the 6MP molecule is probably adsorbed on the silver colloid through the N1 atom of the purine ring and possibly the S atom, and adopts a tilted orientation to the surface. A reduction in the number of adsorbed molecules under basic conditions is proposed, since the SERS spectrum recorded at 10-6 M concentration at neutral pH value resembles the SERS spectra obtained under basic conditions at 10-5 M concentration. At acidic pH values a stronger interaction through the N9 and N3 atoms is suggested with an end-on orientation.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Assessment of coagulation pretreatment of leachate by response surface methodology.

PubMed

Lessoued, Ridha; Souahi, Fatiha; Castrillon Pelaez, Leonor

2017-11-01

Coagulation-flocculation is a relatively simple technique that can be used successfully for the treatment of old leachate by poly-aluminum chloride (PAC). The main objectives of this study are to design the experiments, build models and optimize the operating parameters, dosage m and pH, using the central composite design and response surface method. Developed for chemical organic matter (COD) and turbidity responses, the quadratic polynomial model is suitable for prediction within the range of simulated variables as it showed that the optimum conditions were m of 5.55 g/L at pH 7.05, with a determination coefficient R² at 99.33%, 99.92% and adjusted R² at 98.85% and 99.86% for both COD and turbidity. We confirm that the initial pH and PAC dosage have significant effects on COD and turbidity removal. The experimental data and model predictions agreed well and the removal efficiency of COD, turbidity, Fe, Pb and Cu reached respectively 61%, 96.4%, 97.1%, 99% and 100%.

Optimization of Polyplex Formation between DNA Oligonucleotide and Poly(ʟ-Lysine): Experimental Study and Modeling Approach.

PubMed

Vasiliu, Tudor; Cojocaru, Corneliu; Rotaru, Alexandru; Pricope, Gabriela; Pinteala, Mariana; Clima, Lilia

2017-06-17

The polyplexes formed by nucleic acids and polycations have received a great attention owing to their potential application in gene therapy. In our study, we report experimental results and modeling outcomes regarding the optimization of polyplex formation between the double-stranded DNA (dsDNA) and poly(ʟ-Lysine) (PLL). The quantification of the binding efficiency during polyplex formation was performed by processing of the images captured from the gel electrophoresis assays. The design of experiments (DoE) and response surface methodology (RSM) were employed to investigate the coupling effect of key factors (pH and N/P ratio) affecting the binding efficiency. According to the experimental observations and response surface analysis, the N/P ratio showed a major influence on binding efficiency compared to pH. Model-based optimization calculations along with the experimental confirmation runs unveiled the maximal binding efficiency (99.4%) achieved at pH 5.4 and N/P ratio 125. To support the experimental data and reveal insights of molecular mechanism responsible for the polyplex formation between dsDNA and PLL, molecular dynamics simulations were performed at pH 5.4 and 7.4.

Optimization of Polyplex Formation between DNA Oligonucleotide and Poly(l-Lysine): Experimental Study and Modeling Approach

PubMed Central

Vasiliu, Tudor; Cojocaru, Corneliu; Rotaru, Alexandru; Pricope, Gabriela; Pinteala, Mariana; Clima, Lilia

2017-01-01

The polyplexes formed by nucleic acids and polycations have received a great attention owing to their potential application in gene therapy. In our study, we report experimental results and modeling outcomes regarding the optimization of polyplex formation between the double-stranded DNA (dsDNA) and poly(l-Lysine) (PLL). The quantification of the binding efficiency during polyplex formation was performed by processing of the images captured from the gel electrophoresis assays. The design of experiments (DoE) and response surface methodology (RSM) were employed to investigate the coupling effect of key factors (pH and N/P ratio) affecting the binding efficiency. According to the experimental observations and response surface analysis, the N/P ratio showed a major influence on binding efficiency compared to pH. Model-based optimization calculations along with the experimental confirmation runs unveiled the maximal binding efficiency (99.4%) achieved at pH 5.4 and N/P ratio 125. To support the experimental data and reveal insights of molecular mechanism responsible for the polyplex formation between dsDNA and PLL, molecular dynamics simulations were performed at pH 5.4 and 7.4. PMID:28629130

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

PubMed Central

Gao, Xiaodong; Root, Robert A.; Farrell, James; Ela, Wendell; Chorover, Jon

2014-01-01

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 – 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92–2.94 and 3.41–3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms. PMID:25382933

Large area graphene ion sensitive field effect transistors with tantalum pentoxide sensing layers for pH measurement at the Nernstian limit

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

Fakih, Ibrahim, E-mail: ibrahim.fakih@mail.mcgill.ca; Sabri, Shadi; Szkopek, Thomas, E-mail: thomas.szkopek@mcgill.ca

2014-08-25

We have fabricated and characterized large area graphene ion sensitive field effect transistors (ISFETs) with tantalum pentoxide sensing layers and demonstrated pH sensitivities approaching the Nernstian limit. Low temperature atomic layer deposition was used to deposit tantalum pentoxide atop large area graphene ISFETs. The charge neutrality point of graphene, inferred from quantum capacitance or channel conductance, was used to monitor surface potential in the presence of an electrolyte with varying pH. Bare graphene ISFETs exhibit negligible response, while graphene ISFETs with tantalum pentoxide sensing layers show increased sensitivity reaching up to 55 mV/pH over pH 3 through pH 8. Applying themore » Bergveld model, which accounts for site binding and a Guoy-Chapman-Stern picture of the surface-electrolyte interface, the increased pH sensitivity can be attributed to an increased buffer capacity reaching up to 10{sup 14} sites/cm{sup 2}. ISFET response was found to be stable to better than 0.05 pH units over the course of two weeks.« less

Large area graphene ion sensitive field effect transistors with tantalum pentoxide sensing layers for pH measurement at the Nernstian limit

NASA Astrophysics Data System (ADS)

Fakih, Ibrahim; Sabri, Shadi; Mahvash, Farzaneh; Nannini, Matthieu; Siaj, Mohamed; Szkopek, Thomas

2014-08-01

We have fabricated and characterized large area graphene ion sensitive field effect transistors (ISFETs) with tantalum pentoxide sensing layers and demonstrated pH sensitivities approaching the Nernstian limit. Low temperature atomic layer deposition was used to deposit tantalum pentoxide atop large area graphene ISFETs. The charge neutrality point of graphene, inferred from quantum capacitance or channel conductance, was used to monitor surface potential in the presence of an electrolyte with varying pH. Bare graphene ISFETs exhibit negligible response, while graphene ISFETs with tantalum pentoxide sensing layers show increased sensitivity reaching up to 55 mV/pH over pH 3 through pH 8. Applying the Bergveld model, which accounts for site binding and a Guoy-Chapman-Stern picture of the surface-electrolyte interface, the increased pH sensitivity can be attributed to an increased buffer capacity reaching up to 1014 sites/cm2. ISFET response was found to be stable to better than 0.05 pH units over the course of two weeks.

Modelling ammonia volatilization from animal slurry applied with trail hoses to cereals

NASA Astrophysics Data System (ADS)

Sommer, S. G.; Olesen, J. E.

In Europe ammonia (NH 3), volatilization from animal manure is the major source of NH 3 in the atmosphere. From March to July 1997, NH 3 volatilization from trail hose applied slurry was measured for seven days after application in six experiments. A statistical analysis of data showed that NH 3 volatilization rate during the first 4-5 h after slurry application increased significantly ( P<5%) with wind speed and soil slurry surface water content. NH 3 volatilization in the six measuring periods during the experiments increased significantly ( P<5%) with relative water content of the soil slurry surface, global radiation, pH, and decreased with increasing rainfall during each measuring period and rainfall accumulated from onset of each experiment. A mechanistic model of NH 3 volatilization was developed. Model inputs are climate variables, soil characteristics and total ammoniacal nitrogen (TAN=ammonium+ammonia) in the soil surface layer. A pH submodel for predicting pH at the surface of the soil slurry liquid was developed. The measured NH 3 volatilization was compared with model simulations. The simulated results explained 27% of the variation in measured NH 3 volatilization rates during all seven days, but 48% of measured volatilization rates during the first 24 h. Calculations with the model showed that applying slurry in the morning or in the afternoon reduced volatilization by 50% compared with a noon application. Spreading the slurry with trail hoses to a 60 cm high crop reduced losses by 75% compared with a spreading onto bare soil. Ammonia volatilization was 50% lower when the soil had dried out after slurry application compared with a wet slurry surface.

A physics-based model for maintenance of the pH gradient in the gastric mucus layer.

PubMed

Lewis, Owen L; Keener, James P; Fogelson, Aaron L

2017-12-01

It is generally accepted that the gastric mucus layer provides a protective barrier between the lumen and the mucosa, shielding the mucosa from acid and digestive enzymes and preventing autodigestion of the stomach epithelium. However, the precise mechanisms that contribute to this protective function are still up for debate. In particular, it is not clear what physical processes are responsible for transporting hydrogen protons, secreted within the gastric pits, across the mucus layer to the lumen without acidifying the environment adjacent to the epithelium. One hypothesis is that hydrogen may be bound to the mucin polymers themselves as they are convected away from the mucosal surface and eventually degraded in the stomach lumen. It is also not clear what mechanisms prevent hydrogen from diffusing back toward the mucosal surface, thereby lowering the local pH. In this work we investigate a physics-based model of ion transport within the mucosal layer based on a Nernst-Planck-like equation. Analysis of this model shows that the mechanism of transporting protons bound to the mucus gel is capable of reproducing the trans-mucus pH gradients reported in the literature. Furthermore, when coupled with ion exchange at the epithelial surface, our analysis shows that bicarbonate secretion alone is capable of neutralizing the epithelial pH, even in the face of enormous diffusive gradients of hydrogen. Maintenance of the pH gradient is found to be robust to a wide array of perturbations in both physiological and phenomenological model parameters, suggesting a robust physiological control mechanism. NEW & NOTEWORTHY This work combines modeling techniques based on physical principles, as well as novel numerical simulations to test the plausibility of one hypothesized mechanism for proton transport across the gastric mucus layer. Results show that this mechanism is able to maintain the extreme pH gradient seen in in vivo experiments and suggests a highly robust regulation mechanism to maintain this gradient in the face of dynamic lumen composition. Copyright © 2017 the American Physiological Society.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions. PMID:29772775

Optimization of CMCase production from sorghum straw by Aspergillus terreus SUK-1 under solid substrate fermentation using response surface methodology

NASA Astrophysics Data System (ADS)

Tibin, El Mubarak Musa; Al-Shorgani, Najeeb Kaid Naseer; Abuelhassan, Nawal Noureldaim; Hamid, Aidil Abdul; Kalil, Mohd Sahaid; Yusoff, Wan Mohtar Wan

2013-11-01

The cellulase production using sorghum straw as substrate by fungal culture of Aspergillus terreus SUK-1 was investigated in solid substrate fermentation (SSF). The optimum CMCase was achieved by testing most effective fermentation parameters which were: incubation temperature, pH and moisture content using Response Surface Methodology (RSM) based on Central Composite Design (CCD). The carboxymethyl cellulase activity (CMCase) was measured as the defining factor. The results were analysed by analysis of variance (ANOVA) and the regression quadratic model was obtained. The model was found to be significant (p<0.05) and the effect of temperature (25-40°C) and pH (4-7) was found to be not significant on CMCase activity whereas the moisture content was significant in the SSF conditions employed. The high yield of predicted CMCase activity (0.2 U/ml) was obtained under the optimized conditions (temperature 40 □C, pH 5.4 and moisture content of 80%). The model was validated by applying the optimized conditions and it was found that the model was valid.

Theoretical study on the interactions between chlordecone hydrate and acidic surface groups of activated carbon under basic pH conditions.

PubMed

Melchor-Rodríguez, Kenia; Gamboa-Carballo, Juan José; Ferino-Pérez, Anthuan; Passé-Coutrin, Nady; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

2018-05-01

A theoretical study of the influence of acidic surface groups (SG) of activated carbon (AC) on chlordecone hydrate (CLDh) adsorption is presented, in order to help understanding the adsorption process under basic pH conditions. A seven rings aromatic system (coronene) with a functional group in the edge was used as a simplified model of AC to evaluate the influence of SG in the course of adsorption from aqueous solution at basic pH conditions. Two SG were modeled in their deprotonated form: carboxyl and hydroxyl (COO - and O - ), interacting with CLDh. In order to model the solvation process, all systems under study were calculated with up to three water molecules. Multiple Minima Hypersurface (MMH) methodology was employed to study the interactions of CLDh with SG on AC using PM7 semiempirical Hamiltonian, to explore the potential energy surfaces of the systems and evaluate their thermodynamic association energies. The re-optimization of representative structures obtained from MMH was done using M06-2X Density Functional Theory. The Quantum Theory of Atoms in Molecules (QTAIM) was used to characterize the interaction types. As result, the association of CLDh with acidic SG at basic pH conditions preferentially occurs between the two alcohol groups of CLDh with COO - and O - groups and by dispersive interactions of chlorine atoms of CLDh with the graphitic surface. On the other hand, the presence of covalent interactions between the negatively charged oxygen of SG and one hydrogen atom of CLDh alcohol groups (O - ⋯HO interactions) without water molecules, was confirmed by QTAIM study. It can be concluded that the interactions of CLDh with acidic SG of AC under basic pH conditions confirms the physical mechanisms of adsorption process. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption of polyelectrolyte-like proteins to silica surfaces and the impact of pH on the response to ionic strength. A Monte Carlo simulation and ellipsometry study.

PubMed

Hyltegren, Kristin; Skepö, Marie

2017-05-15

The adsorbed amount of the polyelectrolyte-like protein histatin 5 on a silica surface depends on the pH and the ionic strength of the solution. Interestingly, an increase in ionic strength affects the adsorbed amount differently depending on the pH of the solution, as shown by ellipsometry measurements (Hyltegren, 2016). We have tested the hypothesis that the same (qualitative) trends can be found also from a coarse-grained model that takes all charge-charge interactions into account within the frameworks of Gouy-Chapman and Debye-Hückel theories. Using the same coarse-grained model as in our previous Monte Carlo study of single protein adsorption (Hyltegren, 2016), simulations of systems with many histatin 5 molecules were performed and then compared with ellipsometry measurements. The strength of the short-ranged attractive interaction between the protein and the surface was varied. The coarse-grained model does not qualitatively reproduce the pH-dependence of the experimentally observed trends in adsorbed amount as a function of ionic strength. However, the simulations cast light on the balance between electrostatic attraction between protein and surface and electrostatic repulsion between adsorbed proteins, the deficiencies of the Langmuir isotherm, and the implications of protein charge regulation in concentrated systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Enhanced removal of As (V) from aqueous solution using modified hydrous ferric oxide nanoparticles

PubMed Central

Huo, Lijuan; Zeng, Xibai; Su, Shiming; Bai, Lingyu; Wang, Yanan

2017-01-01

Hydrous ferric oxide (HFO) is most effective with high treatment capacity on arsenate [As(V)] sorption although its transformation and aggregation nature need further improvement. Here, HFO nanoparticles with carboxymethyl cellulose (CMC) or starch as modifier was synthesized for the purpose of stability improvement and As(V) removal from water. Comparatively, CMC might be the optimum stabilizer for HFO nanoparticles because of more effective physical and chemical stability. The large-pore structure, high surface specific area, and the non-aggregated nature of CMC-HFO lead to increased adsorption sites, and thus high adsorption capacities of As(V) without pre-treatment (355 mg·g−1), which is much greater than those reported in previous studies. Second-order equation and dual-mode isotherm model could be successfully used to interpret the sorption kinetics and isotherms of As(V), respectively. FTIR, XPS and XRD analyses suggested that precipitation and surface complexation were primary mechanisms for As(V) removal by CMC modified HFO nanoparticles. A surface complexation model (SCM) was used to simulate As adsorption over pH 2.5–10.4. The predominant adsorbed arsenate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The immobilized arsenic remained stable when aging for 270 d at room temperature. PMID:28098196

Enhanced removal of As (V) from aqueous solution using modified hydrous ferric oxide nanoparticles

NASA Astrophysics Data System (ADS)

Huo, Lijuan; Zeng, Xibai; Su, Shiming; Bai, Lingyu; Wang, Yanan

2017-01-01

Hydrous ferric oxide (HFO) is most effective with high treatment capacity on arsenate [As(V)] sorption although its transformation and aggregation nature need further improvement. Here, HFO nanoparticles with carboxymethyl cellulose (CMC) or starch as modifier was synthesized for the purpose of stability improvement and As(V) removal from water. Comparatively, CMC might be the optimum stabilizer for HFO nanoparticles because of more effective physical and chemical stability. The large-pore structure, high surface specific area, and the non-aggregated nature of CMC-HFO lead to increased adsorption sites, and thus high adsorption capacities of As(V) without pre-treatment (355 mg·g-1), which is much greater than those reported in previous studies. Second-order equation and dual-mode isotherm model could be successfully used to interpret the sorption kinetics and isotherms of As(V), respectively. FTIR, XPS and XRD analyses suggested that precipitation and surface complexation were primary mechanisms for As(V) removal by CMC modified HFO nanoparticles. A surface complexation model (SCM) was used to simulate As adsorption over pH 2.5-10.4. The predominant adsorbed arsenate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The immobilized arsenic remained stable when aging for 270 d at room temperature.

Removal of methylene blue from aqueous solution by wood millet carbon optimization using response surface methodology

NASA Astrophysics Data System (ADS)

Ghaedi, Mehrorang; Kokhdan, Syamak Nasiri

2015-02-01

The use of cheep, non-toxic, safe and easily available adsorbent are efficient and recommended material and alternative to the current expensive substance for pollutant removal from wastewater. The activated carbon prepared from wood waste of local tree (millet) extensively was applied for quantitative removal of methylene blue (MB), while simply. It was used to re-used after heating and washing with alkaline solution of ethanol. This new adsorbent was characterized by using BET surface area measurement, FT-IR, pH determination at zero point of charge (pHZPC) and Boehm titration method. Response surface methodology (RSM) by at least the number of experiments main and interaction of experimental conditions such as pH of solution, contact time, initial dye concentration and adsorbent dosage was optimized and set as pH 7, contact time 18 min, initial dye concentration 20 ppm and 0.2 g of adsorbent. It was found that variable such as pH and amount of adsorbent as solely or combination effects seriously affect the removal percentage. The fitting experimental data with conventional models reveal the applicability of isotherm models Langmuir model for their well presentation and description and Kinetic real rate of adsorption at most conditions efficiently can be represented pseudo-second order, and intra-particle diffusion. It novel material is good candidate for removal of huge amount of MB (20 ppm) in short time (18 min) by consumption of small amount (0.2 g).

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

Comparison of adsorption of Remazol Black B and Acidol Red on microporous activated carbon felt.

PubMed

Donnaperna, L; Duclaux, L; Gadiou, R; Hirn, M-P; Merli, C; Pietrelli, L

2009-11-15

The adsorption of two anionic dyes, Remazol Black B (RB5) and Acidol Red 2BE-NW (AR42), onto a microporous activated carbon felt was investigated. The characterization of carbon surface chemistry by X-ray microanalysis, Boehm titrations, and pH-PZC measurements indicates that the surface oxygenated groups are mainly acidic. The rate of adsorption depends on the pH and the experimental data fit the intraparticle diffusion model. The pore size distribution obtained by DFT analysis shows that the mean pore size is close to 1nm, which indicates that a slow intraparticle diffusion process control the adsorption. The adsorption isotherms were measured for different pH values. The Khan and the Langmuir-Freundlich models lead to the best agreement with experimental data for RB5 and AR42, respectively. These isotherm simulations and the pH dependence of adsorption show that the adsorption capacity is mainly controlled by nondispersive electrostatic interactions for pH values below 4. The adsorption kinetics, the irreversibility of the process, and the influence of the pH indicate that the rate of adsorption in this microporous felt proceeds through two steps. The first one is fast and results from direct interaction of dye molecules with the external surface of the carbon material (which account for 10% of the whole surface area); in the second, slow step, the adsorption rate is controlled by the slow diffusion of dye molecules into the narrow micropores. The influence of temperature on the adsorption isotherms was studied and the thermodynamic parameters were obtained. They show that the process is spontaneous and exothermic.

pH-dependence of single-protein adsorption and diffusion at a liquid chromatographic interface.

PubMed

Kisley, Lydia; Poongavanam, Mohan-Vivekanandan; Kourentzi, Katerina; Willson, Richard C; Landes, Christy F

2016-02-01

pH is a common mobile phase variable used to control protein separations due to the tunable nature of amino acid and adsorbent charge. Like other column variables such as column density and ligand loading density, pH is usually optimized empirically. Single-molecule spectroscopy extracts molecular-scale data to provide a framework for mechanistic optimization of pH. The adsorption and diffusion of a model globular protein, α-lactalbumin, was studied by single-molecule microscopy at a silica-aqueous interface analogous to aqueous normal phase and hydrophilic interaction chromatography and capillary electrophoresis interfaces at varied pH. Electrostatic repulsion resulting in free diffusion was observed at pH above the isoelectric point of the protein. In contrast, at low pH strong adsorption and surface diffusion with either no (D ∼ 0.01 μm(2) /s) or translational (D ∼ 0.3 μm(2) /s) motion was observed where the protein likely interacted with the surface through electrostatic, hydrophobic, and hydrogen bonding forces. The fraction of proteins immobilized could be increased by lowering the pH. These results show that retention of proteins at the silica interface cannot be viewed solely as an adsorption/desorption process and that the type of surface diffusion, which ultimately leads to ensemble chromatographic separations, can be controlled by tuning long-range electrostatic and short-range hydrophobic and hydrogen bonding forces with pH. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Response of O2 and pH to ENSO in the California Current System in a high-resolution global climate model

NASA Astrophysics Data System (ADS)

Turi, Giuliana; Alexander, Michael; Lovenduski, Nicole S.; Capotondi, Antonietta; Scott, James; Stock, Charles; Dunne, John; John, Jasmin; Jacox, Michael

2018-02-01

Coastal upwelling systems, such as the California Current System (CalCS), naturally experience a wide range of O2 concentrations and pH values due to the seasonality of upwelling. Nonetheless, changes in the El Niño-Southern Oscillation (ENSO) have been shown to measurably affect the biogeochemical and physical properties of coastal upwelling regions. In this study, we use a novel, high-resolution global climate model (GFDL-ESM2.6) to investigate the influence of warm and cold ENSO events on variations in the O2 concentration and the pH of the CalCS coastal waters. An assessment of the CalCS response to six El Niño and seven La Niña events in ESM2.6 reveals significant variations in the response between events. However, these variations overlay a consistent physical and biogeochemical (O2 and pH) response in the composite mean. Focusing on the mean response, our results demonstrate that O2 and pH are affected rather differently in the euphotic zone above ˜ 100 m. The strongest O2 response reaches up to several hundreds of kilometers offshore, whereas the pH signal occurs only within a ˜ 100 km wide band along the coast. By splitting the changes in O2 and pH into individual physical and biogeochemical components that are affected by ENSO variability, we found that O2 variability in the surface ocean is primarily driven by changes in surface temperature that affect the O2 solubility. In contrast, surface pH changes are predominantly driven by changes in dissolved inorganic carbon (DIC), which in turn is affected by upwelling, explaining the confined nature of the pH signal close to the coast. Below ˜ 100 m, we find conditions with anomalously low O2 and pH, and by extension also anomalously low aragonite saturation, during La Niña. This result is consistent with findings from previous studies and highlights the stress that the CalCS ecosystem could periodically undergo in addition to impacts due to climate change.

Mechanistic Analysis of Cocrystal Dissolution as a Function of pH and Micellar Solubilization

PubMed Central

2016-01-01

The purpose of this work is to provide a mechanistic understanding of the dissolution behavior of cocrystals under the influence of ionization and micellar solubilization. Mass transport models were developed by applying Fick’s law of diffusion to dissolution with simultaneous chemical reactions in the hydrodynamic boundary layer adjacent to the dissolving cocrystal surface to predict the pH at the dissolving solid–liquid interface (i.e., interfacial pH) and the flux of cocrystals. To evaluate the predictive power of these models, dissolution studies of carbamazepine–saccharin (CBZ-SAC) and carbamazepine–salicylic acid (CBZ-SLC) cocrystals were performed at varied pH and surfactant concentrations above the critical stabilization concentration (CSC), where the cocrystals were thermodynamically stable. The findings in this work demonstrate that the pH dependent dissolution behavior of cocrystals with ionizable components is dependent on interfacial pH. This mass transport analysis demonstrates the importance of pH, cocrystal solubility, diffusivity, and micellar solubilization on the dissolution rates of cocrystals. PMID:26877267

Mechanistic Analysis of Cocrystal Dissolution as a Function of pH and Micellar Solubilization.

PubMed

Cao, Fengjuan; Amidon, Gordon L; Rodriguez-Hornedo, Nair; Amidon, Gregory E

2016-03-07

The purpose of this work is to provide a mechanistic understanding of the dissolution behavior of cocrystals under the influence of ionization and micellar solubilization. Mass transport models were developed by applying Fick's law of diffusion to dissolution with simultaneous chemical reactions in the hydrodynamic boundary layer adjacent to the dissolving cocrystal surface to predict the pH at the dissolving solid-liquid interface (i.e., interfacial pH) and the flux of cocrystals. To evaluate the predictive power of these models, dissolution studies of carbamazepine-saccharin (CBZ-SAC) and carbamazepine-salicylic acid (CBZ-SLC) cocrystals were performed at varied pH and surfactant concentrations above the critical stabilization concentration (CSC), where the cocrystals were thermodynamically stable. The findings in this work demonstrate that the pH dependent dissolution behavior of cocrystals with ionizable components is dependent on interfacial pH. This mass transport analysis demonstrates the importance of pH, cocrystal solubility, diffusivity, and micellar solubilization on the dissolution rates of cocrystals.

Atomic level insights into realistic molecular models of dendrimer-drug complexes through MD simulations.

PubMed

Jain, Vaibhav; Maiti, Prabal K; Bharatam, Prasad V

2016-09-28

Computational studies performed on dendrimer-drug complexes usually consider 1:1 stoichiometry, which is far from reality, since in experiments more number of drug molecules get encapsulated inside a dendrimer. In the present study, molecular dynamic (MD) simulations were implemented to characterize the more realistic molecular models of dendrimer-drug complexes (1:n stoichiometry) in order to understand the effect of high drug loading on the structural properties and also to unveil the atomistic level details. For this purpose, possible inclusion complexes of model drug Nateglinide (Ntg) (antidiabetic, belongs to Biopharmaceutics Classification System class II) with amine- and acetyl-terminated G4 poly(amidoamine) (G4 PAMAM(NH 2 ) and G4 PAMAM(Ac)) dendrimers at neutral and low pH conditions are explored in this work. MD simulation analysis on dendrimer-drug complexes revealed that the drug encapsulation efficiency of G4 PAMAM(NH 2 ) and G4 PAMAM(Ac) dendrimers at neutral pH was 6 and 5, respectively, while at low pH it was 12 and 13, respectively. Center-of-mass distance analysis showed that most of the drug molecules are located in the interior hydrophobic pockets of G4 PAMAM(NH 2 ) at both the pH; while in the case of G4 PAMAM(Ac), most of them are distributed near to the surface at neutral pH and in the interior hydrophobic pockets at low pH. Structural properties such as radius of gyration, shape, radial density distribution, and solvent accessible surface area of dendrimer-drug complexes were also assessed and compared with that of the drug unloaded dendrimers. Further, binding energy calculations using molecular mechanics Poisson-Boltzmann surface area approach revealed that the location of drug molecules in the dendrimer is not the decisive factor for the higher and lower binding affinity of the complex, but the charged state of dendrimer and drug, intermolecular interactions, pH-induced conformational changes, and surface groups of dendrimer do play an important role in the stabilization of complex. Interestingly, it was observed from the equilibrated structures of dendrimer-drug complexes at low pH that encapsulated drug molecules in the G4 PAMAM(NH 2 ) formed cluster, while in the case of nontoxic G4 PAMAM(Ac) they were uniformly distributed inside the dendritic cavities. Thus, the latter dendrimer is suggested to be suitable nanovehicle for the delivery of Ntg. This computational analysis highlighted the importance of realistic molecular models of dendrimer-drug complexes (1:n) in order to obtain reliable results.

Atomic level insights into realistic molecular models of dendrimer-drug complexes through MD simulations

NASA Astrophysics Data System (ADS)

Jain, Vaibhav; Maiti, Prabal K.; Bharatam, Prasad V.

2016-09-01

Computational studies performed on dendrimer-drug complexes usually consider 1:1 stoichiometry, which is far from reality, since in experiments more number of drug molecules get encapsulated inside a dendrimer. In the present study, molecular dynamic (MD) simulations were implemented to characterize the more realistic molecular models of dendrimer-drug complexes (1:n stoichiometry) in order to understand the effect of high drug loading on the structural properties and also to unveil the atomistic level details. For this purpose, possible inclusion complexes of model drug Nateglinide (Ntg) (antidiabetic, belongs to Biopharmaceutics Classification System class II) with amine- and acetyl-terminated G4 poly(amidoamine) (G4 PAMAM(NH2) and G4 PAMAM(Ac)) dendrimers at neutral and low pH conditions are explored in this work. MD simulation analysis on dendrimer-drug complexes revealed that the drug encapsulation efficiency of G4 PAMAM(NH2) and G4 PAMAM(Ac) dendrimers at neutral pH was 6 and 5, respectively, while at low pH it was 12 and 13, respectively. Center-of-mass distance analysis showed that most of the drug molecules are located in the interior hydrophobic pockets of G4 PAMAM(NH2) at both the pH; while in the case of G4 PAMAM(Ac), most of them are distributed near to the surface at neutral pH and in the interior hydrophobic pockets at low pH. Structural properties such as radius of gyration, shape, radial density distribution, and solvent accessible surface area of dendrimer-drug complexes were also assessed and compared with that of the drug unloaded dendrimers. Further, binding energy calculations using molecular mechanics Poisson-Boltzmann surface area approach revealed that the location of drug molecules in the dendrimer is not the decisive factor for the higher and lower binding affinity of the complex, but the charged state of dendrimer and drug, intermolecular interactions, pH-induced conformational changes, and surface groups of dendrimer do play an important role in the stabilization of complex. Interestingly, it was observed from the equilibrated structures of dendrimer-drug complexes at low pH that encapsulated drug molecules in the G4 PAMAM(NH2) formed cluster, while in the case of nontoxic G4 PAMAM(Ac) they were uniformly distributed inside the dendritic cavities. Thus, the latter dendrimer is suggested to be suitable nanovehicle for the delivery of Ntg. This computational analysis highlighted the importance of realistic molecular models of dendrimer-drug complexes (1:n) in order to obtain reliable results.

Endoscopic sensing of alveolar pH.

PubMed

Choudhury, D; Tanner, M G; McAughtrie, S; Yu, F; Mills, B; Choudhary, T R; Seth, S; Craven, T H; Stone, J M; Mati, I K; Campbell, C J; Bradley, M; Williams, C K I; Dhaliwal, K; Birks, T A; Thomson, R R

2017-01-01

Previously unobtainable measurements of alveolar pH were obtained using an endoscope-deployable optrode. The pH sensing was achieved using functionalized gold nanoshell sensors and surface enhanced Raman spectroscopy (SERS). The optrode consisted of an asymmetric dual-core optical fiber designed for spatially separating the optical pump delivery and signal collection, in order to circumvent the unwanted Raman signal generated within the fiber. Using this approach, we demonstrate a ~100-fold increase in SERS signal-to-fiber background ratio, and demonstrate multiple site pH sensing with a measurement accuracy of ± 0.07 pH units in the respiratory acini of an ex vivo ovine lung model. We also demonstrate that alveolar pH changes in response to ventilation.

Surface properties of magnetite in high temperature aqueous electrolyte solutions: A review.

PubMed

Vidojkovic, Sonja M; Rakin, Marko P

2017-07-01

Deposits and scales formed on heat transfer surfaces in power plant water/steam circuits have a significant negative impact on plant reliability, availability and performance, causing tremendous economic consequences and subsequent increases in electricity cost. Consequently, the improvement of the understanding of deposition mechanisms on power generating surfaces is defined as a high priority in the power industry. The deposits consist principally of iron oxides, which are steel corrosion products and usually present in colloidal form. Magnetite (Fe 3 O 4 ) is the predominant and most abundant compound found in water/steam cycles of all types of power plants. The crucial factor that governs the deposition process and influences the deposition rate of magnetite is the electrostatic interaction between the metal wall surfaces and the suspended colloidal particles. However, there is scarcity of data on magnetite surface properties at elevated temperatures due to difficulties in their experimental measurement. In this paper a generalized overview of existing experimental data on surface characteristics of magnetite at high temperatures is presented with particular emphasis on possible application in the power industry. A thorough analysis of experimental techniques, mathematical models and results has been performed and directions for future investigations have been considered. The state-of-the-art assessment showed that for the characterization of magnetite/aqueous electrolyte solution interface at high temperatures acid-base potentiometric titrations and electrophoresis were the most beneficial and dependable techniques which yielded results up to 290 and 200°C, respectively. Mass titrations provided data on magnetite surface charge up to 320°C, however, this technique is highly sensitive to the minor concentrations of impurities present on the surface of particle. Generally, fairly good correlation between the isoelectric point (pH iep ) and point of zero charge (pH pzc ) values has been obtained. All obtained results showed that the surface of magnetite particles is negatively charged in typical high temperature thermal power plant water, which indicates the low probability of aggregation and deposition on plant metal surfaces. The results also gave strong evidence on decline of pH iep and pH pzc with temperature in the same manner as neutral pH of water. The thermodynamic parameters of magnetite surface protonation reactions were in good agreement with each other and obtained using one site/two pK and mainly one site/one pK model. All collected data provided evidences for interaction between particles, probability of deposition and eventual attachment to the steel surface at various pH and temperatures and can serve as a foundation for future surface studies aimed at optimizing plant performances and reducing of magnetite deposition. In future works it would be indispensable to provide the surface experimental data for extended temperature ranges, typical solution chemistries and metal surfaces of power plant structural components and thus obtain entire set of results useful in modeling the surface behavior and control of deposition process in power reactors and thermal plant circuits. Moreover, the acquired results will be applicable and greatly valuable to all other types of power plants, industrial facilities and technological processes using the high temperature water medium. Copyright © 2016 Elsevier B.V. All rights reserved.

Probing surface charge potentials of clay basal planes and edges by direct force measurements.

PubMed

Zhao, Hongying; Bhattacharjee, Subir; Chow, Ross; Wallace, Dean; Masliyah, Jacob H; Xu, Zhenghe

2008-11-18

The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8.

Insight into the stability of poly(diallydimethylammoniumchloride) and polybrene poly cationic coatings in capillary electrophoresis.

PubMed

Pei, Lei; Lucy, Charles A

2014-10-24

Polycationic polymers are widely used in capillary electrophoresis (CE) as surface coatings to prevent protein adsorption and control electroosmotic flow (EOF). Such semi-permanent coatings are formed by flushing the capillary with a quaternary amine-based polymer such as poly(diallydimethylammonium chloride) (PDADMAC) or polybrene. Compared to covalent capillary coatings, the claimed advantages of adsorptive polycation coatings are their simple preparation and that they are not limited to the pH 2-8 range as are covalent coatings. However, while the latter is commonly claimed, few studies have demonstrated the stability of polycationic coatings at extreme pH. Herein PDADMAC and polybrene are studied as model cationic coatings. PDADMAC with higher molecular weight (M.W.) demonstrated higher EOF stability at pH 9.5, with PDADMAC of M.W. less than 200,000 being unstable at pH 9.5. X-ray photoelectron spectroscopy (XPS) shows that the quaternary amines of PDADMAC and polybrene were slowly converted to tertiary amines in alkaline solution and more rapidly when adsorbed on a silica surface. The degraded polycation deprotonated at pH >7, resulting in loss of polymer from the surface and diminishing EOF. Successive multiple ionic layer (SMIL) coatings show greater alkaline stability by distancing the polycation from the surface. Separations of inorganic anions at pH 9.5 illustrate the degradation behavior and enhanced stability of higher M.W. polycationic coatings. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption behaviour of methylene blue onto Jordanian diatomite: a kinetic study.

PubMed

Al-Ghouti, Mohammad A; Khraisheh, Majeda A M; Ahmad, Mohammad N M; Allen, Stephen

2009-06-15

The effect of initial concentration, particle size, mass of the adsorbent, pH and agitation speed on adsorption behaviour of methylene blue (MB) onto Jordanian diatomite has been investigated. The maximum adsorption capacity, q, increased from 75 to 105 mg/g when pH of the dye solution increased from 4 to 11. It is clear that the ionisable charge sites on the diatomite surface increased when pH increased from 4 to 11. When the solution pH was above the pH(ZPC), the diatomite surface had a negative charge, while at low pH (pH<5.4) it has a positive charge. The adsorption capacity increased from 88.6 to 143.3mg/g as the initial MB concentrations increased from 89.6 to 225.2mg/dm(3). The experimental results were also applied to the pseudo-first and -second order kinetic models. It is noticed that the whole experimental data of MB adsorption onto diatomite did not follow the pseudo-first order model and had low correlation coefficients (R(2)<0.3). The calculated adsorption capacity, q(e,cal), values obtained from pseudo-first order kinetic model did not give acceptable values, q(e,exp.) The maximum uptake capacity seems to be independent of the particle size of the diatomite when the particle size distribution is less than 250-500 microm. While at larger particle size 250-500 microm, the maximum uptake capacity was dependent on the particle size. It would imply that the MB adsorption is limited by the external surface and that intraparticle diffusion is reduced. The effect of the agitation speeds on the removal of MB from aqueous solution using the diatomite is quite low. The MB removal increased from 43 to 100% when mass of the diatomite increased from 0.3 to 1.7 g.

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.

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Fate and transport of uranium (VI) in weathered saprolite

DOE PAGES

Kim, Young-Jin; Brooks, Scott C.; Zhang, Fan; ...

2014-11-09

We conducted batch and column experiments to investigate sorption and transport of uranium (U) in the presence of saprolite derived from interbedded shale, limestone, and sandstone sequences. Sorption kinetics were measured at two initial concentrations (C0; 1, 10 mM) and three soil:solution ratios (Rs/w; 0.005, 0.25, 2 kg/L) at pH 4.5 (pH of the saprolite). The rate of U loss from solution (mmole/L/h) increased with increasing Rs/w. Uranium sorption exhibited a fast phase with 80% sorption in the first eight hours for all C0 and Rs/w values and a slow phase during which the reaction slowly approached (pseudo) equilibrium overmore » the next seven days. The pH-dependency of U sorption was apparent in pH sorption edges. U(VI) sorption increased over the pH range 4e6, then decreased sharply at pH > 7.5. U(VI) sorption edges were well described by a surface complexation model using calibrated parameters and the reaction network proposed by Waite et al. (1994). Sorption isotherms measured using the same Rs/w and pH values showed a solids concentration effect where U(VI) sorption capacity and affinity decreased with increasing solids concentration. Moreover, this effect may have been due to either particle aggregation or competition between U(VI) and exchangeable cations for sorption sites. The surface complexation model with calibrated parameters was able to predict the general sorption behavior relatively well, but failed to reproduce solid concentration effects, implying the importance of appropriate design if batch experiments are to be utilized for dynamic systems. Transport of U(VI) through the packed column was significantly retarded. We also conducted transport simulations using the reactive transport model HydroGeoChem (HGC) v5.0 that incorporated the surface complexation reaction network used to model the batch data. Model parameters reported by Waite et al. (1994) provided a better prediction of U transport than optimized parameters derived from our sorption edges. The results presented in this study highlight the challenges in defining appropriate conditions for batch-type experiments used to extrapolate parameters for transport models, and also underline a gap in our ability to transfer batch results to transport simulations.« less

The effect of pH on chronic aquatic nickel toxicity is dependent on the pH itself: Extending the chronic nickel bioavailability models.

PubMed

Nys, Charlotte; Janssen, Colin R; Van Sprang, Patrick; De Schamphelaere, Karel A C

2016-05-01

The environmental quality standard for Ni in the European Commission's Water Framework Directive is bioavailability based. Although some of the available chronic Ni bioavailability models are validated only for pH ≤ 8.2, a considerable fraction of European surface waters has a pH > 8.2. Therefore, the authors investigated the effect of a change in pH from 8.2 to 8.7 on chronic Ni toxicity in 3 invertebrate (Daphnia magna, Lymnaea stagnalis, and Brachionus calyciflorus) and 2 plant species (Pseudokirchneriella subcapitata and Lemna minor). Nickel toxicity was almost always significantly higher at pH 8.7 than at pH 8.2. To test whether the existing chronic Ni bioavailability models developed for pH ≤ 8.2 can be used at higher pH levels, Ni toxicity at pH 8.7 was predicted based on Ni toxicity observed at pH 8.2. This resulted in a consistent underestimation of toxicity. The results suggest that the effect of pH on Ni(2+) toxicity is dependent on the pH itself: the slope of the pH effect is steeper above than below pH 8.2 for species for which a species-specific bioavailability model exists. Therefore, the existing chronic Ni bioavailability models were modified to allow predictions of chronic Ni toxicity to invertebrates and plants in the pH range of 8.2 to 8.7 by applying a pH slope (SpH ) dependent on the pH of the target water. These modified Ni bioavailability models resulted in more accurate predictions of Ni toxicity to all 5 species (within 2-fold error), without the bias observed using the bioavailability models developed for pH ≤ 8.2. The results of the present study can decrease the uncertainty in implementing the bioavailability-based environmental quality standard under the Water Framework Directive for high-pH regions in Europe. © 2015 SETAC.

Kinetics of scheelite dissolution in groundwater: defining the release rate of tungsten contamination from a natural source

NASA Astrophysics Data System (ADS)

Montgomery, S. D.; Mckibben, M. A.

2011-12-01

Tungsten, an emerging contaminant, has no EPA standard for its permissible levels in drinking water. At sites in California, Nevada, and Arizona there may be a correlation between elevated levels of tungsten in drinking water and clusters of childhood acute lymphocytic leukemia (ALL). Developing a better understanding of how tungsten is released from rocks into surface and groundwaters is therefore of growing environmental interest. Knowledge of tungstate ore mineral weathering processes, particularly the rates of dissolution of scheelite (CaWO4) in groundwater, could improve models of how tungsten is released and transported in natural waters. Our research is focusing on experimental determination of the rates and products of tungstate mineral dissolution in synthetic groundwater, as a function of temperature, pH and mineral surface area. The initial rate method is being used to develop rate laws. Batch reactor experiments are conducted within constant temperature circulation baths over a pH range of 2-9. Cleaned scheelite powder with grain diameters of 106-150um is placed between two screens in a sample platform and then placed inside a two liter Teflon vessel filled with synthetic groundwater. Ports on the vessel allow sample extraction, temperature and pH measurement, gas inflow, and water circulation. Aliquots of solution are taken periodically for product analysis by ICP -MS. Changes in mineral surface characteristics are monitored using SEM and EDS methods. Results so far reveal that the dissolution of scheelite is incongruent at both neutral and low pH. Solid tungstic acid forms on scheelite mineral surfaces under acidic conditions, implying that this phase controls the dissolution rate in acidic environments. The influence of dissolved CO2 and resultant calcium carbonate precipitation on the dissolution of scheelite at higher pH is also being investigated. The rate law being developed for scheelite dissolution will be useful in reactive-transport computer codes designed to model tungsten contamination in a variety of surface and groundwater settings.

Desorption of plutonium from montmorillonite: An experimental and modeling study

DOE PAGES

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-15

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

Desorption of plutonium from montmorillonite: An experimental and modeling study

NASA Astrophysics Data System (ADS)

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-01

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. We evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with Kd values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in Kd, indicating that true sorption equilibrium was not achieved within the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. A conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50-100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.

Carbonate dissolution in mixed waters due to ocean acidification

NASA Astrophysics Data System (ADS)

Koski, K.; Wilson, J. L.

2009-12-01

Much of the anthropogenically released carbon dioxide has been stored as a dissolved gas in the ocean, causing a 0.1 decrease in ocean surface pH, with models predicting that by 2100 the surface ocean pH will be 0.5 below pre-industrial levels. In mixed ocean water - fresh water environments (e.g. estuaries, coastal aquifers, and edges of ice sheets), the decreased ocean pH couples with the mixed water geochemistry to make water more undersaturated with respect to calcium carbonate than ocean acidification alone. Mixed-water calcite dissolution may be one of the first directly observable effects of ocean acidification, as the ocean water and the fresh water can both be saturated with respect to calcium carbonate while their mixture will be undersaturated. We present a basic quantitative model describing mixed water dissolution in coastal or island freshwater aquifers, using temporally changing ocean pH, sea level, precipitation, and groundwater pumping. The model describes the potential for an increased rate of speleogenesis and porosity/permeability development along the lower edge of a fresh water lens aquifer. The model accounts the indirect effects of rising sea level and a growing coastal population on these processes. Applications are to freshwater carbonate aquifers on islands (e.g. the Bahamas) and in coastal areas (e.g. the unconfined Floridan aquifer of the United States, the Yucatan Peninsula of Mexico).

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.

Local pH at the surface of hen egg white lysozyme

NASA Astrophysics Data System (ADS)

Otosu, Takuhiro; Kobayashi, Kaito; Yamaguchi, Shoichi

2018-02-01

The microenvironment at the surface of hen-egg-white lysozyme (HEWL) was examined by analyzing the change in pKa of fluorescein isothiocyanate (FITC) upon binding to the N-terminus of HEWL. The result showed that the local pH at the HEWL surface is higher than the bulk pH. Furthermore, the data showed that the difference between the local and bulk pH becomes larger with decreasing pH, suggesting HEWL repels more protons at lower pH. Because the local pH affects the protonation states of functional amino-acids at the protein surface, the results provide the fundamental insight into the microenvironment at the protein surface.

Prediction of purification of biopharmeceuticals with molecular dynamics

NASA Astrophysics Data System (ADS)

Ustach, Vincent; Faller, Roland

Purification of biopharmeceuticals remains the most expensive part of protein-based drug production. In ion exchange chromatography (IEX), prediction of the elution ionic strength of host cell and target proteins has the potential to reduce the parameter space for scale-up of protein production. The complex shape and charge distribution of proteins and pores complicates predictions of the interactions in these systems. All-atom molecular dynamics methods are beyond the scope of computational limits for mass transport regimes. We present a coarse-grained model for proteins for prediction of elution pH and ionic strength. By extending the raspberry model for colloid particles to surface shapes and charge distributions of proteins, we can reproduce the behavior of proteins in IEX. The average charge states of titratatable amino acid residues at relevant pH values are determined by extrapolation from all-atom molecular dynamics at pH 7. The pH specific all-atom electrostatic field is then mapped onto the coarse-grained surface beads of the raspberry particle. The hydrodynamics are reproduced with the lattice-Boltzmann scheme. This combination of methods allows very long simulation times. The model is being validated for known elution procedures by comparing the data with experiments. Defense Threat Reduction Agency (Grant Number HDTRA1-15-1-0054).

Electrochemical modelling of QD-phospholipid interactions.

PubMed

Zhang, Shengwen; Chen, Rongjun; Malhotra, Girish; Critchley, Kevin; Vakurov, Alexander; Nelson, Andrew

2014-04-15

The aggregation of quantum dots (QDs) and capping of individual QDs affects their activity towards biomembrane models. Electrochemical methods using a phospholipid layer on mercury (Hg) membrane model have been used to determine the phospholipid monolayer activity of thioglycollic acid (TGA) coated quantum dots (QDs) as an indicator of biomembrane activity. The particles were characterised for size and charge. The activity of the QDs towards dioleoyl phosphatidylcholine (DOPC) monolayers is pH dependent, and is most active at pH 8.2 within the pH range 8.2-6.5 examined in this work. This pH dependent activity is the result of increased particle aggregation coupled to decreasing surface charge emanating from the TGA carboxylic groups employed to stabilize the QD dispersion in aqueous media. Capping the QDs with CdS/ZnS lowers the particles' activity to phospholipid monolayers. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Corrosive effects of fluoride on titanium under artificial biofilm.

PubMed

Fukushima, Azusa; Mayanagi, Gen; Sasaki, Keiichi; Takahashi, Nobuhiro

2018-01-01

This study aimed to investigate the effect of sodium fluoride (NaF) on titanium corrosion using a biofilm model, taking environmental pH into account. Streptococcus mutans cells were used as the artificial biofilm, and pH at the bacteria-titanium interface was monitored after the addition of 1% glucose with NaF (0, 225 or 900ppmF) at 37°C for 90min. In an immersion test, the titanium samples were immersed in the NaF solution (0, 225 or 900ppm F; pH 4.2 or 6.5) for 30 or 90min. Before and after pH monitoring or immersion test, the electrochemical properties of the titanium surface were measured using a potentiostat. The amount of titanium eluted into the biofilm or the immersion solution was measured using inductively coupled plasma mass spectrometry. The color difference (ΔE*ab) and gloss of the titanium surface were determined using a spectrophotometer. After incubation with biofilm, pH was maintained at around 6.5 in the presence of NaF. There was no significant change in titanium surface and elution, regardless of the concentration of NaF. After immersion in 900ppm NaF solution at pH 4.2, corrosive electrochemical change was induced on the surface, titanium elution and ΔE*ab were increased, and gloss was decreased. NaF induces titanium corrosion in acidic environment in vitro, while NaF does not induce titanium corrosion under the biofilm because fluoride inhibits bacterial acid production. Neutral pH fluoridated agents may still be used to protect the remaining teeth, even when titanium-based prostheses are worn. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Optimizing isothiocyanate formation during enzymatic glucosinolate breakdown by adjusting pH value, temperature and dilution in Brassica vegetables and Arabidopsis thaliana

NASA Astrophysics Data System (ADS)

Hanschen, Franziska S.; Klopsch, Rebecca; Oliviero, Teresa; Schreiner, Monika; Verkerk, Ruud; Dekker, Matthijs

2017-01-01

Consumption of glucosinolate-rich Brassicales vegetables is associated with a decreased risk of cancer with enzymatic hydrolysis of glucosinolates playing a key role. However, formation of health-promoting isothiocyanates is inhibited by the epithiospecifier protein in favour of nitriles and epithionitriles. Domestic processing conditions, such as changes in pH value, temperature or dilution, might also affect isothiocyanate formation. Therefore, the influences of these three factors were evaluated in accessions of Brassica rapa, Brassica oleracea, and Arabidopsis thaliana. Mathematical modelling was performed to determine optimal isothiocyanate formation conditions and to obtain knowledge on the kinetics of the reactions. At 22 °C and endogenous plant pH, nearly all investigated plants formed nitriles and epithionitriles instead of health-promoting isothiocyanates. Response surface models, however, clearly demonstrated that upon change in pH to domestic acidic (pH 4) or basic pH values (pH 8), isothiocyanate formation considerably increases. While temperature also affects this process, the pH value has the greatest impact. Further, a kinetic model showed that isothiocyanate formation strongly increases due to dilution. Finally, the results show that isothiocyanate intake can be strongly increased by optimizing the conditions of preparation of Brassicales vegetables.

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

NASA Astrophysics Data System (ADS)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering capacity to previously studied non-halophilic bacteria. The titration data were used to determine the number of types, concentrations, and associated deprotonation constants of functional groups on the bacterial surface; the neptunium adsorption measurements were used to constrain binding constant values for the important neptunium (V)-bacterial surface species. Together, these results can be incorporated into geochemical speciation models to aid in the prediction of neptunium (V) mobility in complex bacteria-bearing geochemical systems.

Endoscopic sensing of alveolar pH

PubMed Central

Choudhury, D.; Tanner, M. G.; McAughtrie, S.; Yu, F.; Mills, B.; Choudhary, T. R.; Seth, S.; Craven, T. H.; Stone, J. M.; Mati, I. K.; Campbell, C. J.; Bradley, M.; Williams, C. K. I.; Dhaliwal, K.; Birks, T. A.; Thomson, R. R.

2016-01-01

Previously unobtainable measurements of alveolar pH were obtained using an endoscope-deployable optrode. The pH sensing was achieved using functionalized gold nanoshell sensors and surface enhanced Raman spectroscopy (SERS). The optrode consisted of an asymmetric dual-core optical fiber designed for spatially separating the optical pump delivery and signal collection, in order to circumvent the unwanted Raman signal generated within the fiber. Using this approach, we demonstrate a ~100-fold increase in SERS signal-to-fiber background ratio, and demonstrate multiple site pH sensing with a measurement accuracy of ± 0.07 pH units in the respiratory acini of an ex vivo ovine lung model. We also demonstrate that alveolar pH changes in response to ventilation. PMID:28101415

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

PubMed

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

Adsorption of transgenic insecticidal Cry1Ab protein to silica particles. Effects on transport and bioactivity.

PubMed

Madliger, Michael; Gasser, Christoph A; Schwarzenbach, René P; Sander, Michael

2011-05-15

Bt crops are genetically modified to be resistant against insect pests by expressing insecticidal Cry proteins. The processes governing the fate and bioavailability of the expressed transgenic Cry proteins in soils are poorly understood. We studied adsorption of Cry1Ab to negatively charged silica (SiO(2)) particles, a major soil constituent and a model for negatively charged mineral surfaces, at pH 5 to 10 and ionic strengths I = 10 mM to 250 mM, both in solution depletion and saturated column transport experiments. Cry1Ab-SiO(2) interactions were dominated by patch-controlled electrostatic attraction (PCEA), as evident from increasing Cry1Ab attraction to SiO(2) with decreasing I at pH at which both Cry1Ab and SiO(2) were net negatively charged. Experimental and modeling evidence is provided that the surface heterogeneity of SiO(2) particles modulated PCEA, leading to a fraction of adsorption sites with slow Cry1Ab desorption kinetics. Desorption rates from these sites increased upon increasing the solution pH. In toxicity bioassays, we demonstrated that Cry1Ab retained insecticidal activity when adsorbed to SiO(2), suggesting high protein conformational stability during adsorption-desorption cycles. Models predicting Cry1A protein adsorption in soils therefore need to account for combined effects of the nonuniform protein surface charge distribution and of sorbent surface heterogeneity.

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

NASA Astrophysics Data System (ADS)

Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

2006-04-01

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir, which can play an important role in the regulation of silica fluxes in terrestrial aquatic environments.

Preparation of Curcumin Loaded Egg Albumin Nanoparticles Using Acetone and Optimization of Desolvation Process.

PubMed

Aniesrani Delfiya, D S; Thangavel, K; Amirtham, D

2016-04-01

In this study, acetone was used as a desolvating agent to prepare the curcumin-loaded egg albumin nanoparticles. Response surface methodology was employed to analyze the influence of process parameters namely concentration (5-15%w/v) and pH (5-7) of egg albumin solution on solubility, curcumin loading and entrapment efficiency, nanoparticles yield and particle size. Optimum processing conditions obtained from response surface analysis were found to be the egg albumin solution concentration of 8.85%w/v and pH of 5. At this optimum condition, the solubility of 33.57%, curcumin loading of 4.125%, curcumin entrapment efficiency of 55.23%, yield of 72.85% and particles size of 232.6 nm were obtained and these values were related to the values which are predicted using polynomial model equations. Thus, the model equations generated for each response was validated and it can be used to predict the response values at any concentration and pH.

Adsorption Characteristics of Pb(2+) onto Wine Lees-Derived Biochar.

PubMed

Zhu, Qihong; Wu, Jun; Wang, Lilin; Yang, Gang; Zhang, Xiaohong

2016-08-01

Biochar has great advantages in soil amendment and polluted soil remediation. Herein, the pore and adsorption properties of wine lees-derived biochar were explored. Specifically, the adsorption isotherm and kinetics of Pb(2+) onto wine lees-derived biochar were examined. Experimental results revealed that wine lees-derived biochar featured large specific surface area and total pore volume, and high contents of -COOH and -OH on its surface. Adsorption of Pb(2+) onto wine lees-derived biochar proceeded via a multilayer adsorption mechanism, as described by the Freundlich adsorption model. Adsorption kinetics followed the Lagergren pseudo-second-order kinetics model; adsorption equilibrium was achieved within 30-60 min. Furthermore, the effect of solution pH on the adsorption of Pb(2+) was investigated. Within the studied pH range of 3-6, the adsorption capacity increased with increasing pH. Under established optimized conditions, wine lees-derived biochar achieved a Pb(2+) adsorption capacity of 79.12 mg/g.

Removal of Heavy Metals by Adsorption onto Activated Carbon Derived from Pine Cones of Pinus roxburghii.

PubMed

Saif, Muhammad Jawwad; Zia, Khalid Mahmood; Fazal-ur-Rehman; Usman, Muhammad; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid

2015-04-01

Activated carbon derived from cones of Pinus roxburghii (Himalayan Pine) was used as an adsorbent for the removal of copper, nickel and chromium ions from waste water. Surface analysis was carried out to determine the specific surface area and pore size distribution of the pine cone derived activated carbon. Optimal parameters, effect of adsorbent quantity, pH, equilibrium time, agitation speed and temperature were studied. Equilibrium data were evaluated by Langmuir and Freundlich isotherm models. Langmuir isotherm afforded the best fit to the equilibrium data with a maximum adsorption capacity of 14.2, 31.4 and 29.6 mg/g for Cu(II), Ni(II) and Cr(VI) respectively. Maximum adsorption of Cu(II), Ni(II) was observed in the pH range 4.0 to 4.5, whereas the best adsorption of Cr(VI) was observed at pH 2.5. It was found that 180 minutes was sufficient to gain adsorption equilibrium. The adsorption process follows a pseudo-second-order kinetic model.

A semi-grand canonical Monte Carlo simulation model for ion binding to ionizable surfaces: proton binding of carboxylated latex particles as a case study.

PubMed

Madurga, Sergio; Rey-Castro, Carlos; Pastor, Isabel; Vilaseca, Eudald; David, Calin; Garcés, Josep Lluís; Puy, Jaume; Mas, Francesc

2011-11-14

In this paper, we present a computer simulation study of the ion binding process at an ionizable surface using a semi-grand canonical Monte Carlo method that models the surface as a discrete distribution of charged and neutral functional groups in equilibrium with explicit ions modelled in the context of the primitive model. The parameters of the simulation model were tuned and checked by comparison with experimental titrations of carboxylated latex particles in the presence of different ionic strengths of monovalent ions. The titration of these particles was analysed by calculating the degree of dissociation of the latex functional groups vs. pH curves at different background salt concentrations. As the charge of the titrated surface changes during the simulation, a procedure to keep the electroneutrality of the system is required. Here, two approaches are used with the choice depending on the ion selected to maintain electroneutrality: counterion or coion procedures. We compare and discuss the difference between the procedures. The simulations also provided a microscopic description of the electrostatic double layer (EDL) structure as a function of pH and ionic strength. The results allow us to quantify the effect of the size of the background salt ions and of the surface functional groups on the degree of dissociation. The non-homogeneous structure of the EDL was revealed by plotting the counterion density profiles around charged and neutral surface functional groups. © 2011 American Institute of Physics

Carbohydrate-electrolyte drinks exhibit risks for human enamel surface loss

PubMed Central

Passos, Vanara Florêncio; Lima, Juliana Paiva Marques; Santiago, Sérgio Lima; Rodrigues, Lidiany Karla Azevedo

2016-01-01

Objectives The aim of this investigation was to give insights into the impact of carbohydrate-electrolyte drinks on the likely capacity of enamel surface dissolution and the influence of human saliva exposure as a biological protective factor. Materials and Methods The pH, titratable acidity (TA) to pH 7.0, and buffer capacity (β) of common beverages ingested by patients under physical activity were analyzed. Then, we randomly distributed 50 specimens of human enamel into 5 groups. Processed and natural coconut water served as controls for testing three carbohydrate-electrolyte drinks. In all specimens, we measured surface microhardness (Knoop hardness numbers) and enamel loss (profilometry, µm) for baseline and after simulated intake cycling exposure model. We also prepared areas of specimens to be exposed to human saliva overnight prior to the simulated intake cycling exposure. The cycles were performed by alternated immersions in beverages and artificial saliva. ANOVA two-way and Tukey HDS tests were used. Results The range of pH, TA, and β were 2.85 - 4.81, 8.33 - 46.66 mM/L and 3.48 - 10.25 mM/L × pH, respectively. The highest capacity of enamel surface dissolution was found for commercially available sports drinks for all variables. Single time human saliva exposure failed to significantly promote protective effect for the acidic attack of beverages. Conclusions In this study, carbohydrate-electrolyte drinks usually consumed during endurance training may have a greater capacity of dissolution of enamel surface depending on their physicochemical proprieties associated with pH and titratable acidity. PMID:27847745

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

PubMed

Xue, Yongjie; Hou, Haobo; Zhu, Shujing

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

Effect of Salt Concentration on the pH Responses of Strong and Weak Polyelectrolyte Brushes.

PubMed

Zhang, Jian; Kou, Ran; Liu, Guangming

2017-07-11

Strong polyelectrolyte brushes (SPB) and weak polyelectrolyte brushes (WPB) have different origins with response to pH, which makes their pH-responsive properties sensitive to salt concentration in different ways. Herein, we have employed poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) and poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes as model systems for SPB and WPB, respectively, to investigate the effect of salt concentration on the pH responses of SPB and WPB using several surface-sensitive techniques. The pH-responsive properties of the PMETAC brushes are governed by the reorganization of the interchain hydrogen bonds between the grafted chains, whereas the pH response of the PDMAEMA brushes is controlled by the charge of the grafted chains. The response of the properties of the PMETAC brushes including hydration, conformation, and surface wettability becomes weaker with increasing salt concentration induced by the competitive adsorption of counterions to the brushes between OH - and Cl - . The weakening of the pH response of the PMETAC brushes is more remarkable at the relatively high pH values. The pH response of the PDMAEMA brushes also exhibits a salt-concentration dependence. As the salt concentration increases, the weakening of the pH response of the PDMAEMA brushes is attributed to the decrease in osmotic pressure within the brushes at relatively low pH values.

Roughness and pH changes of enamel surface induced by soft drinks in vitro-applications of stylus profilometry, focus variation 3D scanning microscopy and micro pH sensor.

PubMed

Fujii, Mie; Kitasako, Yuichi; Sadr, Alireza; Tagami, Junji

2011-01-01

This study aimed to evaluate enamel surface roughness (Ra) and pH before and after erosion by soft drinks. Enamel was exposed to a soft drink (cola, orange juice or green tea) for 1, 5 or 60 min; Ra was measured using contact-stylus surface profilometry (SSP) and non-contact focus variation 3D microscope (FVM). Surface pH was measured using a micro pH sensor. Data were analyzed at significance level of alpha=0.05. There was a significant correlation in Ra between SSP and FVM. FVM images showed no changes in the surface morphology after various periods of exposure to green tea. Unlike cola and orange juice, exposure to green tea did not significantly affect Ra or pH. A significant correlation was observed between surface pH and Ra change after exposure to the drinks. Optical surface analysis and micro pH sensor may be useful tools for non-damaging, quantitative assessment of soft drinks erosion on enamel.

Phosphorus atomic layer doping in Ge using RPCVD

NASA Astrophysics Data System (ADS)

Yamamoto, Yuji; Kurps, Rainer; Mai, Christian; Costina, Ioan; Murota, Junichi; Tillack, Bernd

2013-05-01

Phosphorus atomic layer doping (P-ALD) in Ge is investigated at temperatures between 100 °C and 400 °C using a single wafer reduced pressure chemical vapor deposition (RPCVD) system. Hydrogen-terminated and hydrogen-free Ge (1 0 0) surfaces are exposed to PH3 at different PH3 partial pressures after interrupting Ge growth. The adsorption and reaction of PH3 proceed on a hydrogen-free Ge surface. For all temperatures and PH3 partial pressures used for the P-ALD, the P dose increased with increasing PH3 exposure time and saturated. The saturation value of the incorporated P dose at 300 °C is ˜1.5 × 1014 cm-3, which is close to a quarter of a monolayer of the Ge (1 0 0) surface. The P dose could be simulated assuming a Langmuir-type kinetics model with a saturation value of Nt = 1.55 × 1014 cm-2 (a quarter of a monolayer), reaction rate constant kr = 77 s-1 and thermal equilibrium constant K = 3.0 × 10-2 Pa-1. An electrically active P concentration of 5-6 × 1019 cm-3, which is a 5-6 times higher thermal solubility of P in Ge, is obtained by multiple P spike fabrication using the P-ALD process.

Adsorption and Reduction of Hexavalent Chromium on the Surface of Vivianite at Acidic Environment

NASA Astrophysics Data System (ADS)

HA, S.; Hyun, S. P.; Lee, W.

2016-12-01

Due to the rapid increase of chemical use in industrial activities, acid spills have frequently occurred in Korea. The acid spill causes soil and water acidification and additional problems such as heavy metal leaching from the soil. Hexavalent chromium (Cr(VI)) is relatively mobile in the environment and toxic and mutagenic. Monoclinic octa-hydrated ferrous phosphate, vivianite, is one of commonly found iron-bearing soil minerals occurring in phosphorous-enriched reducing environments. We have investigated reductive sorption of Cr(VI) on the vivianite surfaces using batch experimental tests under diverse groundwater conditions. Cr(VI) (5 mg/L) was added in 6.5 g/L vivianite suspension buffered at pH 5, 7, and 9, using 0.05 M HEPES or tris buffer solution, to check the effect of pH on the reductive sorption of Cr(VI) on the vivianite surface. The aqueous Cr(VI) removal was fastest at pH 5, followed by pH 7, and pH 9. The effect of ionic strength on the removal kinetics of Cr(VI) was negligible. It could be subsequently removed via sorption and reduction on the surface of vivianite of which reactive chemical species could be aqueous Fe(II), iron oxides, and metavivianite. Adsorption test was conducted using the same amount of Cr(III) to check the selectivity of chromium species on the vivianite surface for the reductive adsorption. Through Cr extraction test, amount of strong-bound Cr to vivianite is similar for Cr(III) and Cr(VI) injection but amount of weak-bound Cr is bigger for Cr(VI) injection. Reaction mechanism for the sorption and reductive transformation of Cr(VI) to Cr(III) species at reactive sites of vivianite surface are discussed based on surface complexation modeling and K-edge Fe X-ray absorption near edge structure (XANES) results. Since vivianite is reacted with Cr(VI), two smooth peaks of absorption edge changed to one sharp peak. Pre-edge that contains 1s-3d transition information tends to show high peak when reaction time is increased and pH is low. This fact indicated that the Fe(II) is oxidized to Fe(III) at the surface of viviante and this phenomena is optimized at pH 5 and longer elapsed time.

Investigation of the factors that influence lead accumulation onto polyethylene: Implication for potable water plumbing pipes.

PubMed

Salehi, Maryam; Jafvert, Chad T; Howarter, John A; Whelton, Andrew J

2018-04-05

The influence of polymer aging, water pH, and aqueous Pb concentration on Pb deposition onto low density polyethylene (LDPE) was investigated. LDPE pellets were aged by ozonation at 85 °C. ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis of aged LDPE surfaces showed that a variety of polar functional groups (>CO<, >CO, >COO) were formed during aging. These functional groups likely provided better nucleation sites for Pb(OH) 2 deposition compared to new LDPE, which did not have these oxygen-containing functional groups. The type and amount of Pb species present on these surfaces were evaluated through XPS. The influence of exposure duration on Pb deposition onto LDPE was modeled using the pseudo-first-order equation. Distribution ratios of 251.5 for aged LDPE and 69.3 for new LDPE showed that Pb precipitates had greater affinity for the surface of aged LDPE compared to new LDPE. Aged LDPE had less Pb surface loading at pH 11 compared to loading at pH 7.8. Pb surface loading for aged LDPE changed linearly with aging duration (from 0.5-7.5 h). Pb surface loading on both new and aged LDPE increased linearly with increasing Pb initial concentration. Greater Pb precipitation rates were found for aged LDPE compared to new LDPE at both tested pH values. Copyright © 2017 Elsevier B.V. All rights reserved.

Shear bond strength of one-step self-etch adhesives to enamel: effect of acid pretreatment.

PubMed

Poggio, Claudio; Scribante, Andrea; Della Zoppa, Federica; Colombo, Marco; Beltrami, Riccardo; Chiesa, Marco

2014-02-01

The purposes of this study were to evaluate the effect of surface pretreatment with phosphoric acid on the enamel bond strength of four-one-step self-etch adhesives with different pH values. One hundred bovine permanent mandibular incisors were used. The materials used in this study included four-one-step self-etch adhesives with different pH values: Adper(™) Easy Bond Self-Etch Adhesive (ph = 0,8-1), Futurabond NR (ph = 1,4), G-aenial Bond (ph = 1,5), Clearfil(3) S Bond (ph = 2,7). One two-step self-etch adhesive (Clearfil SE Bond/ph = 0,8-1) was used as control. The teeth were assigned into two subgroups according to bonding procedure. In the first subgroup (n = 50), no pretreatment agent was applied. In the second subgroup (n = 50), etching was performed using 37% phosphoric acid for 30 s. After adhesive systems application, a nanohybrid composite resin was inserted into the enamel surface. The specimens were placed in a universal testing machine (Model 3343, Instron Corp., Canton, Mass., USA). After the testing procedure, the fractured surfaces were examined with an optical microscope at a magnification of 10× to determine failure modes. The adhesive remnant index (ARI) was used to assess the amount of adhesive left on the enamel surface. Descriptive statistics of the shear bond strength and frequency distribution of ARI scores were calculated. Enamel pretreatment with phosphoric acid significantly increased bond strength values of all the adhesives tested. No significant differences in bond strength were detected among the four different one-step self-etch adhesives with different pH. Two-step self-etch adhesive showed the highest bond strength. © 2013 John Wiley & Sons A/S.

Modeling Silicate Weathering for Elevated CO2 and Temperature

NASA Astrophysics Data System (ADS)

Bolton, E. W.

2016-12-01

A reactive transport model (RTM) is used to assess CO2 drawdown by silicate weathering over a wide range of temperature, pCO2, and infiltration rates for basalts and granites. Although RTM's have been used extensively to model weathering of basalts and granites for present-day conditions, we extend such modeling to higher CO2 that could have existed during the Archean and Proterozoic. We also consider a wide range of surface temperatures and infiltration rates. We consider several model basalt and granite compositions. We normally impose CO2 in equilibrium with the various atmospheric ranges modeled and CO2 is delivered to the weathering zone by aqueous transport. We also consider models with fixed CO2 (aq) throughout the weathering zone as could occur in soils with partial water saturation or with plant respiration, which can strongly influence pH and mineral dissolution rates. For the modeling, we use Kinflow: a model developed at Yale that includes mineral dissolution and precipitation under kinetic control, aqueous speciation, surface erosion, dynamic porosity, permeability, and mineral surface areas via sub-grid-scale grain models, and exchange of volatiles at the surface. Most of the modeling is done in 1D, but some comparisons to 2D domains with heterogeneous permeability are made. We find that when CO2 is fixed only at the surface, the pH tends toward higher values for basalts than granites, in large part due to the presence of more divalent than monovalent cations in the primary minerals, tending to decrease rates of mineral dissolution. Weathering rates increase (as expected) with increasing CO2 and temperature. This modeling is done with the support of the Virtual Planetary Laboratory.

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

Warschkow, O.; McKenzie, D. R.; Curson, N. J.

Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH{sub 3}) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH{sub 2}+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH{sub 2} fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH{sub 3} stoichiometry. Our calculated activation energies describemore » the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.« less

Towards predicting coral calcification responses to ocean acidification: A combined modeling and experimental approach

NASA Astrophysics Data System (ADS)

Mollica, N. R.; Guo, W.; Cohen, A. L.; Foster, G. L.; Barkley, H.

2016-02-01

Experiments show that ocean acidification is detrimental to coral calcification. Nevertheless, coral sensitivities to OA vary and the mechanism(s) underlying these variable responses are not fully understood. One hypothesis is that ocean acidification affects the ability of coral's to regulate the pH of fluid at the site of calcification. We developed a numerical model of coral calcification that simulates corals' pH regulation based on physiochemical principles and predicts the rate of calcification [1]. Here we apply this model to Palauan corals, and seek to test the model's efficacy by comparing the predicted coral calcification responses with experimental measurements. Four coral cores were collected from two sites of different pH (7.84 and 8.04 respectively). Their bulk annual calcification rates, quantified from average density and extension rate measurements, vary from .83 to 1.39 g cm-2 year-1 for the low pH site and from 0.75 to 1.21 g cm-2 year-1for the high pH site. The higher bulk calcification rates observed in corals from the low pH site contrasts the expected general decrease in calcification in low pH seawater, and differs from our model prediction. We suspect this apparent discrepancy arises because fast-calcifying corals in low pH water are able to modulate the pH of fluid at the site of calcification. We test this hypothesis using boron isotope measurements from each coral. In addition, a more accurate measurement of instantaneous calcification, considering the number of corallites per measured area and the exact surface area of each polyp's 3-dimensional calcification site is applied. [1] Guo, W. (2014). AGU Fall Meeting, Abstract B41B-0033.

Structure-charge relationship - the case of hematite (001)

DOE PAGES

Lutzenkirchen, Johannes; Heberling, Frank; Supljika, Filip; ...

2015-01-16

We present a multidisciplinary study on the hematite (001)–aqueous solution interface, in particular the relationship between surface structure (studied via surface diffraction in a humid atmosphere) and the macroscopic charging (studied via surface- and zeta-potential measurements in electrolyte solutions as a function of pH). Upon aging in water changes in the surface structure are observed, that are accompanied by drastic changes in the zeta-potential. Surprisingly the surface potential is not accordingly affected. We interpret our results by increasing hydration of the surface with time and enhanced reactivity of singly-coordinated hydroxyl groups that cause the isoelectric point of the surface tomore » shift to values that are reminiscent of those typically reported for hematite particles. In its initial stages after preparation the hematite surface is very flat and only weakly hydrated. Our model links the entailing weak water structure with the observed low isoelectric point reminiscent of hydrophobic surfaces. The absence of an aging effect on the surface potential vs. pH curves is interpreted as domination of the surface potential by the doubly coordinated hydroxyls, which are present on both surfaces.« less

Surface complexation model of uranyl sorption on Georgia kaolinite

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

2004-01-01

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

The surface properties of Shewanella putrefaciens 200 and S. oneidensis MR-1: the effect of pH and terminal electron acceptors.

PubMed

Furukawa, Yoko; Dale, Jason R

2013-04-08

We investigated the surface characteristics of two strains of Shewanella sp., S. oneidensis MR-1 and S. putrefaciens 200, that were grown under aerobic conditions as well as under anaerobic conditions with trimethylamine oxide (TMAO) as the electron acceptor. The investigation focused on the experimental determination of electrophoretic mobility (EPM) under a range of pH and ionic strength, as well as by subsequent modeling in which Shewanella cells were considered to be soft particles with water- and ion-permeable outermost layers. The soft layer of p200 is significantly more highly charged (i.e., more negative) than that of MR-1. The effect of electron acceptor on the soft particle characteristics of Shewanella sp. is complex. The fixed charge density, which is a measure of the deionized and deprotonated functional groups in the soft layer polymers, is slightly greater (i.e., more negative) for aerobically grown p200 than for p200 grown with TMAO. On the other hand, the fixed charge density of aerobically grown MR1 is slightly less than that of p200 grown with TMAO. The effect of pH on the soft particle characteristics is also complex, and does not exhibit a clear pH-dependent trend. The Shewanella surface characteristics were attributed to the nature of the outermost soft layer, the extracellular polymeric substances (EPS) in case of p200 and lypopolysaccharides (LPS) in case of MR1 which generally lacks EPS. The growth conditions (i.e., aerobic vs. anaerobic TMAO) have an influence on the soft layer characteristics of Shewanella sp. cells. Meanwhile, the clear pH dependency of the mechanical and morphological characteristics of EPS and LPS layers, observed in previous studies through atomic force microscopy, adhesion tests and spectroscopies, cannot be corroborated by the electrohydrodynamics-based soft particle characteristics which does not exhibited a clear pH dependency in this study. While the electrohydrodynamics-based soft-particle model is a useful tool in understanding bacteria's surface properties, it needs to be supplemented with other characterization methods and models (e.g., chemical and micromechanical) in order to comprehensively address all of the surface-related characteristics important in environmental and other aqueous processes.

Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

NASA Astrophysics Data System (ADS)

Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

2011-12-01

The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at pH < 5.0. These results suggested that the contaminated sediments might either contain other more reactive clay minerals such as smectite, or that the long-term acid-leaching process might have altered the surface reactivity of the original sediments. Further studies are needed to identify more reactive mineral facies and understand the effects of acid leaching on the surface reactivity of the sediments.

Dynamics of basaltic glass dissolution - Capturing microscopic effects in continuum scale models

NASA Astrophysics Data System (ADS)

Aradóttir, E. S. P.; Sigfússon, B.; Sonnenthal, E. L.; Björnsson, G.; Jónsson, H.

2013-11-01

The method of 'multiple interacting continua' (MINC) was applied to include microscopic rate-limiting processes in continuum scale reactive transport models of basaltic glass dissolution. The MINC method involves dividing the system up to ambient fluid and grains, using a specific surface area to describe the interface between the two. The various grains and regions within grains can then be described by dividing them into continua separated by dividing surfaces. Millions of grains can thus be considered within the method without the need to explicity discretizing them. Four continua were used for describing a dissolving basaltic glass grain; the first one describes the ambient fluid around the grain, while the second, third and fourth continuum refer to a diffusive leached layer, the dissolving part of the grain and the inert part of the grain, respectively. The model was validated using the TOUGHREACT simulator and data from column flow through experiments of basaltic glass dissolution at low, neutral and high pH values. Successful reactive transport simulations of the experiments and overall adequate agreement between measured and simulated values provides validation that the MINC approach can be applied for incorporating microscopic effects in continuum scale basaltic glass dissolution models. Equivalent models can be used when simulating dissolution and alteration of other minerals. The study provides an example of how numerical modeling and experimental work can be combined to enhance understanding of mechanisms associated with basaltic glass dissolution. Column outlet concentrations indicated basaltic glass to dissolve stoichiometrically at pH 3. Predictive simulations with the developed MINC model indicated significant precipitation of secondary minerals within the column at neutral and high pH, explaining observed non-stoichiometric outlet concentrations at these pH levels. Clay, zeolite and hydroxide precipitation was predicted to be most abundant within the column.

Interfacial charging phenomena of aluminum (hydr)oxides

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

Hiemstra, T.; Yong, H.; Van Riemsdijk, W.H.

1999-08-31

The interfacial charging of Al(OH){sub 3} (gibbsite and bayerite) and Al{sub 2}O{sub 3} has been studied. For Al(OH){sub 3} it can be shown that the very strong variation in charging behavior for different preparations is related to the relative presence of differently reacting crystal planes. The edge faces of the hexagonal gibbsite crystals are proton reactive over the whole pH range, in contrast to the 001 plane, which is mainly uncharged below pH = 10. On this 001 face only doubly coordinated surface groups are found, in contrast to the edges which also have singly coordinated surface groups. The resultsmore » are fully in agreement with the predictions of the Multi site complexation (MUSIC) model. The proton adsorption, electrolyte ion adsorption, and shift of the IEP of gibbsite and aluminum oxide have been modeled simultaneously. For gibbsite, the ion pair formation of Na is larger than that of Cl, as is evidenced by modeling the experimentally observed upward shift on the IEP and charge reversal at high electrolyte concentrations. All these experimental results can be satisfactorily modeled with the MUSIC model, including the experimental surface potential of aluminum oxide (ISFET).« less

A scanning tunneling microscopy study of PH 3 adsorption on Si(1 1 1)-7 × 7 surfaces, P-segregation and thermal desorption

NASA Astrophysics Data System (ADS)

Ji, Jeong-Young; Shen, T.-C.

2007-04-01

PH 3 adsorption on Si(1 1 1)-7 × 7 was studied after various exposures between 0.3 and 60 L at room temperature by means of scanning tunneling microscopy (STM). PH 3-, PH 2-, H-reacted, and unreacted adatoms can be identified by analyzing empty-state STM images at different sample biases. PH x-reacted rest-atoms can be observed in empty-state STM images if neighboring adatoms are hydrogen terminated. Most of the PH 3 adsorbs dissociatively on the surface, generating H- and PH 2-adsorbed rest-atom and adatom sites. Dangling-bonds at rest-atom sites are more reactive than adatom sites and the faulted half of the 7 × 7 unit cell is more reactive than the unfaulted half. Center adatoms are overwhelmingly preferred over corner adatoms for PH 2 adsorption. The saturation P coverage is ˜0.18 ML. Annealing of PH 3-reacted 7 × 7 surfaces at 900 K generates disordered, partially P-covered surfaces, but dosing PH 3 at 900 K forms P/Si(1 1 1)- 6√{3} surfaces. Si deposition at 510 K leaves disordered clusters on the surface, which cannot be reordered by annealing up to 800 K. However, annealing above 900 K recreates P/Si(1 1 1)- 6√{3} surfaces. Surface morphologies formed by sequential rapid thermal annealing are also presented.

Complexation of carboxylate on smectite surfaces.

PubMed

Liu, Xiandong; Lu, Xiancai; Zhang, Yingchun; Zhang, Chi; Wang, Rucheng

2017-07-19

We report a first principles molecular dynamics (FPMD) study of carboxylate complexation on clay surfaces. By taking acetate as a model carboxylate, we investigate its inner-sphere complexes adsorbed on clay edges (including (010) and (110) surfaces) and in interlayer space. Simulations show that acetate forms stable monodentate complexes on edge surfaces and a bidentate complex with Ca 2+ in the interlayer region. The free energy calculations indicate that the complexation on edge surfaces is slightly more stable than in interlayer space. By integrating pK a s and desorption free energies of Al coordinated water calculated previously (X. Liu, X. Lu, E. J. Meijer, R. Wang and H. Zhou, Geochim. Cosmochim. Acta, 2012, 81, 56-68; X. Liu, J. Cheng, M. Sprik, X. Lu and R. Wang, Geochim. Cosmochim. Acta, 2014, 140, 410-417), the pH dependence of acetate complexation has been revealed. It shows that acetate forms inner-sphere complexes on (110) in a very limited mildly acidic pH range while it can complex on (010) in the whole common pH range. The results presented in this study form a physical basis for understanding the geochemical processes involving clay-organics interactions.

Validation of a triangular quantum well model for GaN-based HEMTs used in pH and dipole moment sensing

NASA Astrophysics Data System (ADS)

Rabbaa, S.; Stiens, J.

2012-11-01

Gallium nitride (GaN) is a relatively new semiconductor material that has the potential of replacing gallium arsenide (GaAs) in some of the more recent technological applications, for example chemical sensor applications. In this paper, we introduce a triangular quantum well model for an undoped AlGaN/GaN high electron mobility transistor (HEMT) structure used as a chemical and biological sensor for pH and dipole moment measurements of polar liquids. We have performed theoretical calculations related to the HEMT characteristics and we have compared them with experimental measurements carried out in many previous papers. These calculations include the current-voltage (I-V) characteristics of the device, the surface potential, the change in the drain current with the dipole moment and the drain current as a function of pH. The results exhibit good agreement with experimental measurements for different polar liquids and electrolyte solutions. It is also found that the drain current of the device exhibits a large linear variation with the dipole moment, and that the surface potential and the drain current depend strongly on the pH. Therefore, it can distinguish molecules with slightly different dipole moments and solutions with small variations in pH. The ability of the device to sense biomolecules (such as proteins) with very large dipole moments is investigated.

Optimization of free radical scavenging capacity and pH of Hylocereus polyrhizus peel by Response Surface Methodology

NASA Astrophysics Data System (ADS)

Putranto, A. W.; Dewi, S. R.; Puspitasari, Y.; Nuriah, F. A.

2018-03-01

Red dragon fruit (Hylocereus polyrhizus) peel, a by-product of juice processing, contains a high antioxidant that can be used for nutraceuticals. Hence, it is important to extract and investigate its antioxidant stability. The aim of this study was to optimize the free radical scavenging capacity and pH of H. polyrhizus peel extract using Central Composite Design (CCD) under Response Surface Methodology (RSM). The extraction of H. polyrhizus peel was done by using green-Pulsed Electric Field (PEF)-assisted extraction method. Factors optimized were electric field strength (kV/cm) and extraction time (seconds). The result showed that the correlation between responses (free radical-scavenging capacity and pH) and two factors was quadratic model. The optimum conditions was obtained at the electric field strength of 3.96 kV/cm, and treatment time of 31.9 seconds. Under these conditions, the actual free radical-scavenging capacity and pH were 75.86 ± 0.2 % and 4.8, respectively. The verification model showed that the actual values are in accordance with the predicted values, and have error rate values of free radical-scavenging capacity and pH responses were 0.1% and 3.98%, respectively. We suggest to extract the H. polyrhizus peel using a green and non-thermal extraction technology, PEF-assisted extraction, for research, food applications and nutraceuticals industry.

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

Tang, Guoping; Luo, Wensui; Brooks, Scott C

We conducted batch and recirculating column titration tests with contaminated acidic sediments with controlled CO2 in the headspace, and extended the geochemical model by Gu et al. (2003, GCA) to better understand and quantify the reactions governing trace metal fate in the subsurface. The sediment titration curve showed slow pH increase due to strong buffering by Al precipitation and CO2 uptake. Assuming precipitation of basaluminite at low saturation index (SI=-4), and decreasing cation exchange selectivity coefficient (kNa\\Al=0.3), the predictions are close to the observed pH and Al; and the model explains 1) the observed Ca, Mg, and Mn concentration decreasemore » by cation exchange with sorbed Al, and 2) the decrease of U by surface complexation with Fe hydroxides at low pH, and precipitation as liebigite (Ca2UO2(CO3)3:10H2O) at pH>5.5. Without further adjustment geochemical parameters, the model describes reasonably well previous sediment and column titration tests without CO2 in the headspace, as well as the new large column test. The apparent inhibition of U and Ni decrease in the large column can be explained by formation of aqueous carbonate complexes and/or competition with carbonate for surface sites. These results indicated that ignoring labile solid phase Al would underestimate base requirement in titration of acidic aquifers.« less

Empirical algorithms to estimate water column pH in the Southern Ocean

NASA Astrophysics Data System (ADS)

Williams, N. L.; Juranek, L. W.; Johnson, K. S.; Feely, R. A.; Riser, S. C.; Talley, L. D.; Russell, J. L.; Sarmiento, J. L.; Wanninkhof, R.

2016-04-01

Empirical algorithms are developed using high-quality GO-SHIP hydrographic measurements of commonly measured parameters (temperature, salinity, pressure, nitrate, and oxygen) that estimate pH in the Pacific sector of the Southern Ocean. The coefficients of determination, R2, are 0.98 for pH from nitrate (pHN) and 0.97 for pH from oxygen (pHOx) with RMS errors of 0.010 and 0.008, respectively. These algorithms are applied to Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) biogeochemical profiling floats, which include novel sensors (pH, nitrate, oxygen, fluorescence, and backscatter). These algorithms are used to estimate pH on floats with no pH sensors and to validate and adjust pH sensor data from floats with pH sensors. The adjusted float data provide, for the first time, seasonal cycles in surface pH on weekly resolution that range from 0.05 to 0.08 on weekly resolution for the Pacific sector of the Southern Ocean.

Controlling acrylamide in French fry and potato chip models and a mathematical model of acrylamide formation: acrylamide: acidulants, phytate and calcium.

PubMed

Park, Yeonhwa; Yang, Heewon; Storkson, Jayne M; Albright, Karen J; Liu, Wei; Lindsay, Robert C; Pariza, Michael W

2005-01-01

We previously reported that in potato chip and French fry models, the formation of acrylamide can be reduced by controlling pH during processing steps, either by organic (acidulants) or inorganic acids. Use of phytate, a naturally occurring chelator, with or without Ca++ (or divalent ions), can reduce acrylamide formation in both models. However, since phytate itself is acidic, the question remains as to whether the effect of phytate is due to pH alone or to additional effects. In the French fry model, the effects on acrylamide formation of pH, phytate, and/or Ca++ in various combinations were tested in either blanching or soaking (after blanching) steps. All treatments significantly reduced acrylamide levels compared to control. Among variables tested, pH may be the single most important factor for reducing acrylamide levels, while there were independent effects of phytate and/or Ca++ in this French fry model. We also developed a mathematical formula to estimate the final concentration of acrylamide in a potato chip model, using variables that can affect acrylamide formation: glucose and asparagine concentrations, cut potato surface area and shape, cooking temperature and time, and other processing conditions.

Adsorption and spectroscopic characterization of lactoferrin on hydroxyapatite nanocrystals.

PubMed

Iafisco, Michele; Di Foggia, Michele; Bonora, Sergio; Prat, Maria; Roveri, Norberto

2011-01-28

Lactoferrin (LF), a well-characterized protein of blood plasma and milk with antioxidant, cariostatic, anticarcinogenic and anti-inflammatory properties, has been adsorbed onto biomimetic hydroxyapatite (HA) nanocrystals at two different pH values (7.4 and 9.0). The interaction was herein investigated by spectroscopic, thermal and microscopic techniques. The positive electrostatic surface potential of LF at pH 7.4 allows a strong surface interaction with the slightly negative HA nanocrystals and avoids the protein-protein interaction, leading to the formation of a coating protein monolayer. In contrast, at pH 9.0 the surface potential of LF is a mix of negative and positive zones favouring the protein-protein interaction and reducing the interaction with HA nanocrystals; as a result a double layer of coating protein was formed. These experimental findings are supported by the good fittings of the adsorption isotherms by different theoretical models according to Langmuir, Freundlich and Langmuir-Freundlich models. The nanosized HA does not appreciably affect the conformation of the adsorbed protein. In fact, using FT-Raman and FT-IR, we found that after adsorption the protein was only slightly unfolded with a small fraction of the α-helix structure being converted into turn, while the β-sheet content remained almost unchanged. The bioactive surface of HA functionalized with LF could be utilized to improve the material performance towards the biological environment for biomedical applications.

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

NASA Technical Reports Server (NTRS)

Eick, M. J.; Grossl, P. R.; Golden, D. C.; Sparks, D. L.; Ming, D. W.

1996-01-01

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

Observing a model ion channel gating action in model cell membranes in real time in situ: membrane potential change induced alamethicin orientation change.

PubMed

Ye, Shuji; Li, Hongchun; Wei, Feng; Jasensky, Joshua; Boughton, Andrew P; Yang, Pei; Chen, Zhan

2012-04-11

Ion channels play crucial roles in transport and regulatory functions of living cells. Understanding the gating mechanisms of these channels is important to understanding and treating diseases that have been linked to ion channels. One potential model peptide for studying the mechanism of ion channel gating is alamethicin, which adopts a split α/3(10)-helix structure and responds to changes in electric potential. In this study, sum frequency generation vibrational spectroscopy (SFG-VS), supplemented by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), has been applied to characterize interactions between alamethicin (a model for larger channel proteins) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid bilayers in the presence of an electric potential across the membrane. The membrane potential difference was controlled by changing the pH of the solution in contact with the bilayer and was measured using fluorescence spectroscopy. The orientation angle of alamethicin in POPC lipid bilayers was then determined at different pH values using polarized SFG amide I spectra. Assuming that all molecules adopt the same orientation (a δ distribution), at pH = 6.7 the α-helix at the N-terminus and the 3(10)-helix at the C-terminus tilt at about 72° (θ(1)) and 50° (θ(2)) versus the surface normal, respectively. When pH increases to 11.9, θ(1) and θ(2) decrease to 56.5° and 45°, respectively. The δ distribution assumption was verified using a combination of SFG and ATR-FTIR measurements, which showed a quite narrow distribution in the angle of θ(1) for both pH conditions. This indicates that all alamethicin molecules at the surface adopt a nearly identical orientation in POPC lipid bilayers. The localized pH change in proximity to the bilayer modulates the membrane potential and thus induces a decrease in both the tilt and the bend angles of the two helices in alamethicin. This is the first reported application of SFG to the study of model ion channel gating mechanisms in model cell membranes. © 2012 American Chemical Society

Biosorption of metal ions from aqueous solutions

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

Chen, Jiaping; Yiacoumi, Sotira

1997-01-01

Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

Nonlinear and Dissipation Characteristics of Ocean Surface Waves in Estuarine Environments

DTIC Science & Technology

2014-09-30

transformation and evolution . In addition these modules would allow for feedback between the surface wave and the energy dissipating feature. OBJECTIVES...dissipation on wave processes. 3) Develop and test low-dimension, reduced representations of estuarine effects for inclusion into operational wave models...Sheremet (PI), Miao Tian and Cihan Sahin (Ph.D. students) who are working on modeling nonlinear wave evolution in dissipative environments (mud), and

Albumin adsorption on CoCrMo alloy surfaces

NASA Astrophysics Data System (ADS)

Yan, Yu; Yang, Hongjuan; Su, Yanjing; Qiao, Lijie

2015-12-01

Proteins can adsorb on the surface of artificial joints immediately after being implanted. Although research studying protein adsorption on medical material surfaces has been carried out, the mechanism of the proteins’ adsorption which affects the corrosion behaviour of such materials still lacks in situ observation at the micro level. The adsorption of bovine serum albumin (BSA) on CoCrMo alloy surfaces was studied in situ by AFM and SKPFM as a function of pH and the charge of CoCrMo alloy surfaces. Results showed that when the specimens were uncharged, hydrophobic interaction could govern the process of the adsorption rather than electrostatic interaction, and BSA molecules tended to adsorb on the surfaces forming a monolayer in the side-on model. Results also showed that adsorbed BSA molecules could promote the corrosion process for CoCrMo alloys. When the surface was positively charged, the electrostatic interaction played a leading role in the adsorption process. The maximum adsorption occurred at the isoelectric point (pH 4.7) of BSA.

Modeling the movement of a pH perturbation and its impact on adsorbed zinc and phosphate in a wastewater‐contaminated aquifer

USGS Publications Warehouse

Kent, D.B.; Wilkie, J.A.; Davis, J.A.

2007-01-01

Chemical conditions were perturbed in an aquifer with an ambient pH of 5.9 and wastewater‐derived adsorbed zinc (Zn) and phosphate (P) contamination by injecting a pulse of amended groundwater. The injected groundwater had low concentrations of dissolved Zn and P, a pH value of 4.5 resulting from equilibration with carbon dioxide gas, and added potassium bromide (KBr). Downgradient of the injection, breakthrough of nonreactive Br and total dissolved carbonate concentrations in excess of ambient values (excess TCO2) were accompanied by a decrease in pH values and over twentyfold increases in dissolved Zn concentrations above preinjection values. Peak concentrations of Br and excess TCO2 were followed by slow increases in pH values accompanied by significant increases in dissolved P above preinjection concentrations. The injected tracers mobilized a significant mass of wastewater‐derived Zn. Reactive transport simulations incorporating surface complexation models for adsorption of Zn, P, hydrogen ions, and major cations onto the aquifer sediments, calibrated using laboratory experimental data, captured most of the important trends observed during the experiment. These include increases in Zn concentrations in response to the pH perturbation, perturbations in major cation concentrations, attenuation of the pH perturbation with transport distance, and increases in alkalinity with transport distance. Observed desorption of P in response to chemical perturbations was not predicted, possibly because of a disparity between the range of chemical conditions in the calibration data set and those encountered during the field experiment. Zinc and P desorbed rapidly in response to changing chemical conditions despite decades of contact with the sediments. Surface complexation models with relatively few parameters in the form of logK values and site concentrations show considerable promise for describing the influence of variable chemistry on the transport of adsorbing contaminants.

Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

USGS Publications Warehouse

Heard, I.; Senftle, F.E.

1984-01-01

Solutions of 30% H2O2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H2O2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions (pH < 1.5). After acid demineralization, samples of the same anthracite underwent a significant enhancement of oxidation in both acid and alkaline solutions (pH = 0.4-11.5). As all the iron had been removed from the surface and the reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H2O2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

Modeling the adsorption of hydrogen, sodium, chloride and phthalate on goethite using a strict charge-neutral ion-exchange theory.

PubMed

Schulthess, Cristian P; Ndu, Udonna

2017-01-01

Simultaneous adsorption modeling of four ions was predicted with a strict net charge-neutral ion-exchange theory and its corresponding equilibrium and mass balance equations. An important key to the success of this approach was the proper collection of all the data, particularly the proton adsorption data, and the inclusion of variable concentrations of conjugate ions from the experimental pH adjustments. Using IExFit software, the ion-exchange model used here predicted the competitive retention of several ions on goethite by assuming that the co-adsorption or desorption of all ions occurred in the correct stoichiometries needed to maintain electroneutrality. This approach also revealed that the retention strength of Cl- ions on goethite increases in the presence of phthalate ions. That is, an anion-anion enhancement effect was observed. The retention of Cl- ions was much weaker than phthalate ions, and this also resulted in a higher sensitivity of the Cl- ions toward minor variations in the surface reactivity. The proposed model uses four goethite surface sites. The drop in retention of phthalate ions at low pH was fully described here as resulting from competitive Cl- reactions, which were introduced in increasing concentrations into the matrix as the conjugate base to the acid added to lower the pH.

Variability of pCO2 in surface waters and development of prediction model.

PubMed

Chung, Sewoong; Park, Hyungseok; Yoo, Jisu

2018-05-01

Inland waters are substantial sources of atmospheric carbon, but relevant data are rare in Asian monsoon regions including Korea. Emissions of CO 2 to the atmosphere depend largely on the partial pressure of CO 2 (pCO 2 ) in water; however, measured pCO 2 data are scarce and calculated pCO 2 can show large uncertainty. This study had three objectives: 1) to examine the spatial variability of pCO 2 in diverse surface water systems in Korea; 2) to compare pCO 2 calculated using pH-total alkalinity (Alk) and pH-dissolved inorganic carbon (DIC) with pCO 2 measured by an in situ submersible nondispersive infrared detector; and 3) to characterize the major environmental variables determining the variation of pCO 2 based on physical, chemical, and biological data collected concomitantly. Of 30 samples, 80% were found supersaturated in CO 2 with respect to the overlying atmosphere. Calculated pCO 2 using pH-Alk and pH-DIC showed weak prediction capability and large variations with respect to measured pCO 2 . Error analysis indicated that calculated pCO 2 is highly sensitive to the accuracy of pH measurements, particularly at low pH. Stepwise multiple linear regression (MLR) and random forest (RF) techniques were implemented to develop the most parsimonious model based on 10 potential predictor variables (pH, Alk, DIC, Uw, Cond, Turb, COD, DOC, TOC, Chla) by optimizing model performance. The RF model showed better performance than the MLR model, and the most parsimonious RF model (pH, Turb, Uw, Chla) improved pCO 2 prediction capability considerably compared with the simple calculation approach, reducing the RMSE from 527-544 to 105μatm at the study sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Sustained Release of Naproxen in a New Kind Delivery System of Carbon Nanotubes Hydrogel

PubMed Central

Peng, Xiahui; Zhuang, Qiang; Peng, Dongming; Dong, Qiuli; Tan, Lini; Jiao, Feipeng; Liu, Linqi; Liu, jingyu; Zhao, Chenxi; Wang, Xiaomei

2013-01-01

In this paper, carbon nanotubes (CNTs) were added into chitosan (CS) hydrogels in the form of chitosan modified CNTs (CS-CNTs) composites to prepare carbon nanotubes hydrogels (CNTs-GEL). The products, named CS-MWCNTs, were characterized by scanning electron microscope (SEM) and Fourier transform infrared (FTIR) spectroscopy. Swelling properties and effect of pH on controlled release performance of the two kinds of hydrogels, CNTs- GEL and pure chitosan hydrogels without CNTs (GEL), were investigated respectively. The results showed that CNTs-GEL possess better controlled release performance than GEL. The releasing equilibrium time of CNTs-GEL was longer than that of GEL in both pH = w7.4 and pH=1.2 conditions, although the release ratios of the model drug are similar in the same pH buffer solutions. It is found that release kinetics is better fitted Ritger-Peppas empirical model indicating a fick-diffusion process in pH = 1.2, while in pH = 7.4 it was non-fick diffusion involving surface diffusion and corrosion diffusion processes. PMID:24523738

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

DOE PAGES

Chen, Yongqiang; Xie, Quan; Sari, Ahmad; ...

2017-11-21

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

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

Chen, Yongqiang; Xie, Quan; Sari, Ahmad

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

High-Resolution Microbial Community Succession of Microbially Induced Concrete Corrosion in Working Sanitary Manholes

PubMed Central

Ling, Alison L.; Robertson, Charles E.; Harris, J. Kirk; Frank, Daniel N.; Kotter, Cassandra V.; Stevens, Mark J.; Pace, Norman R.; Hernandez, Mark T.

2015-01-01

Microbially-induced concrete corrosion in headspaces threatens wastewater infrastructure worldwide. Models for predicting corrosion rates in sewer pipe networks rely largely on information from culture-based investigations. In this study, the succession of microbes associated with corroding concrete was characterized over a one-year monitoring campaign using rRNA sequence-based phylogenetic methods. New concrete specimens were exposed in two highly corrosive manholes (high concentrations of hydrogen sulfide and carbon dioxide gas) on the Colorado Front Range for up to a year. Community succession on corroding surfaces was assessed using Illumina MiSeq sequencing of 16S bacterial rRNA amplicons and Sanger sequencing of 16S universal rRNA clones. Microbial communities associated with corrosion fronts presented distinct succession patterns which converged to markedly low α-diversity levels (< 10 taxa) in conjunction with decreasing pH. The microbial community succession pattern observed in this study agreed with culture-based models that implicate acidophilic sulfur-oxidizer Acidithiobacillus spp. in advanced communities, with two notable exceptions. Early communities exposed to alkaline surface pH presented relatively high α-diversity, including heterotrophic, nitrogen-fixing, and sulfur-oxidizing genera, and one community exposed to neutral surface pH presented a diverse transition community comprised of less than 20% sulfur-oxidizers. PMID:25748024

High-resolution microbial community succession of microbially induced concrete corrosion in working sanitary manholes.

PubMed

Ling, Alison L; Robertson, Charles E; Harris, J Kirk; Frank, Daniel N; Kotter, Cassandra V; Stevens, Mark J; Pace, Norman R; Hernandez, Mark T

2015-01-01

Microbially-induced concrete corrosion in headspaces threatens wastewater infrastructure worldwide. Models for predicting corrosion rates in sewer pipe networks rely largely on information from culture-based investigations. In this study, the succession of microbes associated with corroding concrete was characterized over a one-year monitoring campaign using rRNA sequence-based phylogenetic methods. New concrete specimens were exposed in two highly corrosive manholes (high concentrations of hydrogen sulfide and carbon dioxide gas) on the Colorado Front Range for up to a year. Community succession on corroding surfaces was assessed using Illumina MiSeq sequencing of 16S bacterial rRNA amplicons and Sanger sequencing of 16S universal rRNA clones. Microbial communities associated with corrosion fronts presented distinct succession patterns which converged to markedly low α-diversity levels (< 10 taxa) in conjunction with decreasing pH. The microbial community succession pattern observed in this study agreed with culture-based models that implicate acidophilic sulfur-oxidizer Acidithiobacillus spp. in advanced communities, with two notable exceptions. Early communities exposed to alkaline surface pH presented relatively high α-diversity, including heterotrophic, nitrogen-fixing, and sulfur-oxidizing genera, and one community exposed to neutral surface pH presented a diverse transition community comprised of less than 20% sulfur-oxidizers.

New insights into the pH-dependent interfacial adsorption of dog gastric lipase using the monolayer technique.

PubMed

Bénarouche, Anaïs; Point, Vanessa; Parsiegla, Goetz; Carrière, Frédéric; Cavalier, Jean-François

2013-11-01

The access to kinetic parameters of lipolytic enzyme adsorption onto lipids is essential for a better understanding of interfacial enzymology and lipase-lipid interactions. The interfacial adsorption of dog gastric lipase (DGL) was monitored as a function of pH and surface pressure (Π), independently from the catalytic activity, using non-hydrolysable 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) monomolecular films. The acid-stable DGL, which initiates fat digestion in the stomach, was then selected because its adsorption kinetics onto hydrophobic solid surfaces were already studied. This gastric lipase was therefore used as a model enzyme to validate both experimental and theoretical approaches. Results show that the adsorption process of DGL at the lipid/water interface depends on a pH-dependent adsorption equilibrium coefficient which is optimum at pH 5.0 (K(Ads) = 1.7 ± 0.05 × 10(8)M(-1)). KAds values further allowed an indirect estimation of the molar fraction (ΦE*(%), mol%) as well as the molecular area (AE*) of DGL adsorbed onto DLPC monolayer. Based on these data, a model for DGL adsorption onto DLPC monolayer at pH 5.0 is proposed for a surface pressure range of 15-25 mNm(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

Combined Homogeneous Surface Diffusion Model - Design of experiments approach to optimize dye adsorption considering both equilibrium and kinetic aspects.

PubMed

Muthukkumaran, A; Aravamudan, K

2017-12-15

Adsorption, a popular technique for removing azo dyes from aqueous streams, is influenced by several factors such as pH, initial dye concentration, temperature and adsorbent dosage. Any strategy that seeks to identify optimal conditions involving these factors, should take into account both kinetic and equilibrium aspects since they influence rate and extent of removal by adsorption. Hence rigorous kinetics and accurate equilibrium models are required. In this work, the experimental investigations pertaining to adsorption of acid orange 10 dye (AO10) on activated carbon were carried out using Central Composite Design (CCD) strategy. The significant factors that affected adsorption were identified to be solution temperature, solution pH, adsorbent dosage and initial solution concentration. Thermodynamic analysis showed the endothermic nature of the dye adsorption process. The kinetics of adsorption has been rigorously modeled using the Homogeneous Surface Diffusion Model (HSDM) after incorporating the non-linear Freundlich adsorption isotherm. Optimization was performed for kinetic parameters (color removal time and surface diffusion coefficient) as well as the equilibrium affected response viz. percentage removal. Finally, the optimum conditions predicted were experimentally validated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Forsterite surface composition in aqueous solutions: a combined potentiometric, electrokinetic, and spectroscopic approach

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2000-10-01

Surfaces of natural and synthetic forsterite (Fo 91 and Fo 100) in aqueous solutions at 25°C were investigated using surface titrations in batch and limited residence time reactors, column filtration experiments, electrokinetic measurements (streaming potential and electrophoresis techniques), Diffuse Reflectance Infrared Spectroscopy (DRIFT), and X-ray Photoelectron Spectroscopy (XPS). At pH < 9, a Mg-depleted, Si-rich layer (<20 Å thick) is formed on the forsterite surface due to a Mg 2+ ↔ H + exchange reaction. Electrokinetic measurements yield a pH IEP value of 4.5 corresponding to the dominance of SiO 2 in the surface layer at pH < 9. In contrast, surface titrations of fresh powders give an apparent pH PZC of about 10 with the development of a large positive charge (up to 10 -4 mol/m 2 or 10 C/m 2) in the acid pH region. This may be explained by penetration of H + into the first unit cells of forsterite surface. The surface charge of acid-reacted forsterite is one or two orders of magnitude lower than that of unreacted forsterite with an apparent pH PZC at around 6.5 and a pH IEP value of 2.1 which is close to that for amorphous silica and reflects the formation of a silica-rich layer on the surface. XPS analyses indicate the penetration of hydrogen into the surface and the polymerization of silica tetrahedra in this leached layer. At pH > 10, a Si-deficient, Mg-rich surface layer is formed as shown by XPS analyses and the preferential Si release from the surface during column filtration experiments.

Optimization and modeling of laccase production by Trametes versicolor in a bioreactor using statistical experimental design.

PubMed

Tavares, A P M; Coelho, M A Z; Agapito, M S M; Coutinho, J A P; Xavier, A M R B

2006-09-01

Experimental design and response surface methodologies were applied to optimize laccase production by Trametes versicolor in a bioreactor. The effects of three factors, initial glucose concentration (0 and 9 g/L), agitation (100 and 180 rpm), and pH (3.0 and 5.0), were evaluated to identify the significant effects and its interactions in the laccase production. The pH of the medium was found to be the most important factor, followed by initial glucose concentration and the interaction of both factors. Agitation did not seem to play an important role in laccase production, nor did the interaction agitation x medium pH and agitation x initial glucose concentration. Response surface analysis showed that an initial glucose concentration of 11 g/L and pH controlled at 5.2 were the optimal conditions for laccase production by T. versicolor. Under these conditions, the predicted value for laccase activity was >10,000 U/L, which is in good agreement with the laccase activity obtained experimentally (11,403 U/L). In addition, a mathematical model for the bioprocess was developed. It is shown that it provides a good description of the experimental profile observed, and that it is capable of predicting biomass growth based on secondary process variables.

Molecular-orbital models for the catalytic activity and selectivity of coordinatively unsaturated platinum surfaces and complexes

NASA Astrophysics Data System (ADS)

Balazs, A. C.; Johnson, K. H.

1982-01-01

Electronic structures have been calculated for 5-, 6-, and 10-atom Pt clusters, as well as for a Pt(PH 3) 4 coordination complex, using the self-consistent-field X-alpha scattered-wave (SCF-Xα-SW) molecular-orbital technique. The 10-atom cluster models the local geometry of a flat, unreconstructed Pt(100) surface, while the 5- and 6-atom clusters show features of a stepped Pt surface. Pt(PH 3) 4 resembles the chemically similar homogeneous catalyst Pt(PPh 3) 4. Common to all these coordinatively unsaturated complexes are orbitals lying near or coinciding with the highest occupied molecular orbital ("Fermi level") which show pronounced d lobes pointing directly into the vacuum. Under the hypothesis that these molecular orbitals are mainly responsible for the chemical activities of the above species, one can account for the relative similarities and differences in catalytic activity and selectivity displayed by unreconstructed Pt(100) surfaces, stepped Pt surfaces or particles, and isolated Pt(PPh 3) 4 coordination complexes. The relevance of these findings to catalyst-support interactions is also discussed. Finally, relativistic corrections to the electronic structures are calculated and their implications on catalytic properties discussed.

Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

NASA Astrophysics Data System (ADS)

Shibata, T.; Nishiyama, H.

2014-03-01

Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

Response surface methodological approach for the decolorization of simulated dye effluent using Aspergillus fumigatus fresenius.

PubMed

Sharma, Praveen; Singh, Lakhvinder; Dilbaghi, Neeraj

2009-01-30

The aim of our research was to study, effect of temperature, pH and initial dye concentration on decolorization of diazo dye Acid Red 151 (AR 151) from simulated dye solution using a fungal isolate Aspergillus fumigatus fresenius have been investigated. The central composite design matrix and response surface methodology (RSM) have been applied to design the experiments to evaluate the interactive effects of three most important operating variables: temperature (25-35 degrees C), pH (4.0-7.0), and initial dye concentration (100-200 mg/L) on the biodegradation of AR 151. The total 20 experiments were conducted in the present study towards the construction of a quadratic model. Very high regression coefficient between the variables and the response (R(2)=0.9934) indicated excellent evaluation of experimental data by second-order polynomial regression model. The RSM indicated that initial dye concentration of 150 mg/L, pH 5.5 and a temperature of 30 degrees C were optimal for maximum % decolorization of AR 151 in simulated dye solution, and 84.8% decolorization of AR 151 was observed at optimum growth conditions.

Analysis of dental erosion induced by different beverages and validity of equipment for identifying early dental erosion, in vitro study.

PubMed

Jameel, Rafey Ahmad; Khan, Shah Salman; Abdul Rahim, Zubaidah Hj; Bakri, Marina Mohd; Siddiqui, Saima

2016-07-01

To understand early dental erosion induced by different beverages and the equipment for its detection. The study was conducted at the University Malaya Medical Centre, Kuala Lumpur, Malaysia, from June to September 2014, and comprised single-rooted, unpolished teeth divided into six groups. Electron micrographs and other baseline readings for further analyses were taken before and after the exposure to different beverages. The teeth were exposed to the beverages using a modified Nordini's artificial mouth model. The positioning of the teeth on the motorised stage of the equipment was standardised. Of the several beverages used, CocaCola had the lowest pH value of 2.53, while tap water had the highest pH of 5.4. Deionised distilled water, which was used as a reference, had a pH near to neutral /alkaline of 7.3. The fluoride content ranged between 9.38ppm in tea and 0.005ppm in orange juice. Teeth exposed to beverages with low pH and considerably high fluoride underwent slight remineralisation (roughness increase 8% from tea), while beverages with no fluoride content and low pH roughened the enamel surface (Coca Cola roughened upto 37%). Quantitative analyses of tooth erosion, micro-hardness, surface-roughness, and surface-height showed that all beverages exhibited positive erosive effect on the tooth enamel surface (p<0.005). CocaCola was found to be the most erosive agent among both hot and cold beverages (37%), while coffee was more erosive among the hot beverages (29%).

Decreasing DOC trends in soil solution along the hillslopes at two IM sites in southern Sweden--geochemical modeling of organic matter solubility during acidification recovery.

PubMed

Löfgren, Stefan; Gustafsson, Jon Petter; Bringmark, Lage

2010-12-01

Numerous studies report increased concentrations of dissolved organic carbon (DOC) during the last two decades in boreal lakes and streams in Europe and North America. Recently, a hypothesis was presented on how various spatial and temporal factors affect the DOC dynamics. It was concluded that declining sulphur deposition and thereby increased DOC solubility, is the most important driver for the long-term DOC concentration trends in surface waters. If this recovery hypothesis is correct, the DOC levels should increase both in the soil solution as well as in the surrounding surface waters as soil pH rises and the ionic strength declines due to the reduced input of SO(4)(2-) ions. In this project a geochemical model was set up to calculate the net humic charge and DOC solubility trends in soils during the period 1996-2007 at two integrated monitoring sites in southern Sweden, showing clear signs of acidification recovery. The Stockholm Humic Model was used to investigate whether the observed DOC solubility is related to the humic charge and to examine how pH and ionic strength influence it. Soil water data from recharge and discharge areas, covering both podzols and riparian soils, were used. The model exercise showed that the increased net charge following the pH increase was in many cases counteracted by a decreased ionic strength, which acted to decrease the net charge and hence the DOC solubility. Thus, the recovery from acidification does not necessarily have to generate increasing DOC trends in soil solution. Depending on changes in pH, ionic strength and soil Al pools, the trends might be positive, negative or indifferent. Due to the high hydraulic connectivity with the streams, the explanations to the DOC trends in surface waters should be searched for in discharge areas and peat lands. Copyright © 2010 Elsevier B.V. All rights reserved.

Photocatalytic degradation of pentachlorophenol by visible light Ν-F-TiO₂ in the presence of oxalate ions: optimization, modeling, and scavenging studies.

PubMed

Antonopoulou, M; Konstantinou, I

2015-06-01

The efficiency of heterogeneous photocatalysis using N-F-TiO2 as photocatalyst to degrade a priority pollutant, pentachlorophenol (PCP), in the presence of oxalates (OA) was investigated in detail. Response surface methodology was used to optimize the effect of three variables (catalyst concentration, OA/PCP ratio, and pH) on the photocatalytic degradation of pentachlorophenol. A quadratic model was established as a functional relationship between three independent variables and the degradation efficiency of PCP. The results of model fitting and statistical analysis demonstrated that the pH played a key role in the degradation of PCP. Within the studied experimental ranges, the optimum conditions for maximum PCP degradation efficiency (97.5 %) were: catalyst concentration 600 mg L(-1), OA/PCP ratio 2, and pH 10. The contribution of HO(·), O2 (·-), and e(-) produced during the photocatalytic treatment was investigated with the addition of scavengers. The photocatalytic degradation was essentially proceeded through an oxidative mechanism at both acid and alkaline pH values by HO(.) and O2 (·-) radicals attack. It was found that O2 (·-) were the major reactive species involved in PCP degradation in pH 4 and HO(·) in pH 10.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Ethanol mediated As(III) adsorption onto Zn-loaded pinecone biochar: Experimental investigation, modeling, and optimization using hybrid artificial neural network-genetic algorithm approach.

PubMed

Zafar, Mohd; Van Vinh, N; Behera, Shishir Kumar; Park, Hung-Suck

2017-04-01

Organic matters (OMs) and their oxidization products often influence the fate and transport of heavy metals in the subsurface aqueous systems through interaction with the mineral surfaces. This study investigates the ethanol (EtOH)-mediated As(III) adsorption onto Zn-loaded pinecone (PC) biochar through batch experiments conducted under Box-Behnken design. The effect of EtOH on As(III) adsorption mechanism was quantitatively elucidated by fitting the experimental data using artificial neural network and quadratic modeling approaches. The quadratic model could describe the limiting nature of EtOH and pH on As(III) adsorption, whereas neural network revealed the stronger influence of EtOH (64.5%) followed by pH (20.75%) and As(III) concentration (14.75%) on the adsorption phenomena. Besides, the interaction among process variables indicated that EtOH enhances As(III) adsorption over a pH range of 2 to 7, possibly due to facilitation of ligand-metal(Zn) binding complexation mechanism. Eventually, hybrid response surface model-genetic algorithm (RSM-GA) approach predicted a better optimal solution than RSM, i.e., the adsorptive removal of As(III) (10.47μg/g) is facilitated at 30.22mg C/L of EtOH with initial As(III) concentration of 196.77μg/L at pH5.8. The implication of this investigation might help in understanding the application of biochar for removal of various As(III) species in the presence of OM. Copyright © 2016. Published by Elsevier B.V.

Dynamic measurement of the optical properties of bovine enamel demineralization models using four-dimensional optical coherence tomography

NASA Astrophysics Data System (ADS)

Aden, Abdirahman; Anthony, Arthi; Brigi, Carel; Merchant, Muhammad Sabih; Siraj, Huda; Tomlins, Peter H.

2017-07-01

Dental enamel mineral loss is multifactorial and is consequently explored using a variety of in vitro models. Important factors include the presence of acidic pH and its specific ionic composition, which can both influence lesion characteristics. Optical coherence tomography (OCT) has been demonstrated as a promising tool for studying dental enamel demineralization. However, OCT-based characterization and comparison of demineralization model dynamics are challenging without a consistent experimental environment. Therefore, an automated four-dimensional OCT system was integrated with a multispecimen flow cell to measure and compare the optical properties of subsurface enamel demineralization in different models. This configuration was entirely automated, thus mitigating any need to disturb the specimens and ensuring spatial registration of OCT image volumes at multiple time points. Twelve bovine enamel disks were divided equally among three model groups. The model demineralization solutions were citric acid (pH 3.8), acetic acid (pH 4.0), and acetic acid with added calcium and phosphate (pH 4.4). Bovine specimens were exposed to the solution continuously for 48 h. Three-dimensional OCT data were obtained automatically from each specimen at a minimum of 1-h intervals from the same location within each specimen. Lesion dynamics were measured in terms of the depth below the surface to which the lesion extended and the attenuation coefficient. The net loss of surface enamel was also measured for comparison. Similarities between the dynamics of each model were observed, although there were also distinct characteristic differences. Notably, the attenuation coefficients showed a systematic offset and temporal shift with respect to the different models. Furthermore, the lesion depth curves displayed a discontinuous increase several hours after the initial acid challenge. This work demonstrated the capability of OCT to distinguish between different enamel demineralization models by making dynamic quantitative measurements of lesion properties. This has important implications for future applications in clinical dentistry.

Process model for ammonia volatilization from anaerobic swine lagoons incorporating varying wind speeds and biogas bubbling

USDA-ARS?s Scientific Manuscript database

Ammonia volatilization from treatment lagoons varies widely with the total ammonia concentration, pH, temperature, suspended solids, atmospheric ammonia concentration above the water surface, and wind speed. Ammonia emissions were estimated with a process-based mechanistic model integrating ammonia ...

Molecular mechanism of plasma sterilization in solution with the reduced pH method: importance of permeation of HOO radicals into the cell membrane

NASA Astrophysics Data System (ADS)

Takai, Eisuke; Ikawa, Satoshi; Kitano, Katsuhisa; Kuwabara, Junpei; Shiraki, Kentaro

2013-07-01

Sterilization of certain infected areas of the human body surface is necessary for dental and surgical therapies. Because the blood is filled with body fluid, sterilization in solution is essential. In vitro solution sterilization has been successively carried out using a combination of low-temperature atmospheric-pressure plasma and the reduced pH method, where the solution is sufficiently acidic. Here, we show the molecular mechanism of such plasma sterilization in solution based on microbiology. Three kinds of bacteria were inactivated by plasma treatment under various pH conditions. The theoretical and experimental models revealed that the sterilization was characterized by the concentration of hydroperoxy radicals (HOO·), which were dependent on the pH value. Bacterial inactivation rates were proportional to the HOO· concentrations calculated by the theoretical model. To evaluate the penetration of radicals into the cell membrane, a bacterial model using dye-included micelles was used. Decolouration rates of the model were also in proportion with the calculated HOO· concentrations. These results indicate that the key species for plasma sterilization were hydroperoxy radicals. More importantly, the high permeation of hydroperoxy radicals into the cell membrane plays a key role for efficient bactericidal inactivation using the reduced pH method.

ANTICARIOGENIC POTENCIAL OF ACIDULATE SOLUTIONS WITH LOW FLUORIDE CONCENTRATION

PubMed Central

Delbem, Alberto Carlos Botazzo; Tiano, Gilberto Carlos; Alves, Karina Mirela Ribeiro Pinto; Cunha, Robson Frederico

2006-01-01

Objectives: The aim of this study was to verify the anticariogenic effect of acidulate solutions with low NaF concentration, using pH-cycling model and bovine enamel. Material and methods: Enamel blocks were submitted to the surface microhardness (SMH) test and randomly divided in 12 experimental and one placebo groups. The blocks were submitted to pH cycling for 7 days, with daily applications once/day of 0.05% NaF and 0.1% NaF and twice/day of 0.02% NaF solutions. Four different pH: 4.0, 5.0, 6.0 and 7.0 were used. Next, SMH test was again used to determine the surface microhardness percentage change (%SMH). Data obtained for %SMH were homogeneous and passed through variance analyses and Tukey's test (5%) as far as fluoride concentrations and pH. Results: The results showed that pH influenced %SMH in 0.02% NaF and 0.05% NaF solutions with pH 4.0, which had less mineral loss compared to pH 7.0 (p<0.05). The 0.02% NaF - pH 4.0, and 0.05% NaF – pH 7.0 groups showed similar results (p>0.05). A dose-response relationship was observed among the tested solutions, with better anticariogenic effect for the 0.1% NaF solution. Conclusion: The results suggest that the addition of citric acid to acidulate mouth rinses reduce mineral loss. PMID:19089268

Interactions between cells and ionized dendritic biomaterials: Flow cytometry and fluorescence spectroscopic studies

NASA Astrophysics Data System (ADS)

Kannan, R. M.; Kolhe, Parag; Khandare, Jayant; Kannan, Sujatha; Lieh-Lai, Mary

2004-03-01

Dendrimers and hyperbranched polymers are a new class of macromolecules characterized by large density of "tunable" peripheral functional groups. Therefore dendrimers can serve as a model macromolecular system to study the influence of molecular geometry and charge density on transport across biological barriers, especially cellular interfaces. The effect of size, end-functionality, surface charge (pH), and the nature of the cell surface are expected to play an important role in transport, and are investigated using flow cytometry, fluorescene microscopy and UV/Vis spectroscopy. Our results suggest that at physiological pH, cationic polyamidoamine (PAMAM) dendrimers can enter the A549 cancer lung epithelial cells within 5 minutes, perhaps due to the favorable interaction between anionic surface receptors of cells and cationic PAMAM dendrimer, through adsorptive endocytosis. On the other hand, hyperbranched polyol, which is a neutral polymer at physiological pH, enters cells at a much slower rate. The entry of hyperbranched polyol may be because of fluid-phase pinocytosis. Our results also indicate that the dendritic polymers enter the cell surface much more rapidly than linear polymers, and some small drugs, suggesting that the high density of functional groups plays a key role in the interaction with the cell surface, and the subsequent transport inside.

[Enzymatic conversion of tetradecanol in heterogenous phase by yeast-alcohol dehydrogenase].

PubMed

Rothe, U; Schöpp, W; Aurich, H

1976-01-01

Alcohol dehydrogenase from yeast converts long-chain primary alcohols not only in the dissolved state, but also at the surface of undissolved particles. Tetradecanol beads with a defined surface can be produced and employed as model substrate. The reaction rate was determined by the proton release accomplished in the reaction. The initial reaction rate depends on the enzyme concentration. The relation is nonlinear (vi = k-[e]0,4); the numerical value of the exponent (n = 0.4) argues in favour of a reaction occurring at the interface. The Lineweaver-Burk plots become linear if the substrate concentrations are based on the molar surface concentrations of the particles. The pH optimum for the reaction at the surface is displaced by 0.25 pH units towards the alkaline region (compared with ethanol as substrate). The activation energy of the reaction with tetradecanol beads as substrate is 30% lower than that for the ethanol oxydation.

Nickel adsorption on chalk and calcite

NASA Astrophysics Data System (ADS)

Belova, D. A.; Lakshtanov, L. Z.; Carneiro, J. F.; Stipp, S. L. S.

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface.

Synthesis and surface properties of submicron barium sulfate particles

NASA Astrophysics Data System (ADS)

Zhang, Ming; Zhang, Bao; Li, Xinhai; Yin, Zhoulan; Guo, Xueyi

2011-10-01

Barium sulfate particles were synthesized in the presence of EDTA at room temperature. X-ray diffractometry (XRD), Fourier transform infrared resonance (FTIR) and scanning electron microscopy (SEM) were used to characterize the structure and morphology of BaSO 4 particles. The effect of the preparation parameters on the particle size distribution and morphology was investigated. The conditional formation constants of Ba-EDTA at different pH values were calculated. The results show that the size and morphology of BaSO 4 particles can be effectively controlled by adding EDTA in the precipitation process. Among all the operation conditions, the pH value has significant effect on the particle size. The obtained barium sulfate particles are spherical and well dispersed at pH = 9-10. Zeta potentials of BaSO 4 were measured at different pH. The isoelectric point (IEP) of barium sulfate colloid appears at pH 6.92. The model of the solid-solution interface at a particle of BaSO 4 was presented. The FTIR result indicates that the surface of the prepared BaSO 4 absorbs the functional groups of EDTA, which lower the IEP of the barium sulfate particles.

Effect of organic matter on cyanide removal by illuminated titanium dioxide or zinc oxide nanoparticles

PubMed Central

2013-01-01

Effect of different type of organic compounds (humic acid, oxalate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, phenol) on the photocatalytic removal of cyanide with TiO2 or ZnO was studied in this work with variation of the solution pH, contact time, initial cyanide concentration and type of organic compounds. Photocatalytic oxidation efficiency of cyanide with TiO2 was greatly affected by the solution pH. It increased as the solution pH decreased. Also maximum removal of cyanide by ZnO was observed near at neutral pH because of the reduced photocatalytic activity of ZnO at exceedingly low and high pH values originated from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH)2. Removal efficiency of cyanide greatly decreased in the presence of humic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid compared to that without presence of organic compound because of the competitive oxidation as well as surface blocking by relatively large organic compounds. The oxidation pattern of cyanide was better described by first-order kinetic model. Finally photocatalytic reaction with TiO2 or ZnO can be effectively applied to treat synthetic wastewater contaminated with cyanide. PMID:24499704

Adsorption of transgenic insecticidal Cry1Ab protein to SiO2. 2. Patch-controlled electrostatic attraction.

PubMed

Madliger, Michael; Sander, Michael; Schwarzenbach, René P

2010-12-01

Adsorption governs the fate of Cry proteins from genetically modified Bt crops in soils. The effect of ionic strength (I) on the adsorption of Cry1Ab (isoelectric point IEP(Cry1Ab) ≈ 6) to negatively charged quartz (SiO(2)) and positively charged poly-L-lysine (PLL) was investigated at pH 5 to 8, using quartz crystal microbalance with dissipation monitoring and optical waveguide lightmode spectroscopy. Cry1Ab adsorbed via positively and negatively charged surface patches to SiO(2) and PLL, respectively. This patch controlled electrostatic attraction (PCEA) explains the observed increase in Cry1Ab adsorption to sorbents that carried the same net charge as the protein (SiO(2) at pH > IEP(Cry1Ab) and PLL at pH < IEP(Cry1Ab)) with decreasing I. In contrast, the adsorption of two reference proteins, BSA and HEWL, with different adsorption mechanism, were little affected by similar changes of I. Consistent with PCEA, Cry1Ab desorption from SiO(2) at pH > IEP(Cry1Ab) increased with increasing I and pH. Weak Cry1Ab-SiO(2) PCEA above pH 7 resulted in reversible, concentration dependent adsorption. Solution depletion experiments showed that PCEA also governed Cry1Ab adsorption to SiO(2) particles at environmentally relevant concentrations (a few ng mL(-1)). These results imply that models describing Cry1Ab adsorption to charged surfaces in soils need to account for the nonuniform surface charge distribution of the protein.

Colloidal stability of CeO2 nanoparticles coated with either natural organic matter or organic polymers under various hydrochemical conditions

NASA Astrophysics Data System (ADS)

Dippon, Urs; Pabst, Silke; Klitzke, Sondra

2016-04-01

The worldwide marked for engineered nanoparticles (ENPs) is growing and concerns on the environmental fate- and toxicity of ENPs are rising. Understanding the transport of ENPs within and between environmental compartments such as surface water and groundwater is crucial for exposition modeling, risk assessment and ultimately the protection of drinking water resources. The transport of ENPs is strongly influenced by the surface properties and aggregation behavior of the particles, which is strongly controlled by synthetic and natural organic coatings. Both, surface properties and aggregation characteristics are also key properties for the industrial application of ENPs, which leads to the development and commercialization of an increasing number of surface-functionalized ENPs. These include metals and oxides such as Cerium dioxide (CeO2) with various organic coatings. Therefore, we investigate CeO2 ENPs with different surface coatings such as weakly anionic polyvinyl alcohol (PVA) or strongly anionic poly acrylic acid (PAA) with respect to their colloidal stability in aqueous matrix under various hydrochemical conditions (pH, ionic strength) and their transport behavior in sand filter columns. Furthermore, we investigate the interaction of naturally occurring organic matter (NOM) with CeO2 ENPs and its effect on surface charge (zeta potential), colloidal stability and transport. While uncoated CeO2 ENPs aggregate at pH > 4 in aqueous matrix, our results show that PAA and PVA surface coatings as well as NOM sorbed to CeO2-NP surfaces can stabilize CeO2 ENPs under neutral and alkaline pH conditions in 1 mM KCl solution. Under slightly acidic conditions, differences between the three particle types were observed. PVA can stabilize particle suspensions in presence of 1 mM KCl at pH > 4.3, PAA at pH >4.0 and NOM at >3.2. While the presence of KCl did not influence particle size of NOM-CeO2 ENPs, CaCl2 at >2 mM lead to aggregation. Further results on the influence of KCl and CaCl2 on aggregation of coated CeO2 ENPs and transport in sand filter columns will be presented.

Amperometric micro pH measurements in oxygenated saliva.

PubMed

Chaisiwamongkhol, Korbua; Batchelor-McAuley, Christopher; Compton, Richard G

2017-07-24

An amperometric micro pH sensor has been developed based on the chemical oxidation of carbon fibre surfaces (diameter of 9 μm and length of ca. 1 mm) to enhance the population of surface quinone groups for the measurement of salivary pH. The pH analysis utilises the electrochemically reversible two-electron, two-proton behaviour of surface quinone groups on the micro-wire electrodes. A Nernstian response is observed across the pH range 2-8 which is the pH range of many biological fluids. We highlight the measurement of pH in small volumes of biological fluids without the need for oxygen removal and specifically the micro pH electrode is examined by measuring the pH of commercial synthetic saliva and authentic human saliva samples. The results correspond well with those obtained by using commercial glass pH electrodes on large volume samples.

Protein consensus-based surface engineering (ProCoS): a computer-assisted method for directed protein evolution.

PubMed

Shivange, Amol V; Hoeffken, Hans Wolfgang; Haefner, Stefan; Schwaneberg, Ulrich

2016-12-01

Protein consensus-based surface engineering (ProCoS) is a simple and efficient method for directed protein evolution combining computational analysis and molecular biology tools to engineer protein surfaces. ProCoS is based on the hypothesis that conserved residues originated from a common ancestor and that these residues are crucial for the function of a protein, whereas highly variable regions (situated on the surface of a protein) can be targeted for surface engineering to maximize performance. ProCoS comprises four main steps: ( i ) identification of conserved and highly variable regions; ( ii ) protein sequence design by substituting residues in the highly variable regions, and gene synthesis; ( iii ) in vitro DNA recombination of synthetic genes; and ( iv ) screening for active variants. ProCoS is a simple method for surface mutagenesis in which multiple sequence alignment is used for selection of surface residues based on a structural model. To demonstrate the technique's utility for directed evolution, the surface of a phytase enzyme from Yersinia mollaretii (Ymphytase) was subjected to ProCoS. Screening just 1050 clones from ProCoS engineering-guided mutant libraries yielded an enzyme with 34 amino acid substitutions. The surface-engineered Ymphytase exhibited 3.8-fold higher pH stability (at pH 2.8 for 3 h) and retained 40% of the enzyme's specific activity (400 U/mg) compared with the wild-type Ymphytase. The pH stability might be attributed to a significantly increased (20 percentage points; from 9% to 29%) number of negatively charged amino acids on the surface of the engineered phytase.

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box-Behnken design.

PubMed

Singh, Kunwar P; Rai, Premanjali; Pandey, Priyanka; Sinha, Sarita

2012-01-01

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control. A five-factor Box-Behnken experimental design combined with response surface and optimization modeling was used for predicting the THMs levels in chlorinated water. The adequacy of the selected model and statistical significance of the regression coefficients, independent variables, and their interactions were tested by the analysis of variance and t test statistics. The THMs levels predicted by the model were very close to the experimental values (R(2) = 0.95). Optimization modeling predicted maximum (192 μg/l) TMHs formation (highest risk) level in water during chlorination was very close to the experimental value (186.8 ± 1.72 μg/l) determined in laboratory experiments. The pH of water followed by reaction time and temperature were the most significant factors that affect the THMs formation during chlorination. The developed model can be used to determine the optimum characteristics of raw water and chlorination conditions for maintaining the THMs levels within the safe limit.

Surface complexation modeling of proton and Cd adsorption onto an algal cell wall.

PubMed

Kaulbach, Emily S; Szymanowski, Jennifer E S; Fein, Jeremy B

2005-06-01

This study quantifies Cd adsorption onto the cell wall of the algal species Pseudokirchneriella subcapitata by applying a surface complexation approach to model the observed adsorption behavior. We use potentiometric titrations to determine deprotonation constants and site concentrations for the functional groups on the algal cell wall. Adsorption and desorption kinetics experiments illustrate that adsorption of Cd onto the cell wall is rapid and reversible, except under low pH conditions. Adsorption experiments conducted as a function of pH and total Cd concentration yield the stoichiometry and site-specific stability constants for the important Cd-algal surface complexes. We model the acid/base properties of the algal cell wall by invoking four discrete surface functional group types, with pKa values of 3.9 +/- 0.3, 5.4 +/- 0.1, 7.6 +/- 0.3, and 9.6 +/- 0.4. The results of the Cd adsorption experiments indicate that the first, third, and fourth sites contribute to Cd adsorption under the experimental conditions, with calculated log stability constant values of 4.1 +/- 0.5, 5.4 +/- 0.5, and 6.1 +/- 0.4, respectively. Our results suggest that the stabilities of the Cd-surface complexes are high enough for algal adsorption to affect the fate and transport of Cd under some conditions and that on a per gram basis, algae and bacteria exhibit broadly similar extents of Cd adsorption.

3-D Surface Visualization of pH Titration "Topos": Equivalence Point Cliffs, Dilution Ramps, and Buffer Plateaus

ERIC Educational Resources Information Center

Smith, Garon C.; Hossain, Md Mainul; MacCarthy, Patrick

2014-01-01

3-D topographic surfaces ("topos") can be generated to visualize how pH behaves during titration and dilution procedures. The surfaces are constructed by plotting computed pH values above a composition grid with volume of base added in one direction and overall system dilution on the other. What emerge are surface features that…

Theoretical Analysis of Drug Dissolution: I. Solubility and Intrinsic Dissolution Rate.

PubMed

Shekunov, Boris; Montgomery, Eda Ross

2016-09-01

The first-principles approach presented in this work combines surface kinetics and convective diffusion modeling applied to compounds with pH-dependent solubility and in different dissolution media. This analysis is based on experimental data available for approximately 100 compounds of pharmaceutical interest. Overall, there is a linear relationship between the drug solubility and intrinsic dissolution rate expressed through the total kinetic coefficient of dissolution and dimensionless numbers defining the mass transfer regime. The contribution of surface kinetics appears to be significant constituting on average ∼20% resistance to the dissolution flux in the compendial rotating disk apparatus at 100 rpm. The surface kinetics contribution becomes more dominant under conditions of fast laminar or turbulent flows or in cases when the surface kinetic coefficient may decrease as a function of solution composition or pH. Limitations of the well-known convective diffusion equation for rotating disk by Levich are examined using direct computational modeling with simultaneous dissociation and acid-base reactions in which intrinsic dissolution rate is strongly dependent on pH profile and solution ionic strength. It is shown that concept of diffusion boundary layer does not strictly apply for reacting/interacting species and that thin-film diffusion models cannot be used quantitatively in general case. Copyright © 2016. Published by Elsevier Inc.

Modeling selenite adsorption envelopes on oxides, clay minerals, and soils using the triple layer model

USDA-ARS?s Scientific Manuscript database

Selenite adsorption behavior was investigated on amorphous aluminum and iron oxides, clay minerals: kaolinite, montmorillonite, and illite, and 45 surface and subsurface soil samples from the Southwestern and Midwestern regions of the USA as a function of solution pH. Selenite adsorption decreased ...

Cotton growth modeling and assessment using UAS visual-band imagery

USDA-ARS?s Scientific Manuscript database

This paper explores the potential of using unmanned aircraft system (UAS)-based visible-band images to assess cotton growth. By applying the structure-from-motion algorithm, cotton plant height (ph) and canopy cover (cc) were retrieved from the point cloud-based digital surface models (DSMs) and ort...

pH-dependence of pesticide adsorption by wheat-residue-derived black carbon.

PubMed

Yang, Yaning; Chun, Yuan; Sheng, Guangyao; Huang, Minsheng

2004-08-03

The potential of black carbon as an adsorbent for pesticides in soils may be strongly influenced by the properties of the adsorbent and pesticides and by the environmental conditions. This study evaluated the effect of pH on the adsorption of diuron, bromoxynil, and ametryne by a wheat (Triticum aestivum L.) residue derived black carbon (WC) as compared to a commercial activated carbon (AC). The pH drift method indicated that WC had a point of zero charge of 4.2, much lower than that of 7.8 for AC. The density of oxygen-containing surface functional groups, measured by the Boehm titration, on WC was 5.4 times higher than that on AC, resulting in a pesticide adsorption by WC being 30-50% of that by AC, due to the blockage of WC surface by the waters associated with the functional groups. A small decrease (5.5%/unit pH) in diuron adsorption by WC with increase in pH resulted from increased deprotonation of surface functional groups at higher pH values. A much larger decrease (14-21%/unit pH) in bromoxynil adsorption by WC with increase in pH resulted from the deprotonation of both the adsorbate and surface functional groups of the adsorbent. The deprotonation reduced the adsorptive interaction between bromoxynil and the neutral carbon surface and increased the electrical repulsion between the negatively charged WC surface and bromoxynil anions. Deprotonation of ametryne with increase in pH over the low pH range increased its fraction of molecular form and thus adsorption on WC by 15%/unit pH. Further increase in pH resulted in a 20%/unit pH decrease in ametryne adsorption by WC due primarily to the development of a negative charge on the surface of WC. The pH-dependent adsorption of pesticides by black carbon may significantly influence their environmental fate in soils.

Optimization of lactic acid production by pellet-form Rhizopus oryzae in 3-L airlift bioreactor using response surface methodology.

PubMed

Maneeboon, Thanapoom; Vanichsriratana, Wirat; Pomchaitaward, Chaiyaporn; Kitpreechavanich, Vichien

2010-05-01

The influence of two key environmental factors, pH and oxygen transfer coefficient (k(L)a), was evaluated on the lactic acid production as the main answer and, on the size of cell pellets of the fungal strain Rhizopus oryzae KPS106, as second dependant answer by response surface methodology using a central composite design. The results of the analysis of variance and modeling demonstrated that pH and k(L)a had a significant effect on lactic acid production by this strain. However, no interaction was observed between these two experimental factors. pH and k(L)a had no significant influence on the pellet size. Optimal pH and k(L)a of the fermentation medium for lactic acid production from response surface analysis was 5.85 and of 3.6 h(-1), respectively. The predicted and experimental lactic acid maximal values were 75.4 and 72.0 g/l, respectively, with pellets of an average of 2.54 +/- 0.41 mm. Five repeated batches in series were conducted with a mean lactic acid production of 77.54 g/l. The productivity was increased from 0.75 in the first batch to 0.99 g/l h in the last fifth batch.

Development of a carbonate crust on alkaline nuclear waste sludge at the Hanford site.

PubMed

Page, Jason S; Reynolds, Jacob G; Ely, Tom M; Cooke, Gary A

2018-01-15

Hard crusts on aging plutonium production waste have hindered the remediation of the Hanford Site in southeastern Washington, USA. In this study, samples were analyzed to determine the cause of a hard crust that developed on the highly radioactive sludge during 20 years of inactivity in one of the underground tanks (tank 241-C-105). Samples recently taken from the crust were compared with those acquired before the crust appeared. X-ray diffraction and scanning electron microscopy (SEM) indicated that aluminum and uranium phases at the surface had converted from (hydr)oxides (gibbsite and clarkeite) into carbonates (dawsonite and cejkaite) and identified trona as the cementing phase, a bicarbonate that formed at the expense of thermonatrite. Since trona is more stable at lower pH values than thermonatrite, the pH of the surface decreased over time, suggesting that CO 2 from the atmosphere lowered the pH. Thus, a likely cause of crust formation was the absorption of CO 2 from the air, leading to a reduction of the pH and carbonation of the waste surface. The results presented here help establish a model for how nuclear process waste can age and can be used to aid future remediation and retrieval activities. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of environmental factors on pesticide adsorption by black carbon: pH and model dissolved organic matter.

PubMed

Qiu, Yuping; Xiao, Xiaoyu; Cheng, Haiyan; Zhou, Zunlong; Sheng, G Daniel

2009-07-01

Loading two organic acids of known molecular structures onto a black carbon was conducted to study the influence of pH and dissolved organic matter on the adsorption of pesticides. Tannic acid at the loading rates of 100 and 300 micromol/g reduced the surface area of black carbon by 18 and 63%, respectively. This was due principally to the blockage of micropores, as verified by measured pore volumes and pore-size distributions. With a comparatively much smaller molecular structure, gallic acid did not apparently influence these properties. The intrinsic acidities of the two acids increased the surface acidity from 1.88 mmol/g of black carbon to 1.93-2.02 mmol/g after DOM loading, resulting in a reduction in isoelectric point pH from 1.93 to 1.66-1.82. The adsorption of propanil, 2,4-D and prometon by black carbon free and loaded of DOM was dependent on pH because major adsorptive forces were the interactions between neutral pesticide molecules and uncharged carbon surfaces. The adsorption was diminished considerably by the deprotonation of 2,4-D and protonation of prometon, as well as the surface charge change of black carbon. Tannic acid of 100 and 300 micromol/g on black carbon reduced the pesticide adsorption at the equilibrium concentration of 10 mg/L by an average of 46 and 81%, respectively, consistent with the reductions of 42 and 81% in micropore volume. At the equilibrium concentration of 30 mg/L, the mesopore surface became the additional adsorptive domain for propanil. Loading tannic acid made the mesopore surface less accessible, due presumably to the enhanced obstruction by tannic acid.

Fabrication of pH sensitive nanovalves using smart surface coated nanopores

NASA Astrophysics Data System (ADS)

Nieto-Soto, A. M.; Diaz-Maldonado, D. K.; Rios Angarita, F. A.

2017-01-01

A pH sensitive nanovalve was fabricated using different smart surfaces covalently attached to an anodized aluminium oxide membrane (AAO). The smart surfaces were synthesized using a mixture of aliphatic and aminated silanes. Effect on the contact angle of the aliphatic silane chain length was evaluated. The smart surface, in conjunction with a nanoporous membrane, allowed the formation of a hydrophobic plug which controlled the transport of the molecule safranine depending on the pH of the solution. It was demonstrated that mixtures of butyl and methyl-trimethoxysilane with aminopropyl-trimethoxysilane were able to perform as effective nanovalves creating a plug that remained closed at pH>7 and opened up at pH<5.

Acid-base and copper-binding properties of three organic matter fractions isolated from a forest floor soil solution

NASA Astrophysics Data System (ADS)

van Schaik, Joris W. J.; Kleja, Dan B.; Gustafsson, Jon Petter

2010-02-01

Vast amounts of knowledge about the proton- and metal-binding properties of dissolved organic matter (DOM) in natural waters have been obtained in studies on isolated humic and fulvic (hydrophobic) acids. Although macromolecular hydrophilic acids normally make up about one-third of DOM, their proton- and metal-binding properties are poorly known. Here, we investigated the acid-base and Cu-binding properties of the hydrophobic (fulvic) acid fraction and two hydrophilic fractions isolated from a soil solution. Proton titrations revealed a higher total charge for the hydrophilic acid fractions than for the hydrophobic acid fraction. The most hydrophilic fraction appeared to be dominated by weak acid sites, as evidenced by increased slope of the curve of surface charge versus pH at pH values above 6. The titration curves were poorly predicted by both Stockholm Humic Model (SHM) and NICA-Donnan model calculations using generic parameter values, but could be modelled accurately after optimisation of the proton-binding parameters (pH ⩽ 9). Cu-binding isotherms for the three fractions were determined at pH values of 4, 6 and 9. With the optimised proton-binding parameters, the SHM model predictions for Cu binding improved, whereas the NICA-Donnan predictions deteriorated. After optimisation of Cu-binding parameters, both models described the experimental data satisfactorily. Iron(III) and aluminium competed strongly with Cu for binding sites at both pH 4 and pH 6. The SHM model predicted this competition reasonably well, but the NICA-Donnan model underestimated the effects significantly at pH 6. Overall, the Cu-binding behaviour of the two hydrophilic acid fractions was very similar to that of the hydrophobic acid fraction, despite the differences observed in proton-binding characteristics. These results show that for modelling purposes, it is essential to include the hydrophilic acid fraction in the pool of 'active' humic substances.

Adsorption of sunset yellow FCF from aqueous solution by chitosan-modified diatomite.

PubMed

Zhang, Y Z; Li, J; Li, W J; Li, Y

2015-01-01

Sunset yellow (SY) FCF is a hazardous azo dye pollutant found in food processing effluent. This study investigates the use of diatomaceous earth with chitosan (DE@C) as a modified adsorbent for the removal of SY from wastewater. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of SY. The obtained N2 adsorption-desorption isotherm values accord well with IUPAC type II. Our calculations determined a surface area of 69.68 m2 g(-1) for DE@C and an average pore diameter of 4.85 nm. Using response surface methodology, optimized conditions of process variables for dye adsorption were achieved. For the adsorption of SY onto DE@C, this study establishes mathematical models for the optimization of pH, contact time and initial dye concentration. Contact time plays a greater role in the adsorption process than either pH or initial dye concentration. According to the adjusted correlation coefficient (adj-R2>0.97), the models used here are suitable for illustration of the adsorption process. Theoretical experimental conditions included a pH of 2.40, initial dye concentration of 113 mg L(-1) and 30.37 minutes of contact time. Experimental values for the adsorption rate (92.54%) were close to the values predicted by the models (95.29%).

Modeling the adsorption of hydrogen, sodium, chloride and phthalate on goethite using a strict charge-neutral ion-exchange theory

PubMed Central

Ndu, Udonna

2017-01-01

Simultaneous adsorption modeling of four ions was predicted with a strict net charge-neutral ion-exchange theory and its corresponding equilibrium and mass balance equations. An important key to the success of this approach was the proper collection of all the data, particularly the proton adsorption data, and the inclusion of variable concentrations of conjugate ions from the experimental pH adjustments. Using IExFit software, the ion-exchange model used here predicted the competitive retention of several ions on goethite by assuming that the co-adsorption or desorption of all ions occurred in the correct stoichiometries needed to maintain electroneutrality. This approach also revealed that the retention strength of Cl− ions on goethite increases in the presence of phthalate ions. That is, an anion-anion enhancement effect was observed. The retention of Cl− ions was much weaker than phthalate ions, and this also resulted in a higher sensitivity of the Cl− ions toward minor variations in the surface reactivity. The proposed model uses four goethite surface sites. The drop in retention of phthalate ions at low pH was fully described here as resulting from competitive Cl− reactions, which were introduced in increasing concentrations into the matrix as the conjugate base to the acid added to lower the pH. PMID:28464020

Functional polyaniline/multiwalled carbon nanotube composite as an efficient adsorbent material for removing pharmaceuticals from aqueous media.

PubMed

Dutra, Flávia Viana Avelar; Pires, Bruna Carneiro; Nascimento, Tienne Aparecida; Borges, Keyller Bastos

2018-09-01

The composite polyaniline/multiwalled carbon nanotube (PAni/MWCNT, 1:0.1 w/w) was developed with the intention of binding the adsorbent properties of two materials and using it to adsorb pharmaceuticals from aqueous media. PAni/MWCNT was characterized by scanning electron microscopy, thermogravimetry, infrared spectroscopy, pH at the point of zero charge, and the effect on the surface wettability of the material. As proof of concept, adsorption studies were carried out using meloxicam (MLX) as the pharmaceutical and it was evaluated as a function of pH, temperature, ionic strength, contact time and variation in concentration. Kinetics and isothermal models were applied to evaluate the mechanism of the adsorption process. The best MLX adsorption result was at pH 2 with 6 min of contact with PAni/MWCNT. The kinetics models that fitted the experimental data were pseudo-second order and Elovich and the kinetics model was the dual-site Langmuir-Freundlich. Both models suggest that the adsorption occurs by the chemical nature of the surface and in the pores of the energetically heterogeneous composite. The PAni/MWCNT presented an adsorption capacity of 221.2 mg g -1 , a very good value when compared with the literature and can be used to remove pharmaceuticals from aqueous environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Polymerized PolyHEMA photonic crystals: pH and ethanol sensor materials.

PubMed

Xu, Xiangling; Goponenko, Alexander V; Asher, Sanford A

2008-03-12

The surface of monodisperse silica particles synthesized using the Stober process were coated with a thin layer of polystyrene. Surface charge groups were attached by a grafting polymerization of styrene sulfonate. The resulting highly charged monodisperse silica particles self-assemble into crystalline colloidal arrays (CCA) in deionized water. We polymerized hydroxyethyl methacrylate (HEMA) around the CCA to form a HEMA-polymerized crystalline colloidal array (PCCA). Hydrofluoric acid was utilized to etch out the silica particles to produce a three-dimensional periodic array of voids in the HEMA PCCA. The diffraction from the embedded CCA sensitively monitors the concentration of ethanol in water because the HEMA PCCA shows a large volume dependence on ethanol due to a decreased Flory-Huggins mixing parameter. Between pure water and 40% ethanol the diffraction shifts across the entire visible spectral region. We accurately modeled the dependence of the diffraction wavelength on ethanol concentration using Flory theory. We also fabricated a PCCA (which responds to pH changes in both low and high ionic strength solutions) by utilizing a second polymerization to incorporate carboxyl groups into the HEMA PCCA. We were also able to model the pH dependence of diffraction of the HEMA PCCA by using Flory theory. An unusual feature of the pH response is a hysteresis in response to titration to higher and lower pH. This hysteresis results from the formation of a Donnan potential at high pH which shifts the ionic equilibrium. The kinetics of equilibration is very slow due to the ultralow diffusion constant of protons in the carboxylated PCCA as predicted earlier by the Tanaka group.

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

NASA Astrophysics Data System (ADS)

Schindler, Michael; Freund, Michael; Hawthorne, Frank C.; Burns, Peter C.; Maurice, Patricia A.

2009-05-01

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H 2O) 5[(UO 2)(SiO 3(OH)] 2, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb 2+-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl 2-HCl solution of pH 2. They are part of an aged silica coating of composition Si 2O 2(OH) 4(H 2O) n. An amorphous layer forms on the surface of uranophane in a MgCl 2-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO 3) 2-HCl and BaCl 2-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO 3) 2-HCl < BaCl 2-HCl < CaCl 2-HCl < HCl < SrCl 2-HCl < MgCl 2-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl +).

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

Effect of process variables on the sulfate reduction process in bioreactors treating metal-containing wastewaters: factorial design and response surface analyses.

PubMed

Villa-Gomez, D K; Pakshirajan, K; Maestro, R; Mushi, S; Lens, P N L

2015-07-01

The individual and combined effect of the pH, chemical oxygen demand (COD) and SO4 (2-) concentration, metal to sulfide (M/S(2-)) ratio and hydraulic retention time (HRT) on the biological sulfate reduction (SR) process was evaluated in an inverse fluidized bed reactor by factorial design analysis (FDA) and response surface analysis (RSA). The regression-based model of the FDA described the experimental results well and revealed that the most significant variable affecting the process was the pH. The combined effect of the pH and HRT was barely observable, while the pH and COD concentration positive effect (up to 7 and 3 gCOD/L, respectively) enhanced the SR process. Contrary, the individual COD concentration effect only enhanced the COD removal efficiency, suggesting changes in the microbial pathway. The RSA showed that the M/S(2-) ratio determined whether the inhibition mechanism to the SR process was due to the presence of free metals or precipitated metal sulfides.

Cr(VI) Sorption by Nanosized FeS-Coated Sand

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Effects of pH values of hydrogen peroxide bleaching agents on enamel surface properties.

PubMed

Xu, B; Li, Q; Wang, Y

2011-01-01

This study investigated the influence of pH values of bleaching agents on the properties of the enamel surface. Sixty freshly extracted premolars were embedded in epoxy resin and mesiodistally sectioned through the buccal aspect into two parts. The sectioned slabs were distributed among six groups (n=10) and treated using different solutions. Group HCl was treated with HCl solution (pH=3.0) and served as a positive control. Group DW, stored in distilled water (pH=7.0), served as a negative control. Four treatment groups were treated using 30% hydrogen peroxide solutions with different pH values: group HP3 (pH=3.0), group HP5 (pH=5.0), group HP7 (pH=7.0), and group HP8 (pH=8.0). The buccal slabs were subjected to spectrophotometric evaluations. Scanning electron microscopy investigation and Micro-Raman spectroscopy were used to evaluate enamel surface morphological and chemical composition alterations. pH value has a significant influence on the color changes after bleaching (p<0.001). Tukey's multiple comparisons revealed that the order of color changes was HP8, HP7>HP5, HP3>HCl>DW. No obvious morphological alterations were detected on the enamel surface in groups DW, HP7, and HP8. The enamel surface of groups HCl and HP3 showed significant alterations with an erosion appearance. No obvious chemical composition changes were detected with respect to Micro-Raman analysis. Within the limitations of this study, it was concluded that no obvious morphological or chemical composition alterations of enamel surface were detected in the neutral or alkaline bleaching solutions. Bleaching solutions with lower pH values could result in more significant erosion of enamel, which represented a slight whitening effect.

Oxidation of aluminum alloy cladding for research and test reactor fuel

NASA Astrophysics Data System (ADS)

Kim, Yeon Soo; Hofman, G. L.; Robinson, A. B.; Snelgrove, J. L.; Hanan, N.

2008-08-01

The oxide thicknesses on aluminum alloy cladding were measured for the test plates from irradiation tests RERTR-6 and 7A in the ATR (advanced test reactor). The measured thicknesses were substantially lower than those of test plates with similar power from other reactors available in the literature. The main reason is believed to be due to the lower pH (pH 5.1-5.3) of the primary coolant water in the ATR than in the other reactors (pH 5.9-6.5) for which we have data. An empirical model for oxide film thickness predictions on aluminum alloy used as fuel cladding in the test reactors was developed as a function of irradiation time, temperature, surface heat flux, pH, and coolant flow rate. The applicable ranges of pH and coolant flow rates cover most research and test reactors. The predictions by the new model are in good agreement with the in-pile test data available in the literature as well as with the RERTR test data measured in the ATR.

Release of Si from Silicon, a Ferrosilicon (FeSi) Alloy and a Synthetic Silicate Mineral in Simulated Biological Media

PubMed Central

Herting, Gunilla; Jiang, Tao; Sjöstedt, Carin; Odnevall Wallinder, Inger

2014-01-01

Unique quantitative bioaccessibility data has been generated, and the influence of surface/material and test media characteristics on the elemental release process were assessed for silicon containing materials in specific synthetic body fluids at certain time periods at a fixed loading. The metal release test protocol, elaborated by the KTH team, has previously been used for classification, ranking, and screening of different alloys and metals. Time resolved elemental release of Si, Fe and Al from particles, sized less than 50 µm, of two grades of metallurgical silicon (high purity silicon, SiHG, low purity silicon, SiLG), an alloy (ferrosilicon, FeSi) and a mineral (aluminium silicate, AlSi) has been investigated in synthetic body fluids of varying pH, composition and complexation capacity, simple models of for example dermal contact and digestion scenarios. Individual methods for analysis of released Si (as silicic acid, Si(OH)4) in synthetic body fluids using GF-AAS were developed for each fluid including optimisation of solution pH and graphite furnace parameters. The release of Si from the two metallurgical silicon grades was strongly dependent on both pH and media composition with the highest release in pH neutral media. No similar effect was observed for the FeSi alloy or the aluminium silicate mineral. Surface adsorption of phosphate and lactic acid were believed to hinder the release of Si whereas the presence of citric acid enhanced the release as a result of surface complexation. An increased presence of Al and Fe in the material (low purity metalloid, alloy or mineral) resulted in a reduced release of Si in pH neutral media. The release of Si was enhanced for all materials with Al at their outermost surface in acetic media. PMID:25225879

Modeling and predicting the biofilm formation of Salmonella Virchow with respect to temperature and pH.

PubMed

Ariafar, M Nima; Buzrul, Sencer; Akçelik, Nefise

2016-03-01

Biofilm formation of Salmonella Virchow was monitored with respect to time at three different temperature (20, 25 and 27.5 °C) and pH (5.2, 5.9 and 6.6) values. As the temperature increased at a constant pH level, biofilm formation decreased while as the pH level increased at a constant temperature, biofilm formation increased. Modified Gompertz equation with high adjusted determination coefficient (Radj(2)) and low mean square error (MSE) values produced reasonable fits for the biofilm formation under all conditions. Parameters of the modified Gompertz equation could be described in terms of temperature and pH by use of a second order polynomial function. In general, as temperature increased maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation decreased; whereas, as pH increased; maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation increased. Two temperature (23 and 26 °C) and pH (5.3 and 6.3) values were used up to 24 h to predict the biofilm formation of S. Virchow. Although the predictions did not perfectly match with the data, reasonable estimates were obtained. In principle, modeling and predicting the biofilm formation of different microorganisms on different surfaces under various conditions could be possible.

Electrocoagulation and nanofiltration integrated process application in purification of bilge water using response surface methodology.

PubMed

Akarsu, Ceyhun; Ozay, Yasin; Dizge, Nadir; Elif Gulsen, H; Ates, Hasan; Gozmen, Belgin; Turabik, Meral

Marine pollution has been considered an increasing problem because of the increase in sea transportation day by day. Therefore, a large volume of bilge water which contains petroleum, oil and hydrocarbons in high concentrations is generated from all types of ships. In this study, treatment of bilge water by electrocoagulation/electroflotation and nanofiltration integrated process is investigated as a function of voltage, time, and initial pH with aluminum electrode as both anode and cathode. Moreover, a commercial NF270 flat-sheet membrane was also used for further purification. Box-Behnken design combined with response surface methodology was used to study the response pattern and determine the optimum conditions for maximum chemical oxygen demand (COD) removal and minimum metal ion contents of bilge water. Three independent variables, namely voltage (5-15 V), initial pH (4.5-8.0) and time (30-90 min) were transformed to coded values. The COD removal percent, UV absorbance at 254 nm, pH value (after treatment), and concentration of metal ions (Ti, As, Cu, Cr, Zn, Sr, Mo) were obtained as responses. Analysis of variance results showed that all the models were significant except for Zn (P > 0.05), because the calculated F values for these models were less than the critical F value for the considered probability (P = 0.05). The obtained R(2) and Radj(2) values signified the correlation between the experimental data and predicted responses: except for the model of Zn concentration after treatment, the high R(2) values showed the goodness of fit of the model. While the increase in the applied voltage showed negative effects, the increases in time and pH showed a positive effect on COD removal efficiency; also the most effective linear term was found as time. A positive sign of the interactive coefficients of the voltage-time and pH-time systems indicated synergistic effect on COD removal efficiency, whereas interaction between voltage and pH showed an antagonistic effect.

Growth and characterization of organic layers deposited on porous-patterned Si surface

NASA Astrophysics Data System (ADS)

Gorbach, Tamara Ya.; Smertenko, Petro S.; Olkhovik, G. P.; Wisz, Grzegorz

2017-01-01

The organic layers with the thickness from a few nanometers up to few micrometers have been deposited from the chemical solution at room temperature on porous patterned Si surfaces using two medical solutions: thiamine diphosphide (pH=1÷2) and metamizole sodium (pH=6÷7). Based on evolution of morphology, structural and compositional features obtained by scanning electron microscopy, X-ray analysis, reflectance high energy electron diffraction the grown mechanisms in thin organic layers are discussed in the terms of terrace-step-kink model whereas self-organized assemblies evaluated more thick layers. Transport mechanism features and possible photovoltaic properties are discussed on the base of differential current-voltage characteristics.

Neutron reflectivity measurement of protein A-antibody complex at the solid-liquid interface.

PubMed

Mazzer, Alice R; Clifton, Luke A; Perevozchikova, Tatiana; Butler, Paul D; Roberts, Christopher J; Bracewell, Daniel G

2017-05-26

Chromatography is a ubiquitous unit operation in the purification of biopharmaceuticals yet few studies have addressed the biophysical characterisation of proteins at the solution-resin interface. Chromatography and other adsorption and desorption processes have been shown to induce protein aggregation which is undesirable in biopharmaceutical products. In order to advance understanding of how adsorption processes might impact protein stability, neutron reflectivity was used to characterise the structure of adsorbed immunoglobulin G (IgG) on model surfaces. In the first model system, IgG was adsorbed directly to silica and demonstrated a side-on orientation with high surface contact. A maximum dimension of 60Å in the surface normal direction and high density surface coverage were observed under pH 4.1 conditions. In chromatography buffers, pH was found to influence IgG packing density and orientation at the solid-liquid interface. In the second model system, which was designed to mimic an affinity chromatography surface, protein A was attached to a silica surface to produce a configuration representative of a porous glass chromatography resin. Interfacial structure was probed during sequential stages from ligand attachment, through to IgG binding and elution. Adsorbed IgG structures extended up to 250Å away from the surface and showed dependence on surface blocking strategies. The data was suggestive of two IgG molecules bound to protein A with a somewhat skewed orientation and close proximity to the silica surface. The findings provide insight into the orientation of adsorbed antibody structures under conditions encountered during chromatographic separations. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

FY04 LDRD Final Report: Interaction of Viruses with Membranes and Soil Materials

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

Schaldach, C M

2005-02-08

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q{beta} and Norwalk. The environmental surface is modeled as charged Gouy-Chapman plane with and without a finite atomistic region (patch) of opposite charge. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements asmore » a function of pH. The results indicate that the electrostatic interaction between the virus and the planar surface, mitigated by the ionic strength of the solute, is dependent upon the spatial distribution of the amino acid residues in the different viruses. Specifically, the order of interaction energies with the patch (MS2 greatest at 5 mM; Norwalk greatest at 20 mM) is dependent upon the ionic strength of the fluid as a direct result of the viral coat amino acid distributions. We have developed an atomistic-scale method of calculation of the binding energy of viruses to surfaces including electrostatic, van der Waals, electron-overlap repulsion, surface charge polarization (images), and hydrophobic effects. The surface is treated as a Gouy-Chapman plane allowing inclusion of pH and ionic strength effects on the electrostatic potential at each amino acid charge. Van der Waals parameters are obtained from the DREIDING force field and from Hamaker constant measurements. We applied this method to the calculation of the Cowpea Mosaic Virus (CPMV), a negatively charged virus at a pH of 7.0, and find that the viral-gold surface interaction is very long range for both signs of surface potential, a result due to the electrostatic forces. For a negative (Au) surface potential of -0.05 volts, a nearly 4 eV barrier must be overcome to reach 1 nm from the surface.« less

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

The formation and stability of saline minerals at the Martian surface

NASA Astrophysics Data System (ADS)

Tosca, Nicholas James, III

Evaporite minerals have been identified throughout the martian sedimentary record. Because evaporites can record detailed paleo-environmental information and often host fossil biosignatures on Earth, they are priority targets for future exploration. However, understanding processes that control the formation of these minerals on Mars requires an understanding of the behavior of Fe in highly concentrated evaporating fluids. In this study, a model is developed using the Pitzer ion interaction approach that accurately describes thermodynamic properties of the Fe2(SO4)3-H2SO4-H 2O system. Incorporating this model into a multicomponent thermodynamic database enables detailed study of evaporite mineral formation and stability on Mars. From geochemical modeling, the variation in evaporite mineralogy on Mars may be traced to volatile-anion input -- a variable intimately tied to pH. Using the "chemical divide" concept, evaporites at the martian surface can be used as sensitive probes of pH, atmospheric composition, and cation proportion in solution. Applying this approach to saline assemblages in Nakhlite meteorites and in Meridiani Planum sediments reveals two geochemical systems; each characterized by different pH and anion proportion. A complicating factor however is the concomitant oxidation of soluble Fe-bearing minerals. Such a process may have contributed to complex Fe mineralogy observed at Meridiani Planum through diagenesis. Fe-oxidation experiments at high ionic strength show a progression of mineral phases that begins with the formation of schwertmannite and subsequent ageing to jarosite and nano-crystalline goethite; a process strongly controlled by pH. Low water activity and small particle size drive the ageing of goethite to hematite which provides the final step of a mechanism that is consistent with the distribution of Fe-minerals at Meridiani Planum. These results show that the instability of Fe2+-sulfate minerals at the martian surface may lead to the association of Fe-oxide and Fe-hydroxysulfate minerals with evaporite salts. Indeed, such a geologic association has been observed through remote sensing techniques. Thus, as the Fe-sulfates are sensitive to pH, Fe-oxidation and relative humidity, understanding these phase relationships in greater detail will ultimately exploit the presence of these minerals as a unique set of geochemical probes.

Laboratory column experiments and transport modeling to evaluate retardation of uranium in an aquifer downgradient of a uranium in-situ recovery site

DOE PAGES

Dangelmayr, Martin A.; Reimus, Paul W.; Wasserman, Naomi L.; ...

2017-05-01

The purpose of this study was to determine the attenuation potential and retardation of uranium in sediments taken from boreholes at the Smith-Ranch Highland in-situ recovery (ISR) site. Five column experiments with four different sediments were conducted to study the effects of variable mineralogy and alkalinity on uranium breakthrough. Uranium transport was modeled with PHREEQC using a generalized composite surface complexation model (GC SCM) with one, two, and, three generic surfaces, respectively. Reactive surface areas were approximated with PEST using BET derived surface areas to constrain fitting parameters. Uranium breakthrough was delayed by a factor of 1.68, 1.69 and 1.47more » relative to the non-reactive tracer for three of the 5 experiments at an alkalinity of 540 mg/l. A sediment containing smectite and kaolinite retained uranium by a factor of 2.80 despite a lower measured BET surface area. Decreasing alkalinity to 360 mg/l from 540 mg/l increased retardation by a factor of 4.26. Model fits correlated well to overall BET surface area in the three columns where clay content was less than 1%. For the sediment with clay, models consistently understated uranium retardation when reactive surface sites were restricted by BET results. Calcite saturation was shown to be a controlling factor for uranium desorption as the pH of the system changes. A pH of 6 during a secondary background water flush remobilized previously sorbed uranium resulting in a secondary uranium peak at twice the influent concentrations. Furthermore, this study demonstrates the potential of GC SCM models to predict uranium transport in sediments with homogenous mineral composition, but highlights the need for further research to understand the role of sediment clay composition and calcite saturation in uranium transport.« less

Laboratory column experiments and transport modeling to evaluate retardation of uranium in an aquifer downgradient of a uranium in-situ recovery site

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

Dangelmayr, Martin A.; Reimus, Paul W.; Wasserman, Naomi L.

The purpose of this study was to determine the attenuation potential and retardation of uranium in sediments taken from boreholes at the Smith-Ranch Highland in-situ recovery (ISR) site. Five column experiments with four different sediments were conducted to study the effects of variable mineralogy and alkalinity on uranium breakthrough. Uranium transport was modeled with PHREEQC using a generalized composite surface complexation model (GC SCM) with one, two, and, three generic surfaces, respectively. Reactive surface areas were approximated with PEST using BET derived surface areas to constrain fitting parameters. Uranium breakthrough was delayed by a factor of 1.68, 1.69 and 1.47more » relative to the non-reactive tracer for three of the 5 experiments at an alkalinity of 540 mg/l. A sediment containing smectite and kaolinite retained uranium by a factor of 2.80 despite a lower measured BET surface area. Decreasing alkalinity to 360 mg/l from 540 mg/l increased retardation by a factor of 4.26. Model fits correlated well to overall BET surface area in the three columns where clay content was less than 1%. For the sediment with clay, models consistently understated uranium retardation when reactive surface sites were restricted by BET results. Calcite saturation was shown to be a controlling factor for uranium desorption as the pH of the system changes. A pH of 6 during a secondary background water flush remobilized previously sorbed uranium resulting in a secondary uranium peak at twice the influent concentrations. Furthermore, this study demonstrates the potential of GC SCM models to predict uranium transport in sediments with homogenous mineral composition, but highlights the need for further research to understand the role of sediment clay composition and calcite saturation in uranium transport.« less

Water clusters contributed to molecular interactions of ionizable organic pollutants with aromatized biochar via π-PAHB: Sorption experiments and DFT calculations.

PubMed

Zhang, Kun; Chen, Baoliang; Mao, Jiefei; Zhu, Lizhong; Xing, Baoshan

2018-05-08

Molecular interactions between biochars and ionizable organic pollutants (IOPs) are of great concern in natural environments, however the role of water clusters on the biochar surface remain unclear. The pH-dependent adsorption of aniline, phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-methylphenol and 4-nitrophenol onto bamboo wood derived biochar (BW700) as a model was conducted to identify conventional and novel interaction mechanisms between aromatized surface and IOPs. The dissociation constant (pK a,surface ) of surface functional groups of BW700 was characterized by acid-base titration and Zeta potential measurements. The pH-dependent adsorption behavior depended on the pK a,IOP of IOPs and also related to the pK a,surface of biochar surface. An obvious peak of adsorption coefficients (K d ) in the range of solution pH was shaped at pH peak  = (pK a,IOP  + pK a,surface )/2, which cannot be well explained by the conventional mechanisms such as hydrophobic effects, π-π interaction, electrostatic attractions, and hydrogen-binding. The contribution of ice-like adlayer (water clusters) on aromatic surface as H-acceptors is proposed for the first time to the adsorption peak of IOP as H-donors at pH peak . Density functional theory (DFT) calculations provided a possible structure of the complex combined with ice-like adlayer and aromatic substrate of BW700, and indicated that the adsorbing peak resulted from the multiple π-bond and polarization assisted H-bond (π-PAHB) interactions. Three distinct properties of π-PAHB were given, based on multiple π-bond, hydrophobicity-dependence and pH sensitivity. This novel mechanism extends the definition of H-bonds for better understanding the molecular interactions of IOP with carbonaceous materials and their environmental fate. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phenol adsorption on surface-functionalized iron oxide nanoparticles: modeling of the kinetics, isotherm, and mechanism

NASA Astrophysics Data System (ADS)

Yoon, Soon Uk; Mahanty, Biswanath; Ha, Hun Moon; Kim, Chang Gyun

2016-06-01

Phenol adsorption from aqueous solution was carried out using uncoated and methyl acrylic acid (MAA)-coated iron oxide nanoparticles (NPs), having size <10 nm, as adsorbents. Batch adsorption studies revealed that the phenol removal efficiency of MAA-coated NPs (950 mg g-1) is significantly higher than that of uncoated NPs (550 mg g-1) under neutral to acidic conditions. However, this improvement disappears above pH 9. The adsorption data under optimized conditions (pH 7) were modeled with pseudo-first- and pseudo-second-order kinetics and subjected to Freundlich and Langmuir isotherms. The analysis determined that pseudo-second-order kinetics and the Freundlich model are appropriate for both uncoated and MAA-coated NPs (all R 2 > 0.98). X-ray photoelectron spectroscopy analysis of pristine and phenol-adsorbed NPs revealed core-level binding energy and charge for Fe(2 s) and O(1 s) on the NP surfaces. The calculations suggest that phenol adsorption onto MAA-coated NPs is a charge transfer process, where the adsorbate (phenol) acts as an electron donor and the NP surface (Fe, O) as an electron acceptor. However, a physisorption process appears to be the relevant mechanism for uncoated NPs.

Understanding the creation of & reducing surface microroughness during polishing & post-processing of glass optics

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

Suratwala, Tayyab

2016-09-22

In the follow study, we have developed a detailed understanding of the chemical and mechanical microscopic interactions that occur during polishing affecting the resulting surface microroughness of the workpiece. Through targeted experiments and modeling, the quantitative relationships of many important polishing parameters & characteristics affecting surface microroughness have been determined. These behaviors and phenomena have been described by a number of models including: (a) the Ensemble Hertzian Multi Gap (EHMG) model used to predict the removal rate and roughness at atomic force microscope (AFM) scale lengths as a function of various polishing parameters, (b) the Island Distribution Gap (IDG) modelmore » used to predict the roughness at larger scale lengths, (c) the Deraguin-Verwey-Landau-Overbeek (DLVO) 3-body electrostatic colloidal model used to predict the interaction of slurry particles at the interface and roughness behavior as a function of pH, and (d) a diffusion/chemical reaction rate model of the incorporation of impurities species into the polishing surface layer (called the Bielby layer). Based on this improved understanding, novel strategies to polish the workpiece have been developed simultaneously leading to both ultrasmooth surfaces and high material removal rates. Some of these strategies include: (a) use of narrow PSD slurries, (b) a novel diamond conditioning recipe of the lap to increase the active contact area between the workpiece and lap without destroying its surface figure, (c) proper control of pH for a given glass type to allow for a uniform distribution of slurry particles at the interface, and (d) increase in applied load just up to the transition between molecular to plastic removal regime for a single slurry particle. These techniques have been incorporated into a previously developed finishing process called Convergent Polishing leading to not just economical finishing process with improved surface figure control, but also simultaneously leading to low roughness surface with high removal rates.« less

Kinetic model for the short-term dissolution of a rhyolitic glass

USGS Publications Warehouse

White, A.F.; Claassen, H.C.

1980-01-01

Aqueous dissolution experiments with the vitric phase of a rhyolitic tuff were performed at 25??C and constant pH in the range 4.5-7.5. Results suggest interchange of aqueous hydrogen ions for cations situated both on the surface and within the glass. At time intervals from 24 to 900 hr., dissolution kinetics are controlled by ion transport to and from sites within the glass. Experimental data indicate that parabolic diffusion rate of a chemical species from the solid is a nonlinear function of its aqueous concentration. A numerical solution to Fick's second law is presented for diffusion of sodium, which relates it's aqueous concentration to it's concentration on glass surface, by a Freundlich adsorption isotherm. The pH influence on sodium diffusion in the model can be accounted for by use of a pH-dependent diffusion coefficient and a pH-independent adsorption isotherm. ?? 1980.

Parametric and energy consumption optimization of Basic Red 2 removal by electrocoagulation/egg shell adsorption coupling using response surface methodology in a batch system.

PubMed

de Carvalho, Helder Pereira; Huang, Jiguo; Zhao, Meixia; Liu, Gang; Yang, Xinyu; Dong, Lili; Liu, Xingjuan

2016-01-01

In this study, response surface methodology (RSM) model was applied for optimization of Basic Red 2 (BR2) removal using electrocoagulation/eggshell (ES) coupling process in a batch system. Central composite design was used to evaluate the effects and interactions of process parameters including current density, reaction time, initial pH and ES dosage on the BR2 removal efficiency and energy consumption. The analysis of variance revealed high R(2) values (≥85%) indicating that the predictions of RSM models are adequately applicable for both responses. The optimum conditions when the dye removal efficiency of 93.18% and energy consumption of 0.840 kWh/kg were observed were 11.40 mA/cm(2) current density, 5 min and 3 s reaction time, 6.5 initial pH and 10.91 g/L ES dosage.

Molecular-Orbital Models for the Catayltic Activity and Selectivity of Coordinatively Unsaturated Platinum Surfaces and Complexes.

DTIC Science & Technology

1980-12-31

surfaces. Reactions involving the Pt(O)- triphenylphosphine complexes Pt(PPh 3)n, where n = 2, 3, 4, have been shown to have precise analogues on Pt...12], the triphenylphosphine (PPh 3 ) group is modeled by the simpler but chemically similar phosphine (PH3) group. The appropriate Pt-P bond distances...typically refractory oxides ) are of sufficient magnitude as to suggest significant chemical and electronic modifications of the metal at the metal-support

Dual-responsive surfaces modified with phenylboronic acid-containing polymer brush to reversibly capture and release cancer cells.

PubMed

Liu, Hongliang; Li, Yingying; Sun, Kang; Fan, Junbing; Zhang, Pengchao; Meng, Jingxin; Wang, Shutao; Jiang, Lei

2013-05-22

Artificial stimuli-responsive surfaces that can mimic the dynamic function of living systems have attracted much attention. However, there exist few artificial systems capable of responding to dual- or multistimulation as the natural system does. Herein, we synthesize a pH and glucose dual-responsive surface by grafting poly(acrylamidophenylboronic acid) (polyAAPBA) brush from aligned silicon nanowire (SiNW) array. The as-prepared surface can reversibly capture and release targeted cancer cells by precisely controlling pH and glucose concentration, exhibiting dual-responsive AND logic. In the presence of 70 mM glucose, the surface is pH responsive, which can vary from a cell-adhesive state to a cell-repulsive state by changing the pH from 6.8 to 7.8. While keeping the pH at 7.8, the surface becomes glucose responsive--capturing cells in the absence of glucose and releasing cells by adding 70 mM glucose. Through simultaneously changing the pH and glucose concentration from pH 6.8/0 mM glucose to pH 7.8/70 mM glucose, the surface is dual responsive with the capability to switch between cell capture and release for at least 5 cycles. The cell capture and release process on this dual-responsive surface is noninvasive with cell viability higher than 95%. Moreover, topographical interaction between the aligned SiNW array and cell protrusions greatly amplifies the responsiveness and accelerates the response rate of the dual-responsive surface between cell capture and release. The responsive mechanism of the dual-responsive surface is systematically studied using a quartz crystal microbalance, which shows that the competitive binding between polyAAPBA/sialic acid and polyAAPBA/glucose contributes to the dual response. Such dual-responsive surface can significantly impact biomedical and biological applications including cell-based diagnostics, in vivo drug delivery, etc.

[Adsorption behavior and influence factors of p-nitroaniline on high surface area activated carbons prepared from plant stems].

PubMed

Li, Kun-quan; Zheng, Zheng; Luo, Xing-zhang

2010-08-01

Low-cost and high surface area microporous activated carbons were prepared from Spartina alternilora and cotton stalk with KOH activation under the conditions of impregnation ratio of 3.0, activation temperature at 800 degrees C and activation time of 1.5 h. The adsorption behavior of p-nitroaniline on the activated carbons was investigated by batch sorption experiments. The influences of solution pH value, adsorbent dose and temperature were investigated. The adsorption isotherm and thermodynamic characteristics were also discussed. The Spartina alterniflora activated carbon (SA-AC) has a high surface area of 2825 m2 x g(-1) and a micropore volume of 1.192 cm3 x g(-1). The BET surface area and micropore volume of the cotton stalk activated carbon (CS-AC) are 2135 m2 x g(-1) and 1.011 cm3 x g(-1), respectively. The sorption experiments show that both the activated carbons have high sorption capacity for p-nitroaniline. The Langmuir maximum sorption amount was found to be 719 mg x g(-1) for SA-AC and 716 mg x g(-1) for CS-AC, respectively. The sorption was found to depend on solution pH, adsorbent dose, and temperature. The optimum pH for the removal of p-nitroaniline was found to be 7.0. The Freundlich model and Redlich-Peterson model can describe the experimental data effectively. The negative changes in free energy (delta G0) and enthalpy (delta H0) indicate that the sorption is a spontaneous and exothermic procedure. The negative values of the adsorption entropy delta S0 indicate that the mobility of p-nitroaniline on the carbon surface becomes more restricted as compared with that of those in solution.

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

Chatman, Shawn ME; Zarzycki, Piotr P.; Preocanin, Tajana

Time dependent potentiometric pH titrations were used to study the effect of atomic scale surface structure on the protonation behavior of the structurally well defined hematite/aqueous electrolyte interfaces. Our recently proposed thermodynamic model [1,23] was applied to measured acidimetric and alkalimetric titration hysteresis loops, collected from highly organized (001), (012), and (113) crystal face terminations using pH equilibration times ranging from 15 to 30 mins. Hysteresis loop areas indicate that (001) faces equilibrate faster than the (012) and (113) faces, consistent with the different expected ensembles of singly, doubly, and triply coordinated surface sites on each face. Strongly non-linear hystereticmore » pH-potential relationships were found, with slopes exceeding Nernstian, collectively indicating that protonation and deprotonation is much more complex than embodied in present day surface complexation models. The asymmetrical shape of the acidimetric and alkalimetric titration branches were used to illustrate a proposed steric "leaky screen" repulsion/trapping interaction mechanism that stems from high affinity singly-coordinated sites electrostatically and sterically screening lower affinity doubly and triply coordinated sites. Our data indicate that site interaction is the dominant phenomenon defining surface potential accumulation behavior on single crystal faces of metal oxide minerals.« less

Effect of surface site interactions on potentiometric titration of hematite (α-Fe2O3) crystal faces.

PubMed

Chatman, Shawn; Zarzycki, P; Preočanin, T; Rosso, K M

2013-02-01

Time dependent potentiometric pH titrations were used to study the effect of atomic scale surface structure on the protonation behavior of the structurally well-defined hematite/electrolyte interfaces. Our recently proposed thermodynamic model [1,25] was applied to measured acidimetric and alkalimetric titration hysteresis loops, collected from highly organized (001), (012), and (113) crystal face terminations using pH equilibration times ranging from 15 to 30 min. Hysteresis loop areas indicate that (001) faces equilibrate faster than the (012) and (113) faces, consistent with the different expected ensembles of singly-, doubly-, and triply-coordinated surface sites on each face. Strongly non-linear hysteretic pH-potential relationships were found, with slopes exceeding Nernstian, collectively indicating that protonation and deprotonation is much more complex than embodied in present day surface complexation models. The asymmetrical shape of the acidimetric and alkalimetric titration branches were used to illustrate a proposed steric "leaky screen" repulsion/trapping interaction mechanism that stems from high affinity singly-coordinated sites electrostatically and sterically screening lower affinity doubly- and triply-coordinated sites. Our data indicate that site interaction is the dominant phenomenon defining surface potential accumulation behavior on single crystal faces of metal oxide minerals. Copyright © 2012 Elsevier Inc. 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.

The surface pH of glass ionomer cavity lining agents.

PubMed

Woolford, M J

1989-12-01

It is considered that acid release from the surface of glass ionomer (polyalkenoate) cements may be associated with early pulpal sensitivity following the use of these materials. This study was carried out to examine the surface pH of different types of glass ionomer lining cements using a flat-ended pH electrode. It was found that the surface pH remains low for this group of materials during the first hour of setting. Different types of glass ionomer lining cement were also shown to behave differently when considering acid release from the surface. Conclusions regarding the behaviour of glass ionomers should only be made with reference to the specific material tested.

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

USGS Publications Warehouse

Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Deposition mechanisms of TiO2 nanoparticles in a parallel plate system.

PubMed

Chowdhury, Indranil; Walker, Sharon L

2012-03-01

In this study, a microscope-based technique was utilized to understand the fundamental mechanisms involved in deposition of TiO(2) nanoparticles (TNPs). Transport and deposition studies were conducted in a parallel plate (PP) flow chamber with TNP labeled with fluorescein isothiocyanate (FITC) for visualization. Attachment of FITC-labeled TNPs on surfaces is a function of a combination of parameters, including ionic strength (IS), pH and flowrate. Significantly higher deposition rates were observed at pH 5 versus pH 7. This is attributed to the conditions being chemically favorable for deposition at pH 5 as compared to pH 7, as predicted by DLVO theory. Additionally, deposition rates at pH 5 were reduced with IS below 10 mM due to the decrease in range of electrostatic attractive forces. Above 10 mM, aggregate size increased, resulting in higher deposition rates. At pH 7, no deposition was observed below 10 mM and above this concentration, deposition increased with IS. The impact of flowrate was also observed, with decreasing flowrate leading to greater deposition due to the reduction in drag force acting on the aggregate (regardless of pH). Comparisons between experimental and theoretical approximations indicate that non-DLVO type forces also play a significant role. This combination of observations suggest that the deposition of these model nanoparticles on glass surfaces was controlled by a combination of DLVO and non-DLVO-type forces, shear rate, aggregation state, and gravitational force acting on TNPs. Copyright © 2011 Elsevier Inc. All rights reserved.

Charging properties of cassiterite (alfa-SnO2) surfaces

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, L.

The acid-base properties of cassiterite (alfa-SnO2) surfaces at 10 50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH-range 4.0 to 4.5 at all conditions and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical Molecular Dynamics (MD) simulations, was analyzed in detail and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural alfa-TiO2 (rutile), apparently due to the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, while adsorbed rubidium ions form comparable amounts of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on surface charge density (pH), while the distribution of adsorbed Rb+ is almost independent of pH. A Surface Complexation Model (SCM) capable of accurately describing both the measured surface charge and the MD predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH-0.40) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH-range (2.7 10), illustrating the ability of positively and negatively charged surface groups to coexist. Complexation of the medium cations increases significantly with increasing negative surface charge and at pH 10 roughly 40 percent of the terminal sites are predicted to form cation complexes, while anion complexation is minor throughout the studied pH-range.« less

Coeval Formation of Aqueous Minerals on Mars

NASA Astrophysics Data System (ADS)

Fairen, A.; Uceda, E.; Gil, C.; Palmero Rodriguez, A.; Gago-Duport, L.

2015-12-01

Understanding the geochemical conditions on early Mars requires an explanation for the presence of sulfates and phyllosilicates, which must be also consistent with the absence of widespread sedimentary carbonates. In addition, sulfates and phyllosilicates do not generally occur together on Mars, which has been interpreted as a marker for detached mineral formation due to differing planetary environmental conditions separated dramatically, either in time or in space. Here, thermodynamic equilibrium calculations are used to determine the stability boundaries for phyllosilicates, ferrous and ferric sulfates, carbonates and iron oxyhydroxides precipitation on early Mars, at different atmospheric CO2 pressures and both under reducing and oxidizing conditions. Results suggest that phyllosilicates formed in mildly acidic to alkaline aqueous solutions, with a pH>4 for nontronite and a pH>6 for other smectites with low content in Fe and Mg (montmorillonite, saponite). Sulfate deposition dominates in solutions moderately to highly acidic, with a pH<6 conducive to the synthesis of kieserite. In the overlapping phyllosilicates/sulfates pH range, between 4 and 6, a competition for Mg between nontronite and kieserite is expected, and the formation of nontronite would be favored in areas where SiO2 activity in surface waters was high as a result of intense weathering of the early basaltic crust. Carbonates formed at pH>6, overlapping with the synthesis of low-Fe-Mg smectites. Model calculations anticipate the co-precipitation of smectites and siderite or any alteration product that could have resulted from the later substitution of Fe in siderite, such as Mg- or Mn-carbonate, triggering a competition for Mg between magnesite and low-Fe-Mg smectites. As expected, the model does not predict coeval synthesis of carbonates and sulfates. Goethite and other oxyhydroxides precipitate at pH below 2, a range at which jarosite and goethite are the expected iron-bearing phases. These results suggest that the major water-alteration products on the Martian surface were deposited simultaneously in space and in time, creating diverse geochemical conditions over the entire surface of a cold Mars during the wet Noachian/Hesperian times.

Optimization of enzymatic hydrolysis of guar gum using response surface methodology.

PubMed

Mudgil, Deepak; Barak, Sheweta; Khatkar, B S

2014-08-01

Guar gum is a polysaccharide obtained from guar seed endosperm portion. Enzymatically hydrolyzed guar gum is low in viscosity and has several health benefits as dietary fiber. In this study, response surface methodology was used to determine the optimum conditions for hydrolysis that give minimum viscosity of guar gum. Central composite was employed to investigate the effects of pH (3-7), temperature (20-60 °C), reaction time (1-5 h) and cellulase concentration (0.25-1.25 mg/g) on viscosity during enzymatic hydrolysis of guar (Cyamopsis tetragonolobus) gum. A second order polynomial model was developed for viscosity using regression analysis. Results revealed statistical significance of model as evidenced from high value of coefficient of determination (R(2) = 0.9472) and P < 0.05. Viscosity was primarily affected by cellulase concentration, pH and hydrolysis time. Maximum viscosity reduction was obtained when pH, temperature, hydrolysis time and cellulase concentration were 6, 50 °C, 4 h and 1.00 mg/g, respectively. The study is important in optimizing the enzymatic process for hydrolysis of guar gum as potential source of soluble dietary fiber for human health benefits.

Bicarbonate diffusion through mucus.

PubMed

Livingston, E H; Miller, J; Engel, E

1995-09-01

The mucus layer overlying duodenal epithelium maintains a pH gradient against high luminal acid concentrations. Despite these adverse conditions, epithelial surface pH remains close to neutrality. The exact nature of the gradient-forming barrier remains unknown. The barrier consists of mucus into which HCO3- is secreted. Quantification of the ability of HCO3- to establish and maintain the gradient depends on accurate measurement of this ion's diffusion coefficient through mucus. We describe new experimental and mathematical methods for diffusion measurement and report diffusion coefficients for HCO3- diffusion through saline, 5% mucin solutions, and rat duodenal mucus. The diffusion coefficients were 20.2 +/- 0.10, 3.02 +/- 0.31, and 1.81 +/- 0.12 x 10(-6) cm2/s, respectively. Modeling of the mucobicarbonate layer with this latter value suggests that for conditions of high luminal acid strength the neutralization of acid by HCO3- occurs just above the epithelial surface. Under these conditions the model predicts that fluid convection toward the lumen could be important in maintaining the pH gradient. In support of this hypothesis we were able to demonstrate a net luminal fluid flux of 5 microliters.min-1.cm-2 after perfusion of 0.15 N HCl in the rat duodenum.

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

NASA Astrophysics Data System (ADS)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Initial bioadhesion on dental materials as a function of contact time, pH, surface wettability, and isoelectric point.

PubMed

Müller, Christine; Lüders, Anne; Hoth-Hannig, Wiebke; Hannig, Matthias; Ziegler, Christiane

2010-03-16

The adsorption of bovine serum albumin (BSA) on surfaces of dental enamel and of dental materials was investigated by scanning force spectroscopy. This method provides adhesion forces which can be measured as a function of contact time between protein and surface, pH, wettability, and isoelectric point of the surface. Whereas the chosen ceramic and composite materials resemble very well the adhesion on natural enamel, a much stronger adhesion was found for the more hydrophobic surfaces, that is, gold, titanium, poly(methyl methacrylate) (PMMA), and poly(tetrafluoroethylene) (PTFE). On hydrophilic surfaces, adhesion is mainly influenced by the electrostatic forces between protein and surface. However, the conformational change of BSA at pH values above pH 8 has to be taken into account. On the very hydrophobic PTFE surface, the special interface structure between PTFE and water plays an important role which governs BSA adhesion.

Differential potentiometric titration: development of a methodology for determining the point of zero charge of metal (hydr)oxides by one titration curve.

PubMed

Bourikas, Kyriakos; Kordulis, Christos; Lycourghiotis, Alexis

2005-06-01

A new methodology is presented, called differential potentiometric titration (DPT), which allows the determination of the point of zero charge (pzc) of metal (hydr)oxides using only one potentiometric curve. By performing extensive simulations of potentiometric titrations for various model (hydr)oxides, we found that an inflection point in a H+(cons,surf) versus pH potentiometric curve (H+(cons,surf): hydrogen ions consumed on the surface of the (hydr)oxide) and a peak in the corresponding differential curve, dH+(cons,surf)/dpH versus pH, appear at a pH equal to the pzc assumed for a model (hydr)oxide. This distinguishable peak appears at the same position irrespective of the surface ionization and the interfacial model adopted as well as the assumed ionic strength. It was found that the aforementioned peak also appears in the high-resolution differential potentiometric curves experimentally determined for four oxides (SiO2, TiO2, gamma-Al2O3, and MgO) that are widely used in various environmental and other technological applications. The application of DPT to the above-mentioned oxides provided practically the same pzc values as the corresponding ones achieved by using four different techniques as well as the corresponding isoelectric point (iep) values determined by microelectrophoresis. Differences between the pzc and iep values determined using various techniques in the case of MgO were attributed to the increasing dissolution of this oxide as pH decreases and the adsorption of cations (Mg2+, Na+) on the MgO/electrolytic solution interface.

Endogenous cyclo-oxygenase activity regulates mouse gastric surface pH

PubMed Central

Baumgartner, Heidi K; Kirbiyik, Uzay; Coskun, Tamer; Chu, Shaoyou; Montrose, Marshall H

2002-01-01

In the stomach, production of prostaglandins by cyclo-oxygenase (COX) is believed to be important in mucosal defence. We tested the hypothesis that endogenous COX activity is required for protective gastric surface pH control. Intact stomachs of anaesthetized mice were perfused with a weakly buffered solution (150 mmNaCl + 4 mm Homopipes) at pH values from 2.5 to 7.0. Gastric effluents were collected to measure pH and estimate amounts of acid or alkali secretion in nanomoles secreted per minute. A switch from net acid to net alkali secretion was seen in response to acidifying luminal pH with an apparent ‘set point’ between pH 4 and 5. At luminal pH 3, the net alkali secretion (12.7 ± 2.8 nmol OH− equivalents min−1) was abolished (2.2 ± 1.7 nmol OH− min−1) by the non-specific COX inhibitor indomethacin (5 mg kg−1 I.P.). Similar inhibition was observed using a COX-1 inhibitor (SC-560; 10 mg kg−1 I.P.), but not a COX-2 inhibitor (NS-398; 10 mg kg−1 I.P.). Subsequent treatment with 16,16-dimethyl prostaglandin E2 (dm-PGE2; 1 mg kg−1 I.P.) rescued the alkali secretion (21.8 ± 2.7 nmol OH− min−1). In either the absence or presence of the H+,K+-ATPase inhibitor omeprazole (60 mg kg−1 I.P.), indomethacin blocked similar amounts of net alkali secretion (10.5 ± 2.7 and 16.4 ± 3.4 nmol OH− min−1, respectively). We also used in vivo confocal microscopy to examine pH near the mucosal surface. The gastric mucosal surface of anaesthetized mice was exposed and mucosal surface pH was imaged using the fluorescence intensity ratio of Cl-NERF as a pH indicator. Results showed a switch from a continuous net acid to net alkali secretion by the stomach in response to changing superfusate pH from 5 to 3. At luminal pH 3, the relatively alkaline surface pH (4.3 ± 0.1) was acidified (3.6 ± 0.2) by indomethacin, and subsequent dm-PGE2 restored surface pH (4.2 ± 0.2). We conclude that the pre-epithelial alkaline layer is regulated by endogenous COX activity. PMID:12411530

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

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

Using present-day observations to detect when anthropogenic change forces surface ocean carbonate chemistry outside preindustrial bounds

NASA Astrophysics Data System (ADS)

Sutton, Adrienne J.; Sabine, Christopher L.; Feely, Richard A.; Cai, Wei-Jun; Cronin, Meghan F.; McPhaden, Michael J.; Morell, Julio M.; Newton, Jan A.; Noh, Jae-Hoon; Ólafsdóttir, Sólveig R.; Salisbury, Joseph E.; Send, Uwe; Vandemark, Douglas C.; Weller, Robert A.

2016-09-01

One of the major challenges to assessing the impact of ocean acidification on marine life is detecting and interpreting long-term change in the context of natural variability. This study addresses this need through a global synthesis of monthly pH and aragonite saturation state (Ωarag) climatologies for 12 open ocean, coastal, and coral reef locations using 3-hourly moored observations of surface seawater partial pressure of CO2 and pH collected together since as early as 2010. Mooring observations suggest open ocean subtropical and subarctic sites experience present-day surface pH and Ωarag conditions outside the bounds of preindustrial variability throughout most, if not all, of the year. In general, coastal mooring sites experience more natural variability and thus, more overlap with preindustrial conditions; however, present-day Ωarag conditions surpass biologically relevant thresholds associated with ocean acidification impacts on Mytilus californianus (Ωarag < 1.8) and Crassostrea gigas (Ωarag < 2.0) larvae in the California Current Ecosystem (CCE) and Mya arenaria larvae in the Gulf of Maine (Ωarag < 1.6). At the most variable mooring locations in coastal systems of the CCE, subseasonal conditions approached Ωarag = 1. Global and regional models and data syntheses of ship-based observations tended to underestimate seasonal variability compared to mooring observations. Efforts such as this to characterize all patterns of pH and Ωarag variability and change at key locations are fundamental to assessing present-day biological impacts of ocean acidification, further improving experimental design to interrogate organism response under real-world conditions, and improving predictive models and vulnerability assessments seeking to quantify the broader impacts of ocean acidification.

Erosion and attrition of human enamel in vitro part I: interaction effects.

PubMed

Eisenburger, M; Addy, M

2002-01-01

The aim of the study in vitro was to measure the interplay of attrition and erosion of human enamel under several different pH conditions. Cusp and smooth surface enamel specimens were prepared from unerupted human third molar teeth. Cusp and smooth surface specimens opposed each other in a wear machine under a load of 600 g. The machine simulated tooth grinding for 30 min (2280 wear cycles). Six groups of 10 specimens were worn in the following environmental conditions: saline, citric acid at pH values of 3.2, 5.5 or 7.0 and two cycling groups (pH 3.2/saline or saline/pH 3.2). Additionally, 10 smooth surface specimens were exposed to the same fluids without attrition. Tissue loss on smooth surface specimens was determined by profilometry. The worn specimen surfaces were studied by SEM. Attrition depth in saline and pH 7.0 citric acid was 25.5 microm. At pH 3.2 and 5.5 attrition depths were 6.0 and 4.3 microm, respectively. Cycling in saline/citric acid and vice versa produced attrition depths of 9.2 and 7.9 microm, respectively. In the erosion only specimens lesion depths were 3.0, 1.2 and 0 microm at pH 3.2, 5.5 and 7.0 and saline, respectively. Attrition specimens at pH 7.0 and in saline showed very rough surfaces. At low pH enamel surfaces appeared flat and smooth. Enamel wear in neutral conditions is significantly higher than in acidic conditions (p < 0.05), apparently due to a smoothing effect of erosion on contacting surfaces. Copyright 2002 Elsevier Science Ltd.

The removal of chloramphenicol from water through adsorption on activated carbon

NASA Astrophysics Data System (ADS)

Lach, Joanna; Ociepa-Kubicka, Agnieszka

2017-10-01

The presented research investigated the removal of chloramphenicol from water solutions on selected activated carbon available in three grades with different porous structure and surface chemical composition. Two models of adsorption kinetics were examined, i.e. the pseudo-first order and the pseudo-second order models. For all examined cases, the results of tests with higher value of coefficient R2 were described by the equation for pseudo-second order kinetics. The adsorption kinetics was also investigated on the activated carbons modified with ozone. The measurements were taken from the solutions with pH values of 2 and 7. Chloramphenicol was the most efficiently adsorbed on the activated carbon F-300 from the solutions with pH=7, and on the activated carbon ROW 08 Supra from the solutions with pH=2. The adsorption of this antibiotic was in the majority of cases higher from the solutions with pH=2 than pH=7. The modification of the activated carbons with ozone enhanced their adsorption capacities for chloramphenicol. The adsorption is influenced by the modification method of activated carbon (i.e. the duration of ozonation of the activated carbon solution and the solution temperature). The results were described with the Freundlich and Langmuir adsorption isotherm equations. Both models well described the obtained results (high R2 values).

Bacterial growth on a superhydrophobic surface containing silver nanoparticles

NASA Astrophysics Data System (ADS)

Heinonen, S.; Nikkanen, J.-P.; Laakso, J.; Raulio, M.; Priha, O.; Levänen, E.

2013-12-01

The antibacterial effect of silver can be exploited in the food and beverage industry and medicinal applications to reduce biofouling of surfaces. Very small amount of silver ions are enough to destructively affect the metabolism of bacteria. Moreover, superhydrophobic properties could reduce bacterial adhesion to the surface. In this study we fabricated superhydrophobic surfaces that contained nanosized silver particles. The superhydrophobic surfaces were manufactured onto stainless steel as combination of ceramic nanotopography and hydrophobication by fluorosilane. Silver nanoparticles were precipitated onto the surface by a chemical method. The dissolution of silver from the surface was tested in an aqueous environment under pH values of 1, 3, 5, 7, 9, 11 and 13. The pH value was adjusted with nitric acid and ammonia. It was found that dissolution rate of silver increased as the pH of the solution altered from the pH of de-ionized water to lower and higher pH values but dissolution occurred also in de-ionized water. The antimicrobial potential of this coating was investigated using bacterial strains isolated from the brewery equipment surfaces. The results showed that the number of bacteria adhering onto steel surface was significantly reduced (88%) on the superhydrophobic silver containing coating.

Predictive microbiology in food packaging applications

USDA-ARS?s Scientific Manuscript database

Predictive microbiology including growth, inactivation, surface transfer (or cross-contamination), and survival, plays important roles in understanding microbial food safety. Growth models may involve the growth potential of a specified pathogen under different stresses, e.g., temperature, pH, wate...

Optimization of Bromelain-Aided Production of Angiotensin I-Converting Enzyme Inhibitory Hydrolysates from Stone Fish Using Response Surface Methodology.

PubMed

Muhammad Auwal, Shehu; Zarei, Mohammad; Abdul-Hamid, Azizah; Saari, Nazamid

2017-03-31

The stone fish is an under-utilized sea cucumber with many nutritional and ethno-medicinal values. This study aimed to establish the conditions for its optimum hydrolysis with bromelain to generate angiotensin I-converting enzyme (ACE)-inhibitory hydrolysates. Response surface methodology (RSM) based on a central composite design was used to model and optimize the degree of hydrolysis (DH) and ACE-inhibitory activity. Process conditions including pH (4-7), temperature (40-70 °C), enzyme/substrate (E/S) ratio (0.5%-2%) and time (30-360 min) were used. A pH of 7.0, temperature of 40 °C, E/S ratio of 2% and time of 240 min were determined using a response surface model as the optimum levels to obtain the maximum ACE-inhibitory activity of 84.26% at 44.59% degree of hydrolysis. Hence, RSM can serve as an effective approach in the design of experiments to improve the antihypertensive effect of stone fish hydrolysates, which can thus be used as a value-added ingredient for various applications in the functional foods industries.

Toxin studies using an integrated biophysical and structural biology approach.

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

Last, Julie A.; Schroeder, Anne E.; Slade, Andrea Lynn

2005-03-01

Clostridial neurotoxins, such as botulinum and tetanus, are generally thought to invade neural cells through a process of high affinity binding mediated by gangliosides, internalization via endosome formation, and subsequent membrane penetration of the catalytic domain activated by a pH drop in the endosome. This surface recognition and internalization process is still not well understood with regard to what specific membrane features the toxins target, the intermolecular interactions between bound toxins, and the molecular conformational changes that occur as a result of pH lowering. In an effort to elucidate the mechanism of tetanus toxin binding and permeation through the membranemore » a simple yet representative model was developed that consisted of the ganglioside G{sub tlb} incorporated in a bilayer of cholesterol and DPPC (dipalmitoylphosphatidyl choline). The bilayers were stable over time yet sensitive towards the binding and activity of whole toxin. A liposome leakage study at constant pH as well as with a pH gradient, to mimic the processes of the endosome, was used to elucidate the effect of pH on the toxin's membrane binding and permeation capability. Topographic imaging of the membrane surface, via in situ tapping mode AFM, provided nanoscale characterization of the toxin's binding location and pore formation activity.« less

Nitroimidazoles adsorption on activated carbon cloth from aqueous solution.

PubMed

Ocampo-Pérez, R; Orellana-Garcia, F; Sánchez-Polo, M; Rivera-Utrilla, J; Velo-Gala, I; López-Ramón, M V; Alvarez-Merino, M A

2013-07-01

The objective of this study was to analyze the equilibrium and adsorption kinetics of nitroimidazoles on activated carbon cloth (ACC), determining the main interactions responsible for the adsorption process and the diffusion mechanism of these compounds on this material. The influence of the different operational variables, such as ionic strength, pH, temperature, and type of water (ultrapure, surface, and waste), was also studied. The results obtained show that the ACC has a high capacity to adsorb nitroimidazoles in aqueous solution. Electrostatic interactions play an important role at pH<3, which favors the repulsive forces between dimetridazole or metronidazole and the ACC surface. The formation of hydrogen bonds and dispersive interactions play the predominant role at higher pH values. Modifications of the ACC with NH3, K2S2O8, and O3 demonstrated that its surface chemistry plays a predominant role in nitroimidazole adsorption on this material. The adsorption capacity of ACC is considerably high in surface waters and reduced in urban wastewater, due to the levels of alkalinity and dissolved organic matter present in the different types of water. Finally, the results of applying kinetic models revealed that the global adsorption rate of dimetridazole and metronidazole is controlled by intraparticle diffusion. Copyright © 2013 Elsevier Inc. All rights reserved.

Electrostatic model for protein adsorption in ion-exchange chromatography and application to monoclonal antibodies, lysozyme and chymotrypsinogen A.

PubMed

Guélat, Bertrand; Ströhlein, Guido; Lattuada, Marco; Morbidelli, Massimo

2010-08-27

A model for the adsorption equilibrium of proteins in ion-exchange chromatography explicitly accounting for the effect of pH and salt concentration in the limit of highly diluted systems was developed. It is based on the use of DLVO theory to estimate the electrostatic interactions between the charged surface of the ion-exchanger and the proteins. The corresponding charge distributions were evaluated as a function of pH and salt concentration using a molecular approach. The model was verified for the adsorption equilibrium of lysozyme, chymotrypsinogen A and four industrial monoclonal antibodies on two strong cation-exchangers. The adsorption equilibrium constants of these proteins were determined experimentally at various pH values and salt concentrations and the model was fitted with a good agreement using three adjustable parameters for each protein in the whole range of experimental conditions. Despite the simplifications of the model regarding the geometry of the protein-ion-exchanger system, the physical meaning of the parameters was retained. 2010 Elsevier B.V. All rights reserved.

Scanning tunneling microscopy study of low temperature silicon epitaxy on hydrogen/silicon(001) and phosphine adsorption on silicon(111)-7x7

NASA Astrophysics Data System (ADS)

Ji, Jeong-Young

A three-chamber ultra-high-vacuum (UHV) system with preparation, scanning tunneling microscopy (STM), and chemical vapor deposition (CVD) chambers was designed and built. Here, one can perform surface preparation, STM e-beam lithography, precursor gas dosing, ion sputtering, silicon epitaxy, and various measurements such as reflection high energy electron diffraction (RHEED), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES). Processes performed in the ultra-clean preparation and gas-filled CVD chambers can be monitored by transferring the samples back to the STM chamber to take topographical images. Si deposition on H-terminated Si(001)-2x1 surfaces at temperatures 300--530 K was studied by scanning tunneling microscopy. Hydrogen apparently hinders Si adatom diffusion and enhances surface roughening. Post-growth annealing transfers the top layer atoms downward to fill in vacancies in the lower layer, restoring the crystallinity of the thin film. Hydrogen is shown to remain on the growth front up to at least 10 ML. Si deposition onto the H/Si(001)-3x1 surface at 530 K suggests that dihydride units further suppress Si adatom diffusion and increase surface roughness. PH3 adsorption on Si(111)-7x7 was studied for various exposures between 0.3--60 L at room temperature by means of the scanning-tunneling-microscopy (STM). PH3-, PH2-, H-reacted, and unreacted adatoms can be identified by analyzing STM images at different sample biases. Most of PH3 adsorbs dissociatively on the surface at initial exposure, generating H and PH2 adsorption sites, followed by molecular adsorption of PH3. Rest atoms are more reactive than the adatoms and PH 2-reacted rest atom sites are also observed in STM images. Statistical analysis shows that center adatoms are more reactive than corner adatoms and the saturation P coverage is ˜0.22 ML. Finally, 900 K annealing of a PH 3 dosed surface results in a disordered, partially P-covered surface and PH3 dosing at 900 K forms the same surface reconstruction as a P2-adsorbed surface at similar temperature.

Optimization of pH sensing using silicon nanowire field effect transistors with HfO2 as the sensing surface.

PubMed

Zafar, Sufi; D'Emic, Christopher; Afzali, Ali; Fletcher, Benjamin; Zhu, Y; Ning, Tak

2011-10-07

Silicon nanowire field effect transistor sensors with SiO(2)/HfO(2) as the gate dielectric sensing surface are fabricated using a top down approach. These sensors are optimized for pH sensing with two key characteristics. First, the pH sensitivity is shown to be independent of buffer concentration. Second, the observed pH sensitivity is enhanced and is equal to the Nernst maximum sensitivity limit of 59 mV/pH with a corresponding subthreshold drain current change of ∼ 650%/pH. These two enhanced pH sensing characteristics are attributed to the use of HfO(2) as the sensing surface and an optimized fabrication process compatible with silicon processing technology.

Spatial variability of surface-sediment porewater pH and related water-column characteristics in deep waters of the northern South China Sea

NASA Astrophysics Data System (ADS)

Shao, Changgao; Sui, Yi; Tang, Danling; Legendre, Louis

2016-12-01

This study analyzes the pH of surface-sediment porewater (i.e. 2-3 cm below the water-sediment interface), and concentrations of CaCO3 and organic carbon (OC) in 1192 sediment cores from the northern South China Sea, in water depths ranging from 137 to 3702 m. This is the first study in the literature to analyze the large-scale spatial variability of deep-water surface-sediment pH over a large ocean basin. The data showed strong spatial variations in pH. The lowest pH values (<7.3) were observed south of Hainan Island, an area that is affected by summer upwelling and freshwater runoff from the Pearl and Red Rivers. Moderately low pH values (generally 7.3-7.5) occurred in two other areas: a submarine canyon, where sediments originated partly from the Pearl River and correspond to a paleo-delta front during the last glacial period; and southwest of Taiwan Island, where waters are affected by the northern branch of the Kuroshio intrusion current (KIC) and runoff from Taiwan rivers. The surface sediments with the highest pH (⩾7.5, and up to 8.3) were located in a fourth area, which corresponded to the western branch of the KIC where sediments have been intensively eroded by bottom currents. The pH of surface-sediment porewater was significantly linearly related to water depth, bottom-water temperature, and CaCO3 concentration (p < 0.05 for the whole sampling area). This study shows that the pH of surface-sediment porewater can be sensitive to characteristics of the overlying water column, and suggests that it will respond to global warming as changes in surface-ocean temperature and pH progressively reach deeper waters.

Effect of Na+ impregnated activated carbon on the adsorption of NH4(+)-N from aqueous solution.

PubMed

Shi, Mo; Wang, Zhengfang; Zheng, Zheng

2013-08-01

Two kinds of activated carbons modified by Na+ impregnation after pre-treatments involving oxidation by nitric acid or acidification by hydrochloric acid (denoted as AC/N-Na and AC/HCl-Na, respectively), were used as adsorbents to remove NH4(+)-N. The surface features of samples were investigated by BET, SEM, XRD and FT-IR. The adsorption experiments were conducted in equilibrium and kinetic conditions. Influencing factors such as initial solution pH and initial concentration were investigated. A possible mechanism was proposed. Results showed that optimal NH4(+)-N removal efficiency was achieved at a neutral pH condition for the modified ACs. The Langmuir isotherm adsorption equation provided a better fit than other models for the equilibrium study. The adsorption kinetics followed both the pseudo second-order kinetics model and intra-particle kinetic model. Chemical surface analysis indicated that Na+ ions form ionic bonds with available surface functional groups created by pre-treatment, especially oxidation by nitric acid, thus increasing the removal efficiency of the modified ACs for NH4(+)-N. Na(+)-impregnated ACs had a higher removal capability in removing NH4(+)-N than unmodified AC, possibly resulting from higher numbers of surface functional groups and better intra-particle diffusion. The good fit of Langmuir isotherm adsorption to the data indicated the presence of monolayer NH4(+)-N adsorption on the active homogenous sites within the adsorbents. The applicability of pseudo second-order and intra-particle kinetic models revealed the complex nature of the adsorption mechanism. The intra-particle diffusion model revealed that the adsorption process consisted not only of surface adsorption but also intra-particle diffusion.

Determining SAFOD area microearthquake locations solely with the Pilot Hole seismic array data

NASA Astrophysics Data System (ADS)

Oye, Volker; Chavarria, J. Andres; Malin, Peter E.

2004-05-01

In August 2002, an array of 32 three-component geophones was installed in the San Andreas Fault Observatory at Depth (SAFOD) Pilot Hole (PH) at Parkfield, CA. As an independent test of surface-observation-based microearthquake locations, we have located such events using only data recorded on the PH array. We then compared these locations with locations from a combined set of PH and Parkfield High Resolution Seismic Network (HRSN) observations. We determined the uncertainties in the locations as they relate to errors in the travel time picks and the velocity model by the bootstrap method. Based on the PH and combined locations, we find that the ``C2'' cluster to the northeast of the PH has the smallest location uncertainties. Events in this cluster also have the most similar waveforms and largest magnitudes. This confirms earlier suggestions that the C2 cluster is a promising target for the SAFOD Main Hole.

Observation of Iron Specific Interaction with a Charge Neutral Phospholipid

NASA Astrophysics Data System (ADS)

Wang, Wenjie; Zhang, Honghu; Feng, Shuren; San Emeterio, Josue; Kuzmenko, Ivan; Nilsen-Hamilton, Marit; Mallapragada, Surya; Vaknin, David

2015-03-01

Using surface sensitive X-ray scattering and spectroscopic techniques we show that phosphatidyl choline (PC) head groups attract positively charged iron ions and complexes even at pH values that are lower than 3. DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) is a zwitterionic lipid typically used as a model system for cell membranes. Within a large pH range (3 -11), it carries a negative charge on the phosphate group and a positive charge on the quaternary ammonium cation, thus appears charge neutral. Further lowering the pH, i.e. adding a proton to the phosphate group, results in a positively charged headgroup. Surprisingly, we detect significant enrichment of iron at the interface of the DPPC monolayer and the aqueous subphase with the pH maintained at 3 or even lower. With a supposedly charge neutral or even positive surface, the observation of surface bound, charge positive iron ions or iron hydroxides is counter-intuitive and suggests iron-specific interaction with the phospholipid headgroup, which is not governed by electrostatic interaction. The effect of the integration of Mms6, a membrane protein that promotes the formation of magnetic nanocrystals, into the DPPC monolayer will also be discussed. Research supported by the U.S. Department of Energy under Contract No. DE-AC02-07CH11358 and DE-AC02-06CH11357.

A review on the kinetics of microbially induced calcium carbonate precipitation by urea hydrolysis

NASA Astrophysics Data System (ADS)

van Paassen, L. A.

2017-12-01

In this study the kinetics of calcium carbonate precipitation induced by the ureolytic bacteria are reviewed based on experiments and mathematical modelling. The study shows how urea hydrolysis rate depends on the amount of bacteria and the conditions during growth, storage, hydrolysis and precipitation. The dynamics of Microbially Induced Carbonate Precipitation has been monitored in non-seeded liquid batch experiments. Results show that particulary for a fast hydrolysis of urea (>1 M-urea day-1) in a highly concentrated equimolar solution with calcium chloride (>0.25 M) the solubility product of CaCO3 is exceeded within a short period (less than 30 minutes), the supersaturation remains high for an exended period, resulting in prolonged periods of nucleation and crystal growth and extended growth of metastable precursor mineral phases. The pH, being a result of the speciation, quickly rises until critical supersaturation is reached and precipitation is initiated. Then pH drops (sometimes showing oscillating behaviour) to about neutral where it stays until all substrates are depleted. Higher hydrolysis rates lead to higher supersaturation and pH and relatively many small crystals, whereas higher concentrations of urea and calcium chloride mainly lead to lower pH values. The conversion can be reasonably monitored by electrical conductivity and reasonably predicted, using a simplified model based on a single reaction as long as the urea hydrolysis rate is known. Complex geochemical models, which include chemical speciciation through acid-base equilibria and kinetic equations to describe mineral precipitation, do not show significant difference from the simplified model regarding the bulk chemistry and the total amount of precipitates. However, experiments show that ureolytic MICP can result in a highly variable crystal morphologies with large variation in the affected hydraulic properties when applied in a porous medium. In order to calculate the number, size and type of crystals, use of these more complex models is essential. Quantitative prediction to a level at which the pH and conductivity are simulated accurately is not yet possible as experimental data regarding the interaction between existing mineral surfaces are the surface interaction between ions and micro-organisms is still lacking.

Evaluation and improvement of micro-surfacing mix design method and modelling of asphalt emulsion mastic in terms of filler-emulsion interaction

NASA Astrophysics Data System (ADS)

Robati, Masoud

This Doctorate program focuses on the evaluation and improving the rutting resistance of micro-surfacing mixtures. There are many research problems related to the rutting resistance of micro-surfacing mixtures that still require further research to be solved. The main objective of this Ph.D. program is to experimentally and analytically study and improve rutting resistance of micro-surfacing mixtures. During this Ph.D. program major aspects related to the rutting resistance of micro-surfacing mixtures are investigated and presented as follow: 1) evaluation of a modification of current micro-surfacing mix design procedures: On the basis of this effort, a new mix design procedure is proposed for type III micro-surfacing mixtures as rut-fill materials on the road surface. Unlike the current mix design guidelines and specification, the new mix design is capable of selecting the optimum mix proportions for micro-surfacing mixtures; 2) evaluation of test methods and selection of aggregate grading for type III application of micro-surfacing: Within the term of this study, a new specification for selection of aggregate grading for type III application of micro-surfacing is proposed; 3) evaluation of repeatability and reproducibility of micro-surfacing mixture design tests: In this study, limits for repeatability and reproducibility of micro-surfacing mix design tests are presented; 4) a new conceptual model for filler stiffening effect on asphalt mastic of micro-surfacing: A new model is proposed, which is able to establish limits for minimum and maximum filler concentrations in the micro-surfacing mixture base on only the filler important physical and chemical properties; 5) incorporation of reclaimed asphalt pavement and post-fabrication asphalt shingles in micro-surfacing mixture: The effectiveness of newly developed mix design procedure for micro-surfacing mixtures is further validated using recycled materials. The results present the limits for the use of RAP and RAS amount in micro-surfacing mixtures; 6) new colored micro-surfacing formulations with improved durability and performance: The significant improvement of around 45% in rutting resistance of colored and conventional micro-surfacing mixtures is achieved through employing low penetration grade bitumen polymer modified asphalt emulsion stabilized using nanoparticles.

Nickel adsorption on chalk and calcite.

PubMed

Belova, D A; Lakshtanov, L Z; Carneiro, J F; Stipp, S L S

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi=-1.12 on calcite and log KNi=-0.43 and -0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure.

PubMed

Guo, Xuejun; Wu, Zhijun; He, Mengchang; Meng, Xiaoguang; Jin, Xin; Qiu, Nan; Zhang, Jing

2014-07-15

Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl3, was oxidized into Sb(V) probably due to the involvement of O2 in the long duration of sample preservation. Only one Sb-Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0-1.9 attributed to bidentate mononuclear edge-sharing ((2)E) between Sb and HFO. Copyright © 2014 Elsevier B.V. All rights reserved.

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Modeling of bromate formation by ozonation of surface waters in drinking water treatment.

PubMed

Legube, Bernard; Parinet, Bernard; Gelinet, Karine; Berne, Florence; Croue, Jean-Philippe

2004-04-01

The main objective of this paper is to try to develop statistically and chemically rational models for bromate formation by ozonation of clarified surface waters. The results presented here show that bromate formation by ozonation of natural waters in drinking water treatment is directly proportional to the "Ct" value ("Ctau" in this study). Moreover, this proportionality strongly depends on many parameters: increasing of pH, temperature and bromide level leading to an increase of bromate formation; ammonia and dissolved organic carbon concentrations causing a reverse effect. Taking into account limitation of theoretical modeling, we proposed to predict bromate formation by stochastic simulations (multi-linear regression and artificial neural networks methods) from 40 experiments (BrO(3)(-) vs. "Ctau") carried out with three sand filtered waters sampled on three different waterworks. With seven selected variables we used a simple architecture of neural networks, optimized by "neural connection" of SPSS Inc./Recognition Inc. The bromate modeling by artificial neural networks gives better result than multi-linear regression. The artificial neural networks model allowed us classifying variables by decreasing order of influence (for the studied cases in our variables scale): "Ctau", [N-NH(4)(+)], [Br(-)], pH, temperature, DOC, alkalinity.

Influence of Surface Sorption Processes on Spectral Induced Polarization Evaluated Using in-Situ Monitoring of a Na-22 Tracer

NASA Astrophysics Data System (ADS)

Hao, N.; Moysey, S. M.; Powell, B. A.; Ntarlagiannis, D.

2014-12-01

Spectral Induced Polarization (SIP) has been used to monitor subsurface biogeochemical processes in a variety of lab and field studies. However, there are several competing mechanisms that have been proposed to explain the SIP effect. This work targets the influence of ion sorption to mineral surfaces as a controlling factor on SIP utilizing a pH dependent surface adsorption experiment. In this experiment we use silica gel as an idealized medium where the number of available sites for cation sorption, which in this case is limited to Na+ and H+ ions, is influenced by changes in pH via protonation/deprotonation of silanol groups. The experiment uses 22Na as an in situ tracer as the radioactive decay of this nuclide can be continuously and non-invasively monitored using sensors placed outside of a column. The experiment was conducted by continuously pumping a 0.01M NaCl solution spiked with of 1μCi/L 22Na in to the column under three pH conditions (pH 5.0, 6.0 and 8.0). In the experiment, we observed an increasing number of gamma counts caused by the accumulation of sorbed 22Na in the column as we increased the pH from 5.0 to 6.5, and finally to 8.0. Simultaneously, we observed a linearly correlated (R2 = 0.99) rise in the imaginary conductivity response of the SIP measurements. Using the triple layer electrochemical polarization model for grain polarization to simulate our experimental SIP responses, we found that the estimated surface site density is within a factor of two of that estimated from the mass accumulation of sodium. Since the accumulation of sodium on the silica gel surface is responsible for both the increase in gamma radiation and the change in the electrical response, these observations support the theory that mobile ions in the Stern layer of mineral surfaces provide the primary control on SIP signals in silicate materials.

The O2, pH and Ca2+ Microenvironment of Benthic Foraminifera in a High CO2 World

PubMed Central

Glas, Martin S.; Fabricius, Katharina E.; de Beer, Dirk; Uthicke, Sven

2012-01-01

Ocean acidification (OA) can have adverse effects on marine calcifiers. Yet, phototrophic marine calcifiers elevate their external oxygen and pH microenvironment in daylight, through the uptake of dissolved inorganic carbon (DIC) by photosynthesis. We studied to which extent pH elevation within their microenvironments in daylight can counteract ambient seawater pH reductions, i.e. OA conditions. We measured the O2 and pH microenvironment of four photosymbiotic and two symbiont-free benthic tropical foraminiferal species at three different OA treatments (∼432, 1141 and 2151 µatm pCO2). The O2 concentration difference between the seawater and the test surface (ΔO2) was taken as a measure for the photosynthetic rate. Our results showed that O2 and pH levels were significantly higher on photosymbiotic foraminiferal surfaces in light than in dark conditions, and than on surfaces of symbiont-free foraminifera. Rates of photosynthesis at saturated light conditions did not change significantly between OA treatments (except in individuals that exhibited symbiont loss, i.e. bleaching, at elevated pCO2). The pH at the cell surface decreased during incubations at elevated pCO2, also during light incubations. Photosynthesis increased the surface pH but this increase was insufficient to compensate for ambient seawater pH decreases. We thus conclude that photosynthesis does only partly protect symbiont bearing foraminifera against OA. PMID:23166810

In-Situ and Experimental Evidence for Acidic Weathering of Rocks and Soils on Mars

NASA Technical Reports Server (NTRS)

Hurowitz, J. A.; McLennan, S. M.; Tosca, N. J.; Arvidson, R. E.; Michalski, J. R.; Ming, D.; Schroeder, C.; Squyres, S. W.

2006-01-01

Experimental data for alteration of synthetic Martian basalts at pH=0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock analyses from Gusev crater are well described by the relationships apparent from low pH experimental alteration data. A model for rock surface alteration is developed which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low fluid-to-rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low fluid to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of FeO and MgO, consistent with alteration of olivine-bearing basalt and subsequent precipitation of FeO and MgO bearing secondary minerals as the primary control on soil geochemistry.

Role of Self-Association and Supersaturation in Oral Absorption of a Poorly Soluble Weakly Basic Drug.

PubMed

Narang, Ajit S; Badawy, Sherif; Ye, Qingmei; Patel, Dhaval; Vincent, Maria; Raghavan, Krishnaswamy; Huang, Yande; Yamniuk, Aaron; Vig, Balvinder; Crison, John; Derbin, George; Xu, Yan; Ramirez, Antonio; Galella, Michael; Rinaldi, Frank A

2015-08-01

Precipitation of weakly basic drugs in intestinal fluids can affect oral drug absorption. In this study, the implications of self-association of brivanib alaninate in acidic aqueous solution, leading to supersaturation at basic pH condition, on its solubility and oral absorption were investigated. Self-association of brivanib alaninate was investigated by proton NMR spectroscopy, surface tension measurement, dynamic light scattering, isothermal titration calorimetry, and molecular modeling. Drug solubility was determined in various pH media, and its tendency to supersaturate upon pH shift was investigated in buffered and biorelevant aqueous solutions. Pharmacokinetic modeling of human oral drug absorption was utilized for parameter sensitivity analyses of input variables. Brivanib alaninate exhibited continuous, and pH- and concentration-dependent self-association. This phenomenon resulted in positive deviation of drug solubility at acidic pH and the formation of a stable supersaturated drug solution in pH-shift assays. Consistent with the supersaturation phenomenon observed in vitro, oral absorption simulations necessitated invoking long precipitation time in the intestine to successfully predict in vivo data. Self-association of a weakly basic drug in acidic aqueous solution can increase its oral absorption by supersaturation and precipitation resistance at the intestinal pH. This consideration is important to the selection of parameters for oral absorption simulation.

Investigation of pH response and photo-control of wettability on spiropyran-derivatized surfaces

NASA Astrophysics Data System (ADS)

Park, Choong-Do

2009-12-01

One promising method to control a liquid drop on a surface for microfluidic devices is to use the surface tension gradient on a photo-responsive surface by light irradiation. A photo-switchable spiropyran monolayer was prepared on smooth glass or silicon wafers via 3-aminopropylmethyldiethoxysilane linkages. The pH response of the surface-bound spiropyran was investigated by measuring contact angle as a function of pH, since the pH value of the liquids applied to a microfluidic system can vary widely. Based on the contact angle titration and UV-Vis spectroscopic data, a protonation and deprotonation mechanism of the surface-bound spiropyran was proposed. The advancing contact angles under UV and under visible light irradiation at high pH values were about 100 smaller than those at low pH values. The decrease in contact angle under UV light with decreasing pH value was assigned to the protonation of open merocyanine (MC) to MC-OH+. Meanwhile, the decrease in contact angle under visible light was attributed to the protonation of the closed spiropryan (SP), generating a mixed state of MC-OH+ in equilibrium with N-protonated SP-NH+. In order to examine the possibility of light-induced liquid drop motion on the spiropyran-derivatized smooth surfaces, the light-induced surface tension change between SP and MC was estimated using the contact angle hysteresis (CAH) and the Lifshitz---van der Waals/Acid-Base (LWAB) approaches based on the contact angle data. The average light-induced surface energy change between the two isomers under UV and visible light exposure was 1.4 mJ/m 2, implying that the small change in surface tension is not sufficient to move a liquid droplet on the surface. Liquid drop motion requires that the light-induced switching angle be greater than the contact angle hysteresis. However, the light-induced switching angle of the spiropyran-derivatized surface was significantly smaller than the hysteresis. Thus, in order to achieve liquid drop motion on the spiropyran-derivatized surface, a new surface design which employs a combination of chemical modification of a hydrophobic organosilane and micropatterned rough surface morphology was suggested.

Study on kinetics of adsorption of humic acid modified by ferric chloride on U(VI)

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Lv, J. W.; Song, Y.; Dong, X. J.; Fang, Q.

2017-11-01

In order to reveal the adsorption mechanism of the ferric chloride modified humic acid on uranium, the influence of pH value and contact time of adsorption on uranium was studied through a series of batch experiments. Meanwhile, the adsorption kinetics was analyzed with pseudo-first order kinetic model and pseudo-second order kinetic model. The results show that adsorption is affected by the pH value of the solution and by contract time, and the best condition for adsorption on uranium is at pH=5 and the adsorption equilibrium time is about 80 min. Kinetics of HA-Fe adsorption on uranium accords with pseudo-second order kinetic model. The adsorption is mainly chemical adsorption, and complexes were produced by the reaction between uranium ions and the functional groups on the surface of HA-Fe, which can provide reference for further study of humic acid effecting on the migration of U(VI) in soil.

The preparation of Ag-BiVO4 metal composite oxides and its application in efficient photocatalytic oxidative thiophene

NASA Astrophysics Data System (ADS)

Gao, Xiao-Ming; Fu, Feng; Zhang, Li-Ping; Li, Wen-Hong

2013-06-01

A series of Ag-BiVO4 photocatalysts was synthesized by the hydrothemal synthesis method for different pH values. A strong correlation was found among the prepared processing, structure and property of the samples. With increasing pH value from 5 to 9, the crystallinity increases and the as-prepared Ag-BiVO4 sample gradually disappeared from the nanostructures. The light absorption became higher in the UV and visible range, accompanied by a bathochromic shift of the absorption edge. The competitive relations between crystallinity and surface area affecting photocatalytic activity were also discussed. Photocatalytic desulfurization on the as-prepared Ag-BiVO4 samples using thiophene dissolved in n-octane as a model organosulfur compound was performed. It showed that the photocatalytic desulfurization on the as-prepared Ag-BiVO4 sample at pH=7 can be up to 95%, which existed as various size particles and had significant high surface area of 13.768 m2 g-1.

Optimisation of medium composition for probiotic biomass production using response surface methodology.

PubMed

Anvari, Masumeh; Khayati, Gholam; Rostami, Shora

2014-02-01

This study was aimed to optimise lactose, inulin and yeast extract concentration and also culture pH for maximising the growth of a probiotic bacterium, Bifidobacterium animalis subsp. lactis in apple juice and to assess the effects of these factors by using response surface methodology. A second-order central composite design was applied to evaluate the effects of these independent variables on growth of the microorganism. A polynomial regression model with cubic and quadratic terms was used for analysis of the experimental data. It was found that the effects involving inulin, yeast extract and pH on growth of the bacterium were significant, and the strongest effect was given by the yeast extract concentration. Estimated optimum conditions of the factors on the bacterial growth are as follows: lactose concentration=9·5 g/l; inulin concentration=38·5 mg/l; yeast extract concentration=9·6 g/l and initial pH=6·2.

High efficiency protein separation with organosilane assembled silica coated magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Chang, Jeong Ho; Kang, Ki Ho; Choi, Jinsub; Jeong, Young Keun

2008-10-01

This work describes the development of high efficiency protein separation with functionalized organosilanes on the surface of silica coated magnetic nanoparticles. The magnetic nanoparticles were synthesized with average particle size of 9 nm and silica coated magnetic nanoparticles were obtained by controlling the coating thicknesses on magnetic nanoparticles. The silica coating thickness could be uniformly sized with a diameter of 10-40 nm by a sol-gel approach. The surface modification was performed with four kinds of functionalized organosilanes such as carboxyl, aldehyde, amine, and thiol groups. The protein separation work with organosilane assembled silica coated magnetic nanoparticles was achieved for model proteins such as bovine serum albumin (BSA) and lysozyme (LSZ) at different pH conditions. Among the various functionalities, the thiol group showed good separation efficiency due to the change of electrostatic interactions and protein conformational structure. The adsorption efficiency of BSA and LSZ was up to 74% and 90% corresponding pH 4.65 and pH 11.

Differences in the skin surface pH and bacterial microflora due to the long-term application of synthetic detergent preparations of pH 5.5 and pH 7.0. Results of a crossover trial in healthy volunteers.

PubMed

Korting, H C; Hübner, K; Greiner, K; Hamm, G; Braun-Falco, O

1990-01-01

Skin cleansing preparations consisting of identical synthetic detergents but differing in pH-value (pH 5.5 and 7.0) were applied twice daily on the forehead and forearm of healthy volunteers in a randomized crossover trial. The skin surface pH was found to be significantly higher when the neutral preparation had been used, as was the propionibacterial count (p less than 0.05). The number of propionibacteria was significantly linked to the skin pH. Hence even minor differences in the pH of skin cleansing preparations seem to be of importance for the integrity of the skin surface. This should be taken into account when planning the formulation of optimal skin care products.

Narrow pH Range of Surface Water Bodies Receiving Pesticide Input in Europe.

PubMed

Bundschuh, Mirco; Weyers, Arnd; Ebeling, Markus; Elsaesser, David; Schulz, Ralf

2016-01-01

Fate and toxicity of the active ingredients (AI's) of plant protection products in surface waters is often influenced by pH. Although a general range of pH values is reported in literature, an evaluation targeting aquatic ecosystems with documented AI inputs is lacking at the larger scale. Results show 95% of European surface waters (n = 3075) with a documented history of AI exposure fall within a rather narrow pH range, between 7.0 and 8.5. Spatial and temporal variability in the data may at least be partly explained by the calcareous characteristics of parental rock material, the affiliation of the sampling site to a freshwater ecoregion, and the photosynthetic activity of macrophytes (i.e., higher pH values with photosynthesis). Nonetheless, the documented pH range fits well with the standard pH of most ecotoxicological test guidelines, confirming the fate and ecotoxicity of AIs are usually adequately addressed.

Sorption/Desorption Interactions of Plutonium with Montmorillonite

NASA Astrophysics Data System (ADS)

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

2012-12-01

Plutonium (Pu) release to the environment through nuclear weapon development and the nuclear fuel cycle is an unfortunate legacy of the nuclear age. In part due to public health concerns over the risk of Pu contamination of drinking water, predicting the behavior of Pu in both surface and sub-surface water is a topic of continued interest. Typically it was assumed that Pu mobility in groundwater would be severely restricted, as laboratory adsorption studies commonly show that naturally occurring minerals can effectively remove plutonium from solution. However, evidence for the transport of Pu over significant distances at field sites highlights a relative lack of understanding of the fundamental processes controlling plutonium behavior in natural systems. At several field locations, enhanced mobility is due to Pu association with colloidal particles that serve to increase the transport of sorbed contaminants (Kersting et al., 1999; Santschi et al., 2002, Novikov et al., 2006). The ability for mineral colloids to transport Pu is in part controlled by its oxidation state and the rate of plutonium adsorption to, and desorption from, the mineral surface. Previously we have investigated the adsorption affinity of Pu for montmorillonite colloids, finding affinities to be similar over a wide range of Pu concentrations. In the present study we examine the stability of adsorbed Pu on the mineral surface. Pu(IV) at an initial concentration of 10-10 M was pre-equilibrated with montmorillonite in a background electrolyte at pH values of 4, 6 and 8. Following equilibration, aliquots of the suspensions were placed in a flow cell and Pu-free background electrolyte at the relevant pH was passed through the system. Flow rates were varied in order to investigate the kinetics of desorption and hence gain a mechanistic understanding of the desorption process. The flow cell experiments demonstrate that desorption of Pu from the montmorillonite surface cannot be modeled as a simple first order process. Furthermore, a pH dependence was observed, with less desorbed at pH 4 compared to pH 8. We suggest the pH dependence is likely controlled by reoxidation of Pu(IV) to Pu(V) and aqueous speciation. We will present models used to describe desorption behavior and discuss the implications for Pu transport. References: Kersting, A.B.; Efurd, D.W.; Finnegan, D.L.; Rokop, D.J.; Smith, D.K.; Thompson J.L. (1999) Migration of plutonium in groundwater at the Nevada Test Site, Nature, 397, 56-59. Novikov A.P.; Kalmykov, S.N.; Utsunomiya, S.; Ewing, R.C.; Horreard, F.; Merkulov, A.; Clark, S.B.; Tkachev, V.V.; Myasoedov, B.F. (2006) Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia, Science, 314, 638-641. Santschi, P.H.; Roberts, K.; Guo, L. (2002) The organic nature of colloidal actinides transported in surface water environments. Environ. Sci. Technol., 36, 3711-3719. This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. LLNL-ABS-570161

Hydroxymethane sulfonate as a possible explanation for observed high levels of particulate sulfur during severe winter haze episodes in Beijing, China.

NASA Astrophysics Data System (ADS)

Moch, J.; Jacob, D.; Mickley, L. J.; Cheng, Y.; Li, M.; Munger, J. W.; Wang, Y.

2017-12-01

Observed PM2.5 during severe winter haze in Beijing, China, may reach levels as high as 880 μg m-3, with sulfur compounds contributing significantly to PM2.5 composition. Such sulfur has been traditionally assumed to be sulfate, even though models fail to generate such large sulfate enhancements under cold and hazy conditions. We show that particulate sulfur in wintertime Beijing possibly occurs as an S(IV)-HCHO adduct, hydroxymethane sulfonate (HMS), formed by reaction of aqueous-phase HCHO and S(IV) in cloud droplets. We use a 1-D chemistry model extending from the surface through the boundary layer to examine the potential role of HMS during the Beijing haze events of December 2011 and January 2013. Observed and assimilated meteorological fields including cloud liquid water were applied to the model, and we test the sensitivity of HMS formation to cloud pH and ambient SO2 and HCHO. Surface observations from the two haze events show excess ammonium in the aerosol, indicating cloud pH may be relatively high. Model results show that once cloud pH exceeds 4.5, HMS can accumulate rapidly, reaching a few hundred μg m-3 in a few hours. The timing of HMS formation is controlled by the presence of cloud liquid water, with eddy driven diffusion bringing HMS to the surface. The magnitude of HMS peaks is limited by the supply of HCHO. HMS episodes in the model end gradually over 1-3 days as fresh air is entrained into the boundary layer; in observations these episodes typically end when increasing wind speeds destabilize the boundary layer and disperses pollution. We find that consideration of HMS as a source of particulate sulfur significantly improves model match with observations. For example, assuming cloud pH of 5 and average surface SO2 and HCHO levels of 50 ppb and 5.5 ppb, we calculate mean HMS as 43.8 μg m-3 in January 2013, within 7 μg m-3 of observed particulate sulfur. Our 1-D model also captures the timing and magnitude of peak particulate sulfur in January 2013, with HMS approaching 100 μg m-3 during episodes. In contrast, a GEOS-Chem 3-D simulation without HMS chemistry yields peak particulate sulfur of 20 μg m-3. Our findings suggest that SO2 is not the limiting factor in winter haze events in Beijing and that, in order to reduce severe winter haze in this region, policymakers may need to address HCHO sources such as transportation.

Adsorbed Layers of Ferritin at Solid and Fluid Interfaces Studied by Atomic Force Microscopy.

PubMed

Johnson; Yuan; Lenhoff

2000-03-15

The adsorption of the iron storage protein ferritin was studied by liquid tapping mode atomic force microscopy in order to obtain molecular resolution in the adsorbed layer within the aqueous environment in which the adsorption was carried out. The surface coverage and the structure of the adsorbed layer were investigated as functions of ionic strength and pH on two different charged surfaces, namely chemically modified glass slides and mixed surfactant films at the air-water interface, which were transferred to graphite substrates after adsorption. Surface coverage trends with both ionic strength and pH indicate the dominance of electrostatic effects, with the balance shifting between intermolecular repulsion and protein-surface attraction. The resulting behavior is more complex than that seen for larger colloidal particles, which appear to follow a modified random sequential adsorption model monotonically. The structure of the adsorbed layers at the solid surfaces is random, but some indication of long-range order is apparent at fluid interfaces, presumably due to the higher protein mobility at the fluid interface. Copyright 2000 Academic Press.

Synergistic effect of wire bending and salivary pH on surface properties and mechanical properties of orthodontic stainless steel archwires.

PubMed

Hobbelink, Marieke G; He, Yan; Xu, Jia; Xie, Huixu; Stoll, Richard; Ye, Qingsong

2015-01-01

The aim of this study was to investigate the corrosive behaviour of stainless steel archwires in a more clinically relevant way by bending and exposing to various pH. One hundred and twenty pieces of rectangular stainless steel wires (0.43 × 0.64 mm) were randomly assigned into four groups. In each group, there were 15 pieces of bent wires and 15 straight ones. Prior to measurements of the wires, as individual experimental groups (group 1, 2, and 3), the wires were exposed to artificial saliva for 4 weeks at pH 5.6, 6.6, and 7.6, respectively. A control group of wires (group 4) remained in air for the same period of time before sent for measurements. Surface roughness (Ra-value) was measured by a profilometer. Young's modulus and maximum force were determined by a four-point flexural test apparatus. Scanning electron microscopy was used to observe the surface morphology of straight wire. Differences between groups were examined using a two-way analysis of variance (ANOVA). Mean surface roughness values, flexural Young's moduli, and maximum force values of bent wires are significantly different from those of the straight wires, which was the main effect of wire bending, ignoring the influence of pH. A significant effect was found between Ra-values regarding the main effect of pH, ignoring the influence of shape. There was a significant interaction effect of bending and pH on flexural Young's moduli of stainless steel archwires, while pH did not show much impact on the maximum force values of those stainless steel wires. Bigger surface irregularities were seen on SEM images of straight wires immersed in artificial saliva at pH 5.6 compared to artificial saliva at other pH values. Surface depth (Rz) was more sensitive than Ra in revealing surface roughness, both measured from 3D reconstructed SEM images. Ra showed a comparable result of surface roughness to Ra-value measured by the profilometer. Bending has a significant influence on surface roughness and mechanical properties of rectangular SS archwires. pH plays a synergistic effect on the change of mechanical properties of stainless steel (SS) wires along with wire bending.

Ocean circulation and biogeochemistry moderate interannual and decadal surface water pH changes in the Sargasso Sea

USGS Publications Warehouse

Nathalie F. Goodkin,; Bo-Shian Wang,; Chen-Feng You,; Konrad Hughen,; Prouty, Nancy G.; Bates, Nicholas; Scott Doney,

2015-01-01

The oceans absorb anthropogenic CO2 from the atmosphere, lowering surface ocean pH, a concern for calcifying marine organisms. The impact of ocean acidification is challenging to predict as each species appears to respond differently and because our knowledge of natural changes to ocean pH is limited in both time and space. Here we reconstruct 222 years of biennial seawater pH variability in the Sargasso Sea from a brain coral, Diploria labyrinthiformis. Using hydrographic data from the Bermuda Atlantic Time-series Study and the coral-derived pH record, we are able to differentiate pH changes due to surface temperature versus those from ocean circulation and biogeochemical changes. We find that ocean pH does not simply reflect atmospheric CO2 trends but rather that circulation/biogeochemical changes account for >90% of pH variability in the Sargasso Sea and more variability in the last century than would be predicted from anthropogenic uptake of CO2 alone.

Application of quartz crystal microbalance to study the impact of pH and ionic strength on protein-silicone oil interactions.

PubMed

Dixit, Nitin; Maloney, Kevin M; Kalonia, Devendra S

2011-06-30

In this study, we have used quartz crystal microbalance (QCM) to quantitate the adsorption of a protein on silicone oil coated surfaces as a function of protein concentration, pH and ionic strength using a 5 MHz quartz crystal. Protein adsorption isotherms were generated at different solution pH and ionic strengths. Surface saturation concentrations were selected from adsorption isotherms and used to generate adsorption profiles from pH 3.0 to 9.0, and at ionic strengths of 10 mM and 150 mM. At low ionic strength (10mM) and pH 5.0 (close to the isoelectric point of the protein), maximum adsorption of protein to the silicone oil surface was observed. At higher ionic strength (150 mM), no significant pH influence on adsorption was observed. QCM could be used as a reliable technique to study the binding of proteins to silicone oil coated surfaces. Copyright © 2011 Elsevier B.V. All rights reserved.

Anomalous Dynamics of a Lipid Recognition Protein on a Membrane Surface

PubMed Central

Yamamoto, Eiji; Kalli, Antreas C.; Akimoto, Takuma; Yasuoka, Kenji; Sansom, Mark S. P.

2015-01-01

Pleckstrin homology (PH) domains are lipid-binding modules present in peripheral membrane proteins which interact with phosphatidyl-inositol phosphates (PIPs) in cell membranes. We use multiscale molecular dynamics simulations to characterize the localization and anomalous dynamics of the DAPP1 PH domain on the surface of a PIP-containing lipid bilayer. Both translational and rotational diffusion of the PH domain on the lipid membrane surface exhibit transient subdiffusion, with an exponent α ≈ 0.5 for times of less than 10 ns. In addition to a PIP3 molecule at the canonical binding site of the PH domain, we observe additional PIP molecules in contact with the protein. Fluctuations in the number of PIPs associated with the PH domain exhibit 1/f noise. We suggest that the anomalous diffusion and long-term correlated interaction of the PH domain with the membrane may contribute to an enhanced probability of encounter with target complexes on cell membrane surfaces. PMID:26657413

Approaches to modelling uranium (VI) adsorption on natural mineral assemblages

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Fenton, B.R.; Payne, T.E.

2000-01-01

Component additivity (CA) and generalised composite (GC) approaches to deriving a suitable surface complexation model for description of U(VI) adsorption to natural mineral assemblages are pursued in this paper with good success. A single, ferrihydrite-like component is found to reasonably describe uranyl uptake to a number of kaolinitic iron-rich natural substrates at pH > 4 in the CA approach with previously published information on nature of surface complexes, acid-base properties of surface sites and electrostatic effects used in the model. The GC approach, in which little pre-knowledge about generic surface sites is assumed, gives even better fits and would appear to be a method of particular strength for application in areas such as performance assessment provided the model is developed in a careful, stepwise manner with simplicity and goodness of fit as the major criteria for acceptance.

Enriching acid rock drainage related microbial communities from surface-deposited oil sands tailings.

PubMed

Dean, Courtney; Xiao, Yeyuan; Roberts, Deborah J

2016-10-01

Little is known about the microbial communities native to surface-deposited pyritic oil sands tailings, an environment where acid rock drainage (ARD) could occur. The goal of this study was to enrich sulfur-oxidizing organisms from these tailings and determine whether different populations exist at pH levels 7, 4.5, and 2.5. Using growth-based methods provides model organisms for use in the future to predict potential activities and limitations of these organisms and to develop possible control methods. Thiosulfate-fed enrichment cultures were monitored for approximately 1 year. The results showed that the enrichments at pH 4.5 and 7 were established quicker than at pH 2.5. Different microbial community structures were found among the 3 pH environments. The sulfur-oxidizing microorganisms identified were most closely related to Halothiobacillus neapolitanus, Achromobacter spp., and Curtobacterium spp. While microorganisms related to Chitinophagaceae and Acidocella spp. were identified as the only possible iron-oxidizing and -reducing microbes. These results contribute to the general knowledge of the relatively understudied microbial communities that exist in pyritic oil sands tailings and indicate these communities may have a potential role in ARD generation, which may have implications for future tailings management.

Development of pH sensitive microparticles of Karaya gum: By response surface methodology.

PubMed

Raizaday, Abhay; Yadav, Hemant K S; Kumar, S Hemanth; Kasina, Susmitha; Navya, M; Tashi, C

2015-12-10

The objective of the proposed work was to prepare pH sensitive microparticles (MP) of Karaya gum using distilled water as a solvent by spray drying technique. Different formulations were designed, prepared and evaluated by employing response surface methodology and optimal design of experiment technique using Design Expert(®) ver 8.0.1 software. SEM photographs showed that MP were roughly spherical in shape and free from cracks. The particle size and encapsulation efficiency for optimized MP was found to be between 3.89 and 6.5 μm and 81-94% respectively with good flow properties. At the end of the 12th hour the in vitro drug release was found to be 96.9% for the optimized formulation in pH 5.6 phosphate buffer. Low prediction errors were observed for Cmax and AUC0-∞ which demonstrated that the Frusemide IVIVC model was valid. Hence it can be concluded that pH sensitive MP of Karaya gum were effectively prepared by spray drying technique using aqueous solvents and can be used for treating various diseases like chronic hypertension, Ulcerative Colitis and Diverticulitis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ni and Cr addition to alloy waste forms to reduce radionuclide environmental releases

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

Olson, L.

2016-10-11

Reference alloy waste forms (RAW) were fabricated and underwent hybrid corrosion/immersion testing to parameterize the ANL analytical oxidative-dissolution model to enable the calculation of fractional release rates and to determine the effectiveness of Ni and Cr trim additions in reducing release rates of radionuclide surrogates. Figure 1 shows the prototypical multiphase microstructure of the alloys with each phase type contributing about equally to the exposed surface area. The waste forms tested at SRNL were variations of the RAW-6 formulation that uses HT9 as the main alloy component, and are meant to enable evaluation of the impact of Ni and Crmore » trim additions on the release rates of actinides and Tc-99. The test solutions were deaerated alkaline and acidic brines, ranging in pH 3 to pH 10, representing potential repositories with those conditions. The testing approach consisted of 4 major steps; 1) bare surface corrosion measurements at pH values of 3, 5, 8, and 10, 2) hybrid potentiostatic hold/exposure measurements at pH 3, 3) measurement of radionuclide concentrations and relations to anodic current from potentiostatic holds, and 4) identification of corroding phases using SEM/EDS of electrodes.« less

Regression model, artificial neural network, and cost estimation for biosorption of Ni(II)-ions from aqueous solutions by Potamogeton pectinatus.

PubMed

Fawzy, Manal; Nasr, Mahmoud; Adel, Samar; Helmi, Shacker

2018-03-21

This study investigated the application of Potamogeton pectinatus for Ni(II)-ions biosorption from aqueous solutions. FTIR spectra showed that the functional groups of -OH, C-H, -C = O, and -COO- could form an organometallic complex with Ni(II)-ions on the biomaterial surface. SEM/EDX analysis indicated that the voids on the biosorbent surface were blocked due to Ni(II)-ions uptake via an ion exchange mechanism. For Ni(II)-ions of 50 mg/L, the adsorption efficiency recorded 63.4% at pH: 5, biosorbent dosage: 10 g/L, and particle-diameter: 0.125-0.25 mm within 180 minutes. A quadratic model depicted that the plot of removal efficiency against pH or contact time caused quadratic-linear concave up curves, whereas the curve of initial Ni(II)-ions was quadratic-linear convex down. Artificial neural network with a structure of 5 - 6 - 1 was able to predict the adsorption efficiency (R 2 : 0.967). The relative importance of inputs was: initial Ni(II)-ions > pH > contact time > biosorbent dosage > particle-size. Freundlich isotherm described well the adsorption mechanism (R 2 : 0.974), which indicated a multilayer adsorption onto energetically heterogeneous surfaces. The net cost of using P. pectinatus for the removal of Ni(II)-ions (4.25 ± 1.26 mg/L) from real industrial effluents within 30 minutes was 3.4 $USD/m 3 .

Enhanced fluoride adsorption by nano crystalline γ-alumina: adsorption kinetics, isotherm modeling and thermodynamic studies

NASA Astrophysics Data System (ADS)

Chinnakoti, Prathibha; Chunduri, Avinash L. A.; Vankayala, Ranganayakulu K.; Patnaik, Sandeep; Kamisetti, Venkataramaniah

2017-09-01

Nano materials in particular nano oxides with enhanced surface area and an excellent catalytic surface serve as potential adsorbents for defluoridation of water. In the present study nano γ-alumina was synthesized through a simple and low cost, surfactant assisted solution combustion method. As synthesized material was characterized by XRD and FESEM for its phase, size and morphological characteristics. Surface properties have been investigated by BET method. Nano γ-alumina was further used for a detailed adsorption study to remove fluoride from water. Batches of experiments were performed at various experimental conditions such as solution pH, adsorbent dose, initial fluoride concentration and contact time to test the defluoridation ability of γ-alumina. Fluoride Adsorption by nano sized γ-alumina was rapid and reached equilibrium within two hours. The adsorption worked well at pH 4.0, where ˜96 % of fluoride was found to be adsorbed on adsorbent. It was possible to reduce fluoride levels to as low as 0.3 mg/L (within the safe limit of WHO: ≤1.5 mg/L) from an initial fluoride levels of 10 mg/L. This could be achieved using a very small quantity, 1 g/L of γ-alumina at pH 4 within 1 h of contact time. Defluoridation capacity of nano γ-alumina was further investigated by fitting the equilibrium data to various isotherm as well as kinetic models. The present study revealed that γ-alumina could be an efficient adsorbent for treating fluoride contaminated water.

Mechanisms on the Impacts of Alkalinity, pH, and Chloride on Persulfate-Based Groundwater Remediation.

PubMed

Li, Wei; Orozco, Ruben; Camargos, Natalia; Liu, Haizhou

2017-04-04

Persulfate (S 2 O 8 2- )-based in situ chemical oxidation (ISCO) has gained more attention in recent years due to the generation of highly reactive and selective sulfate radical (SO 4 •- ). This study examined the effects of important groundwater chemical parameters, i.e., alkalinity, pH, and chloride on benzene degradation via heterogeneous persulfate activation by three Fe(III)- and Mn(IV)-containing aquifer minerals: ferrihydrite, goethite, and pyrolusite. A comprehensive kinetic model was established to elucidate the mechanisms of radical generation and mineral surface complexation. Results showed that an increase of alkalinity up to 10 meq/L decreased the rates of persulfate decomposition and benzene degradation, which was associated with the formation of unreactive surface carbonato complexes. An increase in pH generally accelerated persulfate decomposition due to enhanced formation of reactive surface hydroxo complexation. A change in the chloride level up to 5 mM had a negligibly effect on the reaction kinetics. Kinetics modeling also suggested that SO 4 •- was transformed to hydroxyl radical (HO • ) and carbonate radical (CO 3 •- ) at higher pHs. Furthermore, the yields of two major products of benzene oxidation, i.e., phenol and aldehyde, were positively correlated with the branching ratio of SO 4 •- reacting with benzene, but inversely correlated with that of HO • or CO 3 •- , indicating that SO 4 •- preferentially oxidized benzene via pathways involving fewer hydroxylation steps compared to HO • or CO 3 •- .

Evidence from mathematical modeling that carbonic anhydrase II and IV enhance CO2 fluxes across Xenopus oocyte plasma membranes

PubMed Central

Musa-Aziz, Raif; Boron, Walter F.

2014-01-01

Exposing an oocyte to CO2/HCO3− causes intracellular pH (pHi) to decline and extracellular-surface pH (pHS) to rise to a peak and decay. The two companion papers showed that oocytes injected with cytosolic carbonic anhydrase II (CA II) or expressing surface CA IV exhibit increased maximal rate of pHi change (dpHi/dt)max, increased maximal pHS changes (ΔpHS), and decreased time constants for pHi decline and pHS decay. Here we investigate these results using refinements of an earlier mathematical model of CO2 influx into a spherical cell. Refinements include 1) reduced cytosolic water content, 2) reduced cytosolic diffusion constants, 3) refined CA II activity, 4) layer of intracellular vesicles, 5) reduced membrane CO2 permeability, 6) microvilli, 7) refined CA IV activity, 8) a vitelline membrane, and 9) a new simulation protocol for delivering and removing the bulk extracellular CO2/HCO3− solution. We show how these features affect the simulated pHi and pHS transients and use the refined model with the experimental data for 1.5% CO2/10 mM HCO3− (pHo = 7.5) to find parameter values that approximate ΔpHS, the time to peak pHS, the time delay to the start of the pHi change, (dpHi/dt)max, and the change in steady-state pHi. We validate the revised model against data collected as we vary levels of CO2/HCO3− or of extracellular HEPES buffer. The model confirms the hypothesis that CA II and CA IV enhance transmembrane CO2 fluxes by maximizing CO2 gradients across the plasma membrane, and it predicts that the pH effects of simultaneously implementing intracellular and extracellular-surface CA are supra-additive. PMID:24965589

Electroreduction of carbon monoxide over a copper nanocube catalyst: Surface structure and pH dependence on selectivity

DOE PAGES

Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders

2016-02-16

The activity and selectivity for CO 2/CO reduction over copper electrodes is strongly dependent on the local surface structure of the catalyst and the pH of the electrolyte. Here we investigate a unique, copper nanocube surface (CuCube) as a CO reduction electrode under neutral and basic pH, using online electrochemical mass spectroscopy (OLEMS) to determine the onset potentials and relative intensities of methane and ethylene production. To relate the unique selectivity to the surface structure, the CuCube surface reactivity is compared to polycrystalline copper and three single crystals under the same reaction conditions. Here, we find that the high selectivitymore » for ethylene over the CuCube surface is most comparable to the Cu(100) surface, which has the cubic unit cell. However, the suppression of methane production over CuCube is unique to that particular surface. Basic pH is also shown to enhance ethylene selectivity on all surfaces, again with the CuCube surface being unique.« less

Novel amelogenin-releasing hydrogel for remineralization of enamel artificial caries

PubMed Central

Fan, Yuwei; Wen, Zezhang T; Liao, Sumei; Lallier, Thomas; Hagan, Joseph L; Twomley, Jefferson T; Zhang, Jian-Feng; Sun, Zhi; Xu, Xiaoming

2013-01-01

Recently, the use of recombinant full-length amelogenin protein in combination with fluoride has shown promising results in the formation of densely packed enamel-like structures. In this study, amelogenin (rP172)-releasing hydrogels containing calcium, phosphate, and fluoride were investigated for remineralization efficacy using in vitro early enamel caries models. The hydrogels were applied to artificial caries lesions on extracted human third molars, and the remineralization efficacy was tested in different models: static gel remineralization in the presence of artificial saliva, pH cyclic treatment at pH 5.4 acetic buffer and pH 7.3 gel remineralization, and treatment with multispecies oral biofilms grown in a continuous flowing constant-depth film fermenter. The surface microhardness of remineralized enamel increased significantly when amelogenin was released from hydrogel. No cytotoxicity was observed when periodontal ligament cells were cultured with the mineralized hydrogels. PMID:23338820

External pH effects on the depolarization-activated K channels in guard cell protoplasts of Vicia faba

PubMed Central

1994-01-01

Previous studies reveal that the pH of the apoplastic solution in the guard cell walls may vary between 7.2 and 5.1 in closed and open stomata, respectively. During these aperture and pH changes, massive K+ fluxes cross the cellular plasma membrane driving the osmotic turgor and volume changes of guard cells. Therefore, we examined the effect of extracellular pH on the depolarization-activated K channels (KD channels), which constitute the K+ efflux pathway, in the plasma membrane of Vicia faba guard cell protoplasts. We used patch clamp, both in whole cells as well as in excised outside-out membrane patches. Approximately 500 KD channels, at least, could be activated by depolarization in one protoplast (density: approximately 0.6 micron-2). Acidification from ph 8.1 to 4.4 decreased markedly the whole-cell conductance, GK, of the KD channels, shifted its voltage dependence, GK- EM, to the right on the voltage axis, slowed the rate of activation and increased the rate of deactivation, whereas the single channel conductance was not affected significantly. Based on the GK-EM shifts, the estimated average negative surface charge spacing near the KD channel is 39 A. To quantify the effects of protons on the rates of transitions between the hypothesized conformational states of the channels, we fitted the experimental macroscopic steady state conductance-voltage relationship and the voltage dependence of time constants of activation and deactivation, simultaneously, with a sequential three-state model CCO. In terms of this model, protonation affects the voltage-dependent properties via a decrease in localized, rather than homogeneous, surface charge sensed by the gating moieties. In terms of either the CO or CCO model, the protonation of a site with a pKa of 4.8 decreases the voltage-independent number of channels, N, that are available for activation by depolarization. PMID:8035163

The Impact of Very High Frequency Surface Reverberation on Coherent Acoustic Propagation and Modeling

DTIC Science & Technology

2015-09-30

in review]. Glowacki, O., G. B. Deane, M. Moskalik, Ph. Blondel, J. Tegowski and M. Blaszczyk, “Underwater acoustic signatures of glacier calving.” Geophys. Res. Let. 2014. DOI: 10.1002/2014GL062859 [published, refereed].

Bacterial desorption from food container and food processing surfaces.

PubMed

McEldowney, S; Fletcher, M

1988-03-01

The desorption ofStaphylococcus aureus, Acinetobacter calcoaceticus, and a coryneform from the surfaces of materials used for manufacturing food containers (glass, tin plate, and polypropylene) or postprocess canning factory conveyor belts (stainless steel and nylon) was investigated. The effect of time, pH, temperature, and adsorbed organic layers on desorption was studied.S. aureus did not detach from the substrata at any pH investigated (between pH 5 and 9).A. calcoaceticus and the coryneform in some cases detached, depending upon pH and substratum composition. The degree of bacterial detachment from the substrata was not related to bacterial respiration at experimental pH values. Bacterial desorption was not affected by temperature (4-30°C) nor by an adsorbed layer of peptone and yeast extract on the substrata. The results indicate that bacterial desorption, hence bacterial removal during cleaning or their transfer via liquids flowing over colonized surfaces, is likely to vary with the surface composition and the bacterial species colonizing the surfaces.

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.

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

PubMed

Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R

2006-04-15

The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

Graphite Screen-Printed Electrodes Applied for the Accurate and Reagentless Sensing of pH.

PubMed

Galdino, Flávia E; Smith, Jamie P; Kwamou, Sophie I; Kampouris, Dimitrios K; Iniesta, Jesus; Smith, Graham C; Bonacin, Juliano A; Banks, Craig E

2015-12-01

A reagentless pH sensor based upon disposable and economical graphite screen-printed electrodes (GSPEs) is demonstrated for the first time. The voltammetric pH sensor utilizes GSPEs which are chemically pretreated to form surface immobilized oxygenated species that, when their redox behavior is monitored, give a Nernstian response over a large pH range (1-13). An excellent experimental correlation is observed between the voltammetric potential and pH over the entire pH range of 1-13 providing a simple approach with which to monitor solution pH. Such a linear response over this dynamic pH range is not usually expected but rather deviation from linearity is encountered at alkaline pH values; absence of this has previously been attributed to a change in the pKa value of surface immobilized groups from that of solution phase species. This non-deviation, which is observed here in the case of our facile produced reagentless pH sensor and also reported in the literature for pH sensitive compounds immobilized upon carbon electrodes/surfaces, where a linear response is observed over the entire pH range, is explained alternatively for the first time. The performance of the GSPE pH sensor is also directly compared with a glass pH probe and applied to the measurement of pH in "real" unbuffered samples where an excellent correlation between the two protocols is observed validating the proposed GSPE pH sensor.

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy

PubMed Central

2017-01-01

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force–distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl– adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl– ions will co-adsorb, thereby changing the observed ordered surface structure. PMID:29140711

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

PubMed

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

Kinetic and isotherm analyses for thorium (IV) adsorptive removal from aqueous solutions by modified magnetite nanoparticle using response surface methodology (RSM)

NASA Astrophysics Data System (ADS)

Karimi, Mohammad; Milani, Saeid Alamdar; Abolgashemi, Hossein

2016-10-01

In this study, the ability and the adsorption capacity of magnetite/aminopropyltriethoxysilane/glutaraldehyde (Fe3O4/APTES/GA) adsorbent were evaluated for the adsorption of thorium (IV) ions from aqueous solutions. The influence of the several variables such as pH (1-5), Th (IV) initial concentration (50-300 mg L-1) and adsorbent concentration (1-5 g L-1) on the Th (IV) adsorption were investigated by response surface methodology (RSM). The results showed that the highest absorption capacity (q) was 107.23 mg g-1 with respect to pH = 4.5, initial concentration of 250 mg L-1 and adsorbent concentration of 1 g L-1 for 90 min. Modeling equilibrium sorption data with the Langmuir, Freundlich and Dubinin-Radushkevich models pointed out that the results were in good agreement with Langmuir model. The experimental kinetic data were well fitted to pseudo-second-order equation with R2 = 0.9739. Also thermodynamic parameters (ΔGo, ΔHo, ΔSo) declared that the Th (IV) adsorption was endothermic and spontaneous.

Optimizing adsorption of fluoride from water by modified banana peel dust using response surface modelling approach

NASA Astrophysics Data System (ADS)

Bhaumik, Ria; Mondal, Naba Kumar

2016-06-01

The present work highlighted the effective application of banana peel dust (BPD) for removal of fluoride (F-) from aqueous solution. The effects of operating parameters such as pH, initial concentration, adsorbent dose, contact time, agitation speed and temperature were analysed using response surface methodology. The significance of independent variables and their interactions were tested by the analysis of variance and t test statistics. Experimental results revealed that BPD has higher F- adsorption capacity (17.43, 26.31 and 39.5 mg/g). Fluoride adsorption kinetics followed pseudo-second-order model with high correlation of coefficient value (0.998). On the other hand, thermodynamic data suggest that adsorption is favoured at lower temperature, exothermic in nature and enthalpy driven. The adsorbents were characterised through scanning electron microscope, Fourier transform infrared spectroscopy and point of zero charges (pHZPC) ranges from pH 6.2-8.2. Finally, error analysis clearly demonstrates that all three adsorbents are well fitted with Langmuir isotherm compared to the other isotherm models. The reusable properties of the material support further development for commercial application purpose.

Gate modulation of proton transport in a nanopore.

PubMed

Mei, Lanju; Yeh, Li-Hsien; Qian, Shizhi

2016-03-14

Proton transport in confined spaces plays a crucial role in many biological processes as well as in modern technological applications, such as fuel cells. To achieve active control of proton conductance, we investigate for the first time the gate modulation of proton transport in a pH-regulated nanopore by a multi-ion model. The model takes into account surface protonation/deprotonation reactions, surface curvature, electroosmotic flow, Stern layer, and electric double layer overlap. The proposed model is validated by good agreement with the existing experimental data on nanopore conductance with and without a gate voltage. The results show that the modulation of proton transport in a nanopore depends on the concentration of the background salt and solution pH. Without background salt, the gated nanopore exhibits an interesting ambipolar conductance behavior when pH is close to the isoelectric point of the dielectric pore material, and the net ionic and proton conductance can be actively regulated with a gate voltage as low as 1 V. The higher the background salt concentration, the lower is the performance of the gate control on the proton transport.

Influence of surface porosity and pH on bacterial adherence to hydroxyapatite and biphasic calcium phosphate bioceramics.

PubMed

Kinnari, Teemu J; Esteban, Jaime; Martin-de-Hijas, Nieves Z; Sánchez-Muñoz, Orlando; Sánchez-Salcedo, Sandra; Colilla, Montserrat; Vallet-Regí, María; Gomez-Barrena, Enrique

2009-01-01

Hydroxyapatite (HA) and biphasic calcium phosphate (BCP) ceramic materials are widely employed as bone substitutes due to their porous and osteoconductive structure. Their porosity and the lowering of surrounding pH as a result of surgical trauma may, however, predispose these materials to bacterial infections. For this reason, the influence of porosity and pH on the adherence of common Gram-positive bacteria to the surfaces of these materials requires investigation. Mercury intrusion porosimetry measurements revealed that the pore size distribution of both bioceramics had, on a logarithmic scale, a sinusoidal frequency distribution ranging from 50 to 300 nm, with a mean pore diameter of 200 nm. Moreover, total porosity was 20 % for HA and 50 % for BCP. Adherence of Staphylococcus aureus and Staphylococcus epidermidis was studied at a physiological pH of 7.4 and at a pH simulating bone infection of 6.8. Moreover, the effect of pH on the zeta potential of HA, BCP and of both staphylococci was evaluated. Results showed that when pH decreased from 7.4 to 6.8, the adherence of both staphylococci to HA and BCP surfaces decreased significantly, although at the same time the negative zeta-potential values of the ceramic surfaces and both bacteria diminished. At both pH values, the number of S. aureus adhered to the HA surface appeared to be lower than that for BCP. A decrease in pH to 6.8 reduced the adherence of both bacterial species (mean 57 %). This study provides evidence that HA and BCP ceramics do not have pores sufficiently large to allow the internalization of staphylococci. Their anti-adherent properties seemed to improve when pH value decreased, suggesting that HA and BCP bioceramics are not compromised upon orthopaedic use.

Predicted pH at the domestic and public supply drinking water depths, Central Valley, California

USGS Publications Warehouse

Rosecrans, Celia Z.; Nolan, Bernard T.; Gronberg, Jo Ann M.

2017-03-08

This scientific investigations map is a product of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project modeling and mapping team. The prediction grids depicted in this map are of continuous pH and are intended to provide an understanding of groundwater-quality conditions at the domestic and public supply drinking water zones in the groundwater of the Central Valley of California. The chemical quality of groundwater and the fate of many contaminants is often influenced by pH in all aquifers. These grids are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to pH. In this work, the median well depth categorized as domestic supply was 30 meters below land surface, and the median well depth categorized as public supply is 100 meters below land surface. Prediction grids were created using prediction modeling methods, specifically boosted regression trees (BRT) with a Gaussian error distribution within a statistical learning framework within the computing framework of R (http://www.r-project.org/). The statistical learning framework seeks to maximize the predictive performance of machine learning methods through model tuning by cross validation. The response variable was measured pH from 1,337 wells and was compiled from two sources: USGS National Water Information System (NWIS) database (all data are publicly available from the USGS: http://waterdata.usgs.gov/ca/nwis/nwis) and the California State Water Resources Control Board Division of Drinking Water (SWRCB-DDW) database (water quality data are publicly available from the SWRCB: http://www.waterboards.ca.gov/gama/geotracker_gama.shtml). Only wells with measured pH and well depth data were selected, and for wells with multiple records, only the most recent sample in the period 1993–2014 was used. A total of 1,003 wells (training dataset) were used to train the BRT model, and 334 wells (hold-out dataset) were used to validate the prediction model. The training r-squared was 0.70, and the root-mean-square error (RMSE) in standard pH units was 0.26. The hold-out r-squared was 0.43, and RMSE in standard pH units was 0.37. Predictor variables consisting of more than 60 variables from 7 sources were assembled to develop a model that incorporates regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrology. Previously developed Central Valley model outputs of textures (Central Valley Textural Model, CVTM; Faunt and others, 2010) and MODFLOW-simulated vertical water fluxes and predicted depth to water table (Central Valley Hydrologic Model, CVHM; Faunt, 2009) were used to represent aquifer textures and groundwater hydraulics, respectively. In this work, wells were attributed to predictor variable values in ArcGIS using a 500-meter buffer.Faunt, C.C., ed., 2009, Groundwater availability in the Central Valley aquifer, California: U.S. Geological Survey Professional Paper 1776, 225 p., accessed at https://pubs.usgs.gov/pp/1766/.Faunt, C.C., Belitz, K., and Hanson, R.T., 2010, Development of a three-dimensional model of sedimentary texture in valley-fill deposits of Central Valley, California, USA: Hydrogeology Journal, v. 18, no. 3, p. 625–649, https://doi.org/10.1007/s10040-009-0539-7.

Inhibitors of acid secretion can benefit gastric wound repair independent of luminal pH effects on the site of damage

PubMed Central

Demitrack, Elise S; Aihara, Eitaro; Kenny, Susan; Varro, Andrea; Montrose, Marshall H

2012-01-01

Background and aims The authors’ goal was to measure pH at the gastric surface (pHo) to understand how acid secretion affects the repair of microscopic injury to the gastric epithelium. Methods Microscopic gastric damage was induced by laser light, during confocal/two-photon imaging of pH-sensitive dyes (Cl-NERF, BCECF) that were superfused over the mucosal surface of the exposed gastric corpus of anaesthetised mice. The progression of repair was measured in parallel with pHo. Experimental conditions included varying pH of luminal superfusates, and using omeprazole (60 mg/kg ip) or famotidine (30 mg/kg ip) to inhibit acid secretion. Results Similar rates of epithelial repair and resting pHo values (~pH 4) were reported in the presence of luminal pH 3 or pH 5. Epithelial repair was unreliable at luminal pH 2 and pHo was lower (2.5±0.2, P <0.05 vs pH 3). Epithelial repair was slower at luminal pH 7 and pHo was higher (6.4±0.1, P<0.001). In all conditions, pHo increased adjacent to damage. At luminal pH 3 or pH 7, omeprazole reduced maximal damage size and accelerated epithelial repair, although only at pH 3 did omeprazole further increase surface pH above the level caused by imposed damage. At luminal pH 7, famotidine also reduced maximal damage size and accelerated epithelial repair. Neither famotidine nor omeprazole raised plasma gastrin levels during the time course of the experiments. Conclusions Epithelial repair in vivo is affected by luminal pH variation, but the beneficial effects of acutely blocking acid secretion extend beyond simply raising luminal and/or surface pH. PMID:21997560

Adsorption/Desorption Transition of Recombinant Human Neurotrophin 4: Physicochemical Characterization.

PubMed

Dąbkowska, Maria; Adamczak, Małgorzata; Barbasz, Jakub; Cieśla, Michał; Machaliński, Bogusław

2017-09-26

Bulk physicochemical properties of neurotrophin 4 (NT-4) in electrolyte solutions and its adsorption/desorption on/from mica surfaces have been studied using dynamic light scattering (DLS), microelectrophoresis, a solution depletion technique (enzyme-linked immunosorbent assay, ELISA), and AFM imaging. Our study presents a determination of the diffusion coefficient, hydrodynamic diameters, electrophoretic mobility, and isoelectric point of the NT-4 under various ionic strength and pH conditions. The size of the NT-4 homodimer for an ionic strength of 0.015 M was substantially independent of pH and equal to 5.1 nm. It has been found that the number of electrokinetic charges per NT-4 molecule was equal to zero for all studied ionic strengths at pH 8.1, which was identified as the isoelectric point (iep). The protein adsorption/desorption on/from mica surfaces was examined as a function of ionic strength and pH. The kinetics of neurotrophin adsorption/desorption were evaluated at pH 3.5, 7.4, and 11 by direct AFM imaging and the ELISA technique. A monotonic increase in the maximum coverage of adsorbed NT-4 molecules with ionic strength (up to 5.5 mg/m 2 ) was observed at pH 3.5. These results were interpreted in terms of the theoretical model postulating an irreversible adsorption of the protein governed by the random sequential adsorption (RSA). Our measurements revealed a significant role of ionic strength, pH, and electrolyte composition in the lateral electrostatic interactions among differently charged NT-4 molecules. The transition between adsorption/desorption processes is found for the region of high pH and low surface concentration of adsorbed neurotrophin molecules at constant ionic strength. Additionally, results presented in this work show that the adsorption behavior of neurotrophin molecules may be governed by intrasolvent electrostatic interactions yielding an aggregation process. Understanding polyvalent neurotrophin interactions may have an impact on the reversibility/irreversibility of adsorption, and hence they might be useful for obtaining well-ordered protein layers, targeting the future development of drug delivery systems for treating neurodegenerative diseases.

Electrochemistry and dissolution kinetics of magnetite and ilmenite

USGS Publications Warehouse

White, A.F.; Peterson, M.L.; Hochella, M.F.

1994-01-01

Natural samples of magnetite and ilmenite were experimentally weathered in pH 1-7 anoxic solutions at temperatures of 2-65 ??C. Reaction of magnetite is described as [Fe2+Fe23+]O4(magnetite) + 2H+ ??? ??[Fe23+]O3(maghemite) + Fe2+ + H2O. Dynamic polarization experiments using magnetite electrodes confirmed that this reaction is controlled by two electrochemical half cells, 3[Fe2+Fe23+]O4(magnetite) ??? 4??[Fe23+]O3(maghemite) + Fe2+ + 2e- and [Fe2+Fe23+]O4(magnetite) + 8 H+ + 2e- ??? 3Fe2+ + 4H2O, which result in solid state Fe3+ reduction, formation of an oxidized layer and release of Fe(II) to solution. XPS data revealed that iron is present in the ferric state in the surfaces of reacted magnetite and ilmenite and that the Ti Fe ratio increased with reaction pH for ilmenite. Short-term (<36 h) release rates of Fe(II) were linear with time. Between pH 1 and 7, rates varied between 0.3 and 13 ?? 10-14 mol ?? cm-2 ?? s-1 for magnetite and 0.05 and 12.3 ?? 10-14 mol ?? cm-2 ?? s-1 for ilmenite. These rates are two orders of magnitude slower than electrochemical rates determined by Tafel and polarization resistance measurements. Discrepancies are due to both differences in geometric and BET surface area estimates and in the oxidation state of the mineral surface. In long-term closed-system experiments (<120 days), Fe(II) release slowed with time due to the passivation of the surfaces by increasing thicknesses of oxide surface layers. A shrinking core model, coupling surface reaction and diffusion transport, predicted that at neutral pH, the mean residence time for sand-size grains of magnetite and ilmenite will exceed 107 years. This agrees with long-term stability of these oxides in the geologic record. ?? 1994.

Application of response surface methodology for optimization of natural organic matter degradation by UV/H2O2 advanced oxidation process

PubMed Central

2014-01-01

Background In this research, the removal of natural organic matter from aqueous solutions using advanced oxidation processes (UV/H2O2) was evaluated. Therefore, the response surface methodology and Box-Behnken design matrix were employed to design the experiments and to determine the optimal conditions. The effects of various parameters such as initial concentration of H2O2 (100–180 mg/L), pH (3–11), time (10–30 min) and initial total organic carbon (TOC) concentration (4–10 mg/L) were studied. Results Analysis of variance (ANOVA), revealed a good agreement between experimental data and proposed quadratic polynomial model (R2 = 0.98). Experimental results showed that with increasing H2O2 concentration, time and decreasing in initial TOC concentration, TOC removal efficiency was increased. Neutral and nearly acidic pH values also improved the TOC removal. Accordingly, the TOC removal efficiency of 78.02% in terms of the independent variables including H2O2 concentration (100 mg/L), pH (6.12), time (22.42 min) and initial TOC concentration (4 mg/L) were optimized. Further confirmation tests under optimal conditions showed a 76.50% of TOC removal and confirmed that the model is accordance with the experiments. In addition TOC removal for natural water based on response surface methodology optimum condition was 62.15%. Conclusions This study showed that response surface methodology based on Box-Behnken method is a useful tool for optimizing the operating parameters for TOC removal using UV/H2O2 process. PMID:24735555

A Uranium Bioremediation Reactive Transport Benchmark

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

Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introducesmore » acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.« less

pH Mapping on Tooth Surfaces for Quantitative Caries Diagnosis Using Micro Ir/IrOx pH Sensor.

PubMed

Ratanaporncharoen, Chindanai; Tabata, Miyuki; Kitasako, Yuichi; Ikeda, Masaomi; Goda, Tatsuro; Matsumoto, Akira; Tagami, Junji; Miyahara, Yuji

2018-04-03

A quantitative diagnostic method for dental caries would improve oral health, which directly affects the quality of life. Here we describe the preparation and application of Ir/IrOx pH sensors, which are used to measure the surface pH of dental caries. The pH level is used as an indicator to distinguish between active and arrested caries. After a dentist visually inspected and defined 18 extracted dentinal caries at various positions as active or arrested caries, the surface pH values of sound and caries areas were directly measured with an Ir/IrOx pH sensor with a diameter of 300 μm as a dental explorer. The average pH values of the sound root, the arrested caries, and active caries were 6.85, 6.07, and 5.30, respectively. The pH obtained with an Ir/IrOx sensor was highly correlated with the inspection results by the dentist, indicating that the types of caries were successfully categorized. This caries testing technique using a micro Ir/IrOx pH sensor provides an accurate quantitative caries evaluation and has potential in clinical diagnosis.

Optimization and performance evaluation for nutrient removal from palm oil mill effluent wastewater using microalgae

NASA Astrophysics Data System (ADS)

Ibrahim, Raheek I.; Wong, Z. H.; Mohammad, A. W.

2015-04-01

Palm oil mill effluent (POME) wastewater was produced in huge amounts in Malaysia, and if it discharged into the environment, it causes a serious problem regarding its high content of nutrients. This study was devoted to POME wastewater treatment with microalgae. The main objective was to find the optimum conditions (retention time, and pH) in the microalgae treatment of POME wastewater considering retention time as a most important parameter in algae treatment, since after the optimum conditions there is a diverse effect of time and pH and so, the process becomes costly. According to our knowledge, there is no existing study optimized the retention time and pH with % removal of nutrients (ammonia nitrogen NH3-N, and orthophosphorous PO43-) for microalgae treatment of POME wastewater. In order to achieve with optimization, a central composite rotatable design with a second order polynomial model was used, regression coefficients and goodness of fit results in removal percentages of nutrients (NH3-N, and PO43-) were estimated.WinQSB technique was used to optimize the surface response objective functionfor the developed model. Also experiments were done to validate the model results.The optimum conditions were found to be 18 day retention time for ammonia nitrogen, and pH of 9.22, while for orthophosphorous, 15 days were indicated as the optimum retention time with a pH value of 9.2.

Impurity effect of iron(III) on the growth of potassium sulfate crystal in aqueous solution

NASA Astrophysics Data System (ADS)

Kubota, Noriaki; Katagiri, Ken-ichi; Yokota, Masaaki; Sato, Akira; Yashiro, Hitoshi; Itai, Kazuyoshi

1999-01-01

Growth rates of the {1 1 0} faces of a potassium sulfate crystal were measured in a flow cell in the presence of traces of impurity Fe(III) (up to 2 ppm) over the range of pH=2.5-6.0. The growth rate was significantly suppressed by the impurity. The effect became stronger as the impurity concentration was increased and at pH<5. It became weaker with increasing supersaturation. It also became weaker as the pH was increased and at pH>5 it finally disappeared completely. The concentration and supersaturation effects on the impurity action were reasonably explained with a model proposed by Kubota and Mullin [J. Crystal Growth, 152 (1995) 203]. The surface coverage of the active sites by Fe(III) is estimated to increase linearly on increasing its concentration in solution in the range examined by growth experiments. The impurity effectiveness factor is confirmed to increase inversely proportional to the supersaturation as predicted by the model. Apart from the discussion based on the model, the pH effect on the impurity action is qualitatively explained by assuming that the first hydrolysis product of aqua Fe(III) complex compound, [Fe(H 2O) 5(OH)] 2+, is both growth suppression and adsorption active, but the second hydrolysis product, [Fe(H 2O) 4(OH) 2] +, is only adsorption active.

Surface charge features of kaolinite particles and their interactions

NASA Astrophysics Data System (ADS)

Gupta, Vishal

Kaolinite is both a blessing and a curse. As an important industrial mineral commodity, kaolinite clays are extensively used in the paper, ceramic, paint, plastic and rubber industries. In all these applications the wettability, aggregation, dispersion, flotation and thickening of kaolinite particles are affected by its crystal structure and surface properties. It is therefore the objective of this research to investigate selected physical and surface chemical properties of kaolinite, specifically the surface charge of kaolinite particles. A pool of advanced analytical techniques such as XRD, XRF, SEM, AFM, FTIR and ISS were utilized to investigate the morphological and surface chemistry features of kaolinite. Surface force measurements revealed that the silica tetrahedral face of kaolinite is negatively charged at pH>4, whereas the alumina octahedral face of kaolinite is positively charged at pH<6, and negatively charged at pH>8. Based on electrophoresis measurements, the apparent iso-electric point for kaolinite particles was determined to be less than pH 3. In contrast, the point of zero charge was determined to be pH 4.5 by titration techniques, which corresponds to the iso-electric point of between pH 4 and 5 as determined by surface force measurements. Results from kaolinite particle interactions indicate that the silica face--alumina face interaction is dominant for kaolinite particle aggregation at low and intermediate pH values, which explains the maximum shear yield stress at pH 5-5.5. Lattice resolution images reveal the hexagonal lattice structure of these two face surfaces of kaolinite. Analysis of the silica face of kaolinite showed that the center of the hexagonal ring of oxygen atoms is vacant, whereas the alumina face showed that the hexagonal surface lattice ring of hydroxyls surround another hydroxyl in the center of the ring. High resolution transmission electron microscopy investigation of kaolinite has indicated that kaolinite is indeed composed of silica/alumina bilayers with a c-spacing of 7.2 A. The surface charge densities of the silica face, the alumina face and the edge surface of kaolinite all influence particle interactions, and thereby affect the mechanical properties of kaolinite suspensions. The improved knowledge of kaolinite surface chemistry from this dissertation research provides a foundation for the development of improved process strategies for both the use and disposal of clay particles such as kaolinite.

Interfacial properties of acidified skim milk.

PubMed

Cases, E; Rampini, C; Cayot, Ph

2005-02-01

The purpose of this study is to investigate the tension properties and dilatational viscoelastic modulus of various skim milk proteins (whole milk, EDTA-treated milk, beta-casein, and beta-lactoglobulin) at an oil/water interface at 20 degrees C. Measurements are performed using a dynamic drop tensiometer for 15,000 s. The aqueous bulk phase is a skim milk simulated ultrafiltrate containing 11 x 10(-3) g L(-1) milk protein. At pH 6.7, beta-casein appears as the best to decrease the interfacial tension, whereas beta-lactoglobulin leads to the highest interfacial viscoelastic modulus value. Whole milk was almost as surface-active as individual beta-casein in terms of the final (steady-state) lowering of the interfacial tension, but the rate of tension lowering was smaller. EDTA treatment improved the rate of tension lowering of whole milk. The acidification of milk, from previous measurements, would lead to the enhancement of surface activity. At t=15,000 s, the order of effectiveness is pH 4.3 > pH 5.3 = pH 5.6 > pH 6.7 whole milk, suggesting that pH 4.3 whole milk is the best surface active. As compared to pH 6.7 whole milk, the use of pH 5.3 and pH 5.6 milk as surface active would result in the use of milk containing more free beta-casein born of pH-dissociated casein micelles.

X-Ray Excited Luminescence Chemical Imaging of Bacterial Growth on Surfaces Implanted in Tissue.

PubMed

Wang, Fenglin; Raval, Yash; Tzeng, Tzuen-Rong J; Anker, Jeffrey N

2015-04-22

A pH sensor film is developed that can be coated on an implant surface and imaged using a combination of X-ray excitation and visible spectroscopy to monitor bacterial infection and treatment of implanted medical devices (IMDs) through tissue. X-ray scintillators in the pH sensor film generate light when an X-ray beam irradiates them. This light first passes through a layer containing pH indicator that alters the spectrum according to pH, then passes through and out of the tissue where it is detected by a spectrometer. A reference region on the film is used to account for spectral distortion from wavelength-dependent absorption and scattering in the tissue. pH images are acquired by moving the sample relative to the X-ray beam and collecting a spectrum at each location, with a spatial resolution limited by the X-ray beam width. Using this X-ray excited luminescence chemical imaging (XELCI) to map pH through ex vivo porcine tissue, a pH drop is detected during normal bacterial growth on the sensor surface, and a restoration of the pH to the bulk value during antibiotic treatment over the course of hours with milli-meter resolution. Overall, XELCI provides a novel approach to noninvasively image surface pH for studying implant infections and treatments. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio calculation of potential energy surfaces for the three lowest triplet states (1 3A'',1 3A,2 3A'') of PH(X,A)-He

NASA Astrophysics Data System (ADS)

Kolczewski, Ch.; Fink, K.; Staemmler, V.; Neitsch, L.

1997-05-01

Quantum chemical ab initio calculations at the complete active space SCF level and with inclusion of correlation effects have been performed for the potential energy surfaces of PH in its X 3Σ- ground state and its first excited triplet state, A 3Π, colliding with He atoms. The PH distance was fixed at its experimental value (of the A 3Π state), the PH-He distance and the HePH angle were varied. All three potential energy surfaces [1 3A'' for PH(X)-He and 1 3A,2 3A'' for the two components of PH(A)-He] are purely repulsive, except for very shallow van der Waals minima with well depths of about 15-40 cm-1. The interaction potentials decay approximately exponentially with increasing PH-He distance and show large angular anisotropies. Legendre expansions for the angular dependence of the potential surfaces converge slowly for V(1 3A'') and the sum potential 1/2[V(2 3A'')+V(1 3A)], but rapidly for the corresponding difference potential 1/2[V(2 3A'')-V(1 3A)]. The present PH(A)-He potentials have been used in the companion paper by Neitsch et al. [J. Chem. Phys. 106, 7642 (1997)], for the calculation of thermal state-to-state rate constants for inelastic PH(A)-He collisions.

Dynamic electrophoretic fingerprinting of the HIV-1 envelope glycoprotein

PubMed Central

2013-01-01

Background Interactions between the HIV-1 envelope glycoprotein (Env) and its primary receptor CD4 are influenced by the physiological setting in which these events take place. In this study, we explored the surface chemistry of HIV-1 Env constructs at a range of pH and salinities relevant to mucosal and systemic compartments through electrophoretic mobility (EM) measurements. Sexual transmission events provide a more acidic environment for HIV-1 compared to dissemination and spread of infection occurring in blood or lymph node. We hypothesize functional, trimeric Env behaves differently than monomeric forms. Results The dynamic electrophoretic fingerprint of trimeric gp140 revealed a change in EM from strongly negative to strongly positive as pH increased from that of the lower female genital tract (pHx) to that of the blood (pHy). Similar findings were observed using a trimeric influenza Haemagglutinin (HA) glycoprotein, indicating that this may be a general attribute of trimeric viral envelope glycoproteins. These findings were supported by computationally modeling the surface charge of various gp120 and HA crystal structures. To identify the behavior of the infectious agent and its target cells, EM measurements were made on purified whole HIV-1 virions and primary T-lymphocytes. Viral particles had a largely negative surface charge, and lacked the regions of positivity near neutral pH that were observed with trimeric Env. T cells changed their surface chemistry as a function of activation state, becoming more negative over a wider range of pH after activation. Soluble recombinant CD4 (sCD4) was found to be positively charged under a wide range of conditions. Binding studies between sCD4 and gp140 show that the affinity of CD4-gp140 interactions depends on pH. Conclusions Taken together, these findings allow a more complete model of the electrochemical forces involved in HIV-1 Env functionality. These results indicate that the influence of the localized environment on the interactions of HIV with target cells are more pronounced than previously appreciated. There is differential chemistry of trimeric, but not monomeric, Env under conditions which mimic the mucosa compared to those found systemically. This should be taken into consideration during design of immunogens which targets virus at mucosal portals of entry. PMID:23514633

Understanding potential exposure sources of perfluorinated carboxylic acids in the workplace.

PubMed

Kaiser, Mary A; Dawson, Barbara J; Barton, Catherine A; Botelho, Miguel A

2010-11-01

This paper integrates perspectives from analytical chemistry, environmental engineering, and industrial hygiene to better understand how workers may be exposed to perfluorinated carboxylic acids when handling them in the workplace in order to identify appropriate exposure controls. Due to the dramatic difference in physical properties of the protonated acid form and the anionic form, this family of chemicals provides unique industrial hygiene challenges. Workplace monitoring, experimental data, and modeling results were used to ascertain the most probable workplace exposure sources and transport mechanisms for perfluorooctanoic acid (PFOA) and its ammonium salt (APFO). PFOA is biopersistent and its measurement in the blood has been used to assess human exposure since it integrates exposure from all routes of entry. Monitoring suggests that inhalation of airborne material may be an important exposure route. Transport studies indicated that, under low pH conditions, PFOA, the undissociated (acid) species, actively partitions from water into air. In addition, solid-phase PFOA and APFO may also sublime into the air. Modeling studies determined that contributions from surface sublimation and loss from low pH aqueous solutions can be significant potential sources of workplace exposure. These findings suggest that keeping surfaces clean, preventing accumulation of material in unventilated areas, removing solids from waste trenches and sumps, and maintaining neutral pH in sumps can lower workplace exposures.

Historical winter weather assessment for snow fence design using a numerical weather model.

DOT National Transportation Integrated Search

2017-03-30

Noriaki Ohara, Ph.D., Assistant Professor (0000-0002-7829-0779) : Snow fence is an effective hazard mitigation measure for the low visibility and low friction of the road surface under : winter weather condition. Prevailing wind directions and snow p...

Statistical analysis and isotherm study of uranium biosorption by Padina sp. algae biomass.

PubMed

Khani, Mohammad Hassan

2011-06-01

The application of response surface methodology is presented for optimizing the removal of U ions from aqueous solutions using Padina sp., a brown marine algal biomass. Box-Wilson central composite design was employed to assess individual and interactive effects of the four main parameters (pH and initial uranium concentration in solutions, contact time and temperature) on uranium uptake. Response surface analysis showed that the data were adequately fitted to second-order polynomial model. Analysis of variance showed a high coefficient of determination value (R (2)=0.9746) and satisfactory second-order regression model was derived. The optimum pH and initial uranium concentration in solutions, contact time and temperature were found to be 4.07, 778.48 mg/l, 74.31 min, and 37.47°C, respectively. Maximized uranium uptake was predicted and experimentally validated. The equilibrium data for biosorption of U onto the Padina sp. were well represented by the Langmuir isotherm, giving maximum monolayer adsorption capacity as high as 376.73 mg/g.

Examination of the polished surface character of fused silica.

PubMed

Tesar, A A; Fuchs, B A; Hed, P P

1992-12-01

Investigation of the surface character of fused silica polished with various compounds dispersed in water identified pH 4 as the optimum condition for high quality. Analyses support the conclusion that at this pH redeposition of hydrated material onto the surface during polishing is limited. Comparative polishing results for Zerodur are included. Improvement of the laser-damage threshold of a coating on the pH 4 polished fused silica is suggested.

Examination of the polished surface character of fused silica

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

Tesar, A.A.; Fuchs, B.A.; Hed, P.P.

1992-12-01

Investigation of the surface character of fused silica polished with various compounds dispersed in water identified pH 4 as the optimum condition for high quality. Analyses support the conclusion that at this pH redeposition of hydrated material onto the surface during polishing is limited. Comparative polishing results for Zerodur are included. Improvement of the laser-damage threshold of a coating on the pH 4 polished fused silica is suggested.

Integrated combined effects of temperature, pH and sodium chloride concentration on biofilm formation by Salmonella enterica ser. Enteritidis and Typhimurium under low nutrient food-related conditions.

PubMed

Iliadis, Ioannis; Daskalopoulou, Aikaterini; Simões, Manuel; Giaouris, Efstathios

2018-05-01

Salmonella enterica is a major foodborne bacterial pathogen. This forms biofilms on surfaces and persists, depending on the strain and the environment. The integrative interaction of temperature (T; 13-39 °C), pH (5-8) and sodium chloride (NaCl) concentration (0.5-8.5%) on biofilm formation by two S. enterica strains (ser. Enteritidis and Typhimurium) was here evaluated under low nutrient conditions. This was achieved using response surface methodology to model the combined effect of each factor on the response, through mathematical quadratic fitting of the outcomes of a sequence of designed experiments. These last were executed by incubating stainless steel coupons carrying sessile bacteria, for 24 h, in 1:10 diluted tryptone soya broth, under 15 different combinations of three independent factors (T, pH and NaCl). For each strain, a second order polynomial model, describing the relationship between biofilm formation (log CFU/cm 2 ) and the factors (T, pH and NaCl), was developed using least square regression analysis. Both derived models predicted the combined influences of these factors on biofilm formation, with agreement between predictions and experimental observations (R 2  ≥ 0.96, P ≤ 0.0001). For both strains, the increase of NaCl content restricted their sessile growth, while under low salinity conditions (NaCl < 4%) biofilm formation was favored as pH increased, regardless of T. Interestingly, under low salt content, and depending on the strain, biofilm formation was either favored or hindered by increasing T. Thus, 34.5 and 13 °C were the T predicted to maximize biofilm formation by strains Enteritidis and Typhimurium, respectively, something which was also experimentally verified. To sum, these models can predict the interactive influences of crucial food-related factors on biofilm growth of a significant foodborne pathogen towards the efforts to limit its persistence in food industry. Copyright © 2018 Elsevier Ltd. All rights reserved.

Searching for Clues to the Processes and Conditions of Past Martian Environments: The Roles of Episodic Solutions, Analog Sites and Fe-O(-H) Phases

NASA Astrophysics Data System (ADS)

King, P. L.; De Deckker, P.

2012-12-01

On Mars, limited solutions (water/brine) were likely present episodically. Gradients in solution abundance may have caused salt precipitation and re-solution, brine reflux, pH gradients, and cycling of anions and cations; we provide an example of such processes in a playa lake. We propose that on Mars, the limited, episodic solutions, pH and abundant Fe-O(-H) phases are significant factors in salt precipitation and in promoting adsorption/desorption of anions and cations. FACTORS LEADING TO EPISODIC SOLUTIONS: Episodic movement of solutions may be driven by punctuated processes that 1) remove surface materials (e.g., impact and sedimentary mass wasting and deflation); 2) add surface materials (e.g., impact, volcanic and sedimentary processes); and 3) increase temperature and/or decrease atmospheric pressure (e.g., seasons, diurnal cycles, variation in obliquity). Removal and addition of surface materials results in topographic gradients that change pressure gradients of any potential groundwater, films, or buried ground ice. For example, episodic fluid flow and salt precipitation/re-solution may occur at topographic discontinuities like craters/basins, channel walls, mounds and dunes. Such areas provide the opportunity to sample multiple fluid sources (with different pH, Eh and total dissolved solids, TDS) and they may be the foci of subsurface solution flow and surface transport. EARTH ANALOG: Interplay of the three processes above is seen in Lake Tyrrell (playa), western Victoria, Australia (McCumber, P, 1991 http://vro.dpi.vic.gov.au). During wetter periods, springs from the regional groundwater (low pH, oxidized, mod-high TDS) mix with lake waters and saline 'reflux' brines (mod. pH, reduced, high TDS) at the lake edge at the base of higher ground. The Br/Cl of the reflux brines indicates mineral re-solution. Gypsum and Fe-O(-H) phases precipitate near the lake edge. During hot, dry climate episodes the lake precipitates gypsum and carbonate, efflorescent salts are common, and these salts may form eolian dunes with fine particles. We may expect similar processes and mineral and chemical gradients in craters/basins on Mars like Gale Crater, the site of the Mars Science Laboratory mission. ROLE OF Fe-O(-H) PHASES: Nanophase Fe-O(-H)-phases are abundant on Mars and their precipitation results in an Fe-poor solution and salts (like Lake Tyrrell). Fe-O(-H) phases precipitate most readily at near-neutral pH; however, the high Fe of Mars' surface allows for pH>1. Nanophase Fe-O(-H)-phases have surface species that promote adsorption; which may be important in dry conditions like Mars. If we take goethite (FeO(OH)), the surface species and aqueous ions in solution are Fe3+ (pH<~2); Fe(OH)2+ (pH~2-3.5); Fe(OH)2+ (pH~3.5-~8); and FeOH4- (pH>~8). Other Fe-O(-H) phases have slightly different pH limits. Thus, at pH<~8, Fe-O(-H) surfaces sequester anions in surface complexes or in Fe-bearing salts (e.g. Fe3+-phosphate and sulfates, especially at pH<4). PO43- species have high adsorption affinity, followed by SO42-, Cl-(O) and Br-(O) species. At pH>~8, adsorption and exchange of cations are likely. These chemical variations may provide us with clues of the past pH on Mars.

The effect of geometrical presentation of multimodal cation-exchange ligands on selective recognition of hydrophobic regions on protein surfaces.

PubMed

Woo, James; Parimal, Siddharth; Brown, Matthew R; Heden, Ryan; Cramer, Steven M

2015-09-18

The effects of spatial organization of hydrophobic and charged moieties on multimodal (MM) cation-exchange ligands were examined by studying protein retention behavior on two commercial chromatographic media, Capto™ MMC and Nuvia™ cPrime™. Proteins with extended regions of surface-exposed aliphatic residues were found to have enhanced retention on the Capto MMC system as compared to the Nuvia cPrime resin. The results further indicated that while the Nuvia cPrime ligand had a strong preference for interactions with aromatic groups, the Capto MMC ligand appeared to interact with both aliphatic and aromatic clusters on the protein surfaces. These observations were formalized into a new set of protein surface property descriptors, which quantified the local distribution of electrostatic and hydrophobic potentials as well as distinguishing between aromatic and aliphatic properties. Using these descriptors, high-performing quantitative structure-activity relationship (QSAR) models (R(2)>0.88) were generated for both the Capto MMC and Nuvia cPrime datasets at pH 5 and pH 6. Descriptors of electrostatic properties were generally common across the four models; however both Capto MMC models included descriptors that quantified regions of aliphatic-based hydrophobicity in addition to aromatic descriptors. Retention was generally reduced by lowering the ligand densities on both MM resins. Notably, elution order was largely unaffected by the change in surface density, but smaller and more aliphatic proteins tended to be more affected by this drop in ligand density. This suggests that modulating the exposure, shape and density of the hydrophobic moieties in multimodal chromatographic systems can alter the preference for surface exposed aliphatic or aromatic residues, thus providing an additional dimension for modulating the selectivity of MM protein separation systems. Copyright © 2015 Elsevier B.V. All rights reserved.

In Situ Monitoring of Pb2+ Leaching from the Galvanic Joint Surface in a Prepared Chlorinated Drinking Water.

PubMed

Ma, Xiangmeng; Armas, Stephanie M; Soliman, Mikhael; Lytle, Darren A; Chumbimuni-Torres, Karin; Tetard, Laurene; Lee, Woo Hyoung

2018-02-20

A novel method using a micro-ion-selective electrode (micro-ISE) technique was developed for in situ lead monitoring at the water-metal interface of a brass-leaded solder galvanic joint in a prepared chlorinated drinking water environment. The developed lead micro-ISE (100 μm tip diameter) showed excellent performance toward soluble lead (Pb 2+ ) with sensitivity of 22.2 ± 0.5 mV decade -1 and limit of detection (LOD) of 1.22 × 10 -6 M (0.25 mg L -1 ). The response time was less than 10 s with a working pH range of 2.0-7.0. Using the lead micro-ISE, lead concentration microprofiles were measured from the bulk to the metal surface (within 50 μm) over time. Combined with two-dimensional (2D) pH mapping, this work clearly demonstrated that Pb 2+ ions build-up across the lead anode surface was substantial, nonuniform, and dependent on local surface pH. A large pH gradient (ΔpH = 6.0) developed across the brass and leaded-tin solder joint coupon. Local pH decreases were observed above the leaded solder to a pH as low as 4.0, indicating it was anodic relative to the brass. The low pH above the leaded solder supported elevated lead levels where even small local pH differences of 0.6 units (ΔpH = 0.6) resulted in about four times higher surface lead concentrations (42.9 vs 11.6 mg L -1 ) and 5 times higher fluxes (18.5 × 10 -6 vs 3.5 × 10 -6 mg cm -2 s -1 ). Continuous surface lead leaching monitoring was also conducted for 16 h.

The effect of retreatment procedure on the pH changes at the surface of root dentin using two different calcium hydroxide pastes

PubMed Central

Kazemipoor, Maryam; Tabrizizadeh, Mehdi; Dastani, Milad; Hakimian, Roqayeh

2012-01-01

Aim: To compare pH changes at the cervical, middle and apical surfaces of root dentin in retreated and non- retreated teeth, after canal obturation with two different calcium hydroxide pastes. Materials and Methods: After instrumentation of 55 extracted teeth, three cavities with 0.75 mm depth and 1.5 mm in diameter were drilled at buccal root surface. The teeth were randomly divided into five groups. Canals in the first two groups were filled with either mixture of calcium hydroxide and saline solution and calcium hydroxide and 2% chlorhexidine (CHX). In the third and fourth groups canals were first obturated with gutta-percha and AH26 sealer, and then materials were removed. After 2 days canals were filled with two different calcium hydroxide pastes similar to the first and the second groups. The pH was measured in the prepared cavities at 1, 3, 7 and 14 days. Results: In the non-retreated groups, pH at the surface of the roots was significantly higher in comparison to the retreated ones (P value < 0.001). pH values were significantly higher in the non-retreated teeth filling with calcium hydroxide and saline solution (P value < 0.001). Conclusion: Regarding to the little pH changes at the surface of dentin in retreated teeth, the hydroxyl ions cannot penetrate into the dentinal tubules. Thus, to achieve higher pH at the root surface in retreated teeth, it is clinically advisable to remove more dentin from the inner walls and to use normal saline as a vehicle for calcium hydroxide rather than acidic pH materials. PMID:23112482

The effect of retreatment procedure on the pH changes at the surface of root dentin using two different calcium hydroxide pastes.

PubMed

Kazemipoor, Maryam; Tabrizizadeh, Mehdi; Dastani, Milad; Hakimian, Roqayeh

2012-10-01

To compare pH changes at the cervical, middle and apical surfaces of root dentin in retreated and non- retreated teeth, after canal obturation with two different calcium hydroxide pastes. After instrumentation of 55 extracted teeth, three cavities with 0.75 mm depth and 1.5 mm in diameter were drilled at buccal root surface. The teeth were randomly divided into five groups. Canals in the first two groups were filled with either mixture of calcium hydroxide and saline solution and calcium hydroxide and 2% chlorhexidine (CHX). In the third and fourth groups canals were first obturated with gutta-percha and AH26 sealer, and then materials were removed. After 2 days canals were filled with two different calcium hydroxide pastes similar to the first and the second groups. The pH was measured in the prepared cavities at 1, 3, 7 and 14 days. In the non-retreated groups, pH at the surface of the roots was significantly higher in comparison to the retreated ones (P value < 0.001). pH values were significantly higher in the non-retreated teeth filling with calcium hydroxide and saline solution (P value < 0.001). Regarding to the little pH changes at the surface of dentin in retreated teeth, the hydroxyl ions cannot penetrate into the dentinal tubules. Thus, to achieve higher pH at the root surface in retreated teeth, it is clinically advisable to remove more dentin from the inner walls and to use normal saline as a vehicle for calcium hydroxide rather than acidic pH materials.

Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase.

PubMed

Hung, Hui-Ming; Hoffmann, Michael R

2015-12-01

The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH < 3 without addition of oxidants other than oxygen suggests an efficient oxidation pathway via sulfite and sulfate radical anions on droplets possibly via the direct interfacial electron transfer from HSO3(-) to O2. The concentrations of HSO3(-) in the aqueous aerosol as a function of pH were controlled by the deprotonation of hydrated sulfur dioxide, SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH < 3 due to relatively low HSO3(-) concentration caused by the fast interfacial reactions. The rapid oxidation of SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ≤ 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world.

Electric double layer at metal oxide surfaces:static properties of the cassiterite-water interface.

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

Vlcek, L.; Zhang, Z.; Machesky, M .L.

2007-03-24

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Electric double layer at metal oxide surfaces: Static properties of the cassiterite - Water Interface

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

Vlcek, Lukas; Zhang, Zhan; Machesky, Michael L.

2007-01-01

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Reverse Micelle Mediated synthesis of Calcium Phosphate Nanocarriers for Controlled Release of Bovine Serum Albumin (BSA)

PubMed Central

Dasgupta, Sudip; Bandyopadhyay, Amit; Bose, Susmita

2010-01-01

Calcium phosphate (CaP) nanoparticle with calcium to phosphorus (Ca:P) molar ratio of 1.5:1 were synthesized using reverse micro emulsion. Ca(NO3)2.4H2O and H3PO4 were used as aqueous phase, cyclohexane as organic phase, and poly(oxyethylene)12 nonylphenol ether (NP-12) as surfactant. Depending on calcination temperature between 600 and 800 °C, CaP nanoparticle showed different phases calcium deficient hydroxyapatite (CDHA) and β-tricalcium phosphate (β-TCP), particle size between 48 and 69 nm, the BET specific average surface area between 73 m2/g and 57 m2/g. Bovine serum albumin (BSA) was used as a model protein to study loading and release behavior. Adsorptive property of BSA was investigated with the change in BET surface area of these nanoparticle and the pH of the suspension. At pH 7.5, maximum amount of BSA was adsorbed onto CaP nanoparticle. The release kinetics of BSA showed a gradual time dependent increase at pH 4.0 and 6.0 buffer solutions. However, the amount of released protein was significantly smaller at pH 7.2. BSA release rate also varied depending on the presence of different phases of CaPs in the system, β-TCP or CDHA. These results suggest that BSA protein release rate can be controlled by changing particle size, surface area and phase composition of CaP nanocarriers. PMID:19435617

Zeta potential orientation dependence of sapphire substrates.

PubMed

Kershner, Ryan J; Bullard, Joseph W; Cima, Michael J

2004-05-11

The zeta potential of planar sapphire substrates for three different crystallographic orientations was measured by a streaming potential technique in the presence of KCl and (CH3)4NCl electrolytes. The streaming potential was measured for large single crystalline C-plane (0001), A-plane (1120), and R-plane (1102) wafers over a full pH range at three or more ionic strengths ranging from 1 to 100 mM. The roughness of the epi-polished wafers was verified using atomic force microscopy to be on the order of atomic scale, and X-ray photoelectron spectroscopy (XPS) was used to ensure that the samples were free of silica and other contaminants. The results reveal a shift in the isoelectric point (iep) of the three samples by as much as two pH units, with the R-plane surface exhibiting the most acidic behavior and the C-plane samples having the highest iep. The iep at all ionic strengths was tightly centered around a single pH for each wafer. These values of iep are substantially different from the range of pH 8-10 consistently reported in the literature for alpha-Al2O3 particles. Particle zeta potential measurements were performed on a model powder using phase analysis light scattering, and the iep was confirmed to occur at pH 8. Modified Auger parameters (MAP) were calculated from XPS spectra of a monolayer of iridium metal deposited on the sapphire by electron beam deposition. A shift in MAP consistent with the observed differences in iep of the surfaces confirms the effect of surface structure on the transfer of charge between the Ir and sapphire, hence accounting for the changes in acidity as a function of crystallographic orientation.

Applying Central Composite Design and Response Surface Methodology to Optimize Growth and Biomass Production of Haemophilus influenzae Type b.

PubMed

Momen, Seyed Bahman; Siadat, Seyed Davar; Akbari, Neda; Ranjbar, Bijan; Khajeh, Khosro

2016-06-01

Haemophilus influenzae type b (Hib) is the leading cause of bacterial meningitis, otitis media, pneumonia, cellulitis, bacteremia, and septic arthritis in infants and young children. The Hib capsule contains the major virulence factor, and is composed of polyribosyl ribitol phosphate (PRP) that can induce immune system response. Vaccines consisting of Hib capsular polysaccharide (PRP) conjugated to a carrier protein are effective in the prevention of the infections. However, due to costly processes in PRP production, these vaccines are too expensive. To enhance biomass, in this research we focused on optimizing Hib growth with respect to physical factors such as pH, temperature, and agitation by using a response surface methodology (RSM). We employed a central composite design (CCD) and a response surface methodology to determine the optimum cultivation conditions for growth and biomass production of H. influenzae type b. The treatment factors investigated were initial pH, agitation, and temperature, using shaking flasks. After Hib cultivation and determination of dry biomass, analysis of experimental data was performed by the RSM-CCD. The model showed that temperature and pH had an interactive effect on Hib biomass production. The dry biomass produced in shaking flasks was about 5470 mg/L, which was under an initial pH of 8.5, at 250 rpm and 35° C. We found CCD and RSM very effective in optimizing Hib culture conditions, and Hib biomass production was greatly influenced by pH and incubation temperature. Therefore, optimization of the growth factors to maximize Hib production can lead to 1) an increase in bacterial biomass and PRP productions, 2) lower vaccine prices, 3) vaccination of more susceptible populations, and 4) lower risk of Hib infections.

Optimization of Bromelain-Aided Production of Angiotensin I-Converting Enzyme Inhibitory Hydrolysates from Stone Fish Using Response Surface Methodology

PubMed Central

Auwal, Shehu Muhammad; Zarei, Mohammad; Abdul-Hamid, Azizah; Saari, Nazamid

2017-01-01

The stone fish is an under-utilized sea cucumber with many nutritional and ethno-medicinal values. This study aimed to establish the conditions for its optimum hydrolysis with bromelain to generate angiotensin I-converting enzyme (ACE)-inhibitory hydrolysates. Response surface methodology (RSM) based on a central composite design was used to model and optimize the degree of hydrolysis (DH) and ACE-inhibitory activity. Process conditions including pH (4–7), temperature (40–70 °C), enzyme/substrate (E/S) ratio (0.5%–2%) and time (30–360 min) were used. A pH of 7.0, temperature of 40 °C, E/S ratio of 2% and time of 240 min were determined using a response surface model as the optimum levels to obtain the maximum ACE-inhibitory activity of 84.26% at 44.59% degree of hydrolysis. Hence, RSM can serve as an effective approach in the design of experiments to improve the antihypertensive effect of stone fish hydrolysates, which can thus be used as a value-added ingredient for various applications in the functional foods industries. PMID:28362352

Fabrication and characterization of akaganeite/graphene oxide nanocomposite for arsenic removal from water

NASA Astrophysics Data System (ADS)

Trang, Nguyen Thi Thuy; Thy, Lu Thi Mong; Cuong, Pham Mai; Tu, Tran Hoang; Hieu, Nguyen Huu

2018-04-01

In this study, akageneite/graphene oxide (β-FeOOH/GO) nanocomposite was fabricated by in situ forced hydrolysis of iron (III) chloride. The structure and morphology of β-FeOOH/GO were characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer-Emmett- Teller (BET) specific surface area. XRD, FTIR, and TEM results indicated that β-FeOOH nanoparticles were successfully decorated on the surface of GO nanosheets. The BET specific surface area of β-FeOOH/GO was observed of 97.94 m2/g. The nanocomposite was used as an adsorbent for removal of arsenic (As5+) from water. Adsorption experiments were carried out to investigate contact time, pH values, and As5+ initial concentrations. The adsorption equilibrium time was reached within 180 minutes. The adsorption was well-fitted by a pseudo-second-order kinetic and Langmuir isotherm model. The maximum adsorption capacity of β-FeOOH/GO for As5+ ions of 94.34 mg/g that was calculated from the Langmuir model at pH 3. Accordingly, the nanocomposite β-FeOOH/GO could be considered as a highly efficient adsorbent for removing arsenic from water.

Oxidative dissolution of silver nanoparticles: A new theoretical approach.

PubMed

Adamczyk, Zbigniew; Oćwieja, Magdalena; Mrowiec, Halina; Walas, Stanisław; Lupa, Dawid

2016-05-01

A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Ratiometric photoluminescence sensing based on Ti3C2 MXene quantum dots as an intracellular pH sensor.

PubMed

Chen, Xu; Sun, Xueke; Xu, Wen; Pan, Gencai; Zhou, Donglei; Zhu, Jinyang; Wang, He; Bai, Xue; Dong, Biao; Song, Hongwei

2018-01-18

Intracellular pH sensing is of importance and can be used as an indicator for monitoring the evolution of various diseases and the health of cells. Here, we developed a new class of surface-functionalized MXene quantum dots (QDs), Ti 3 C 2 , by the sonication cutting and hydrothermal approach and further explored their intracellular pH sensing. The functionalized Ti 3 C 2 QDs exhibit bright excitation-dependent blue photoluminescence (PL) originating from the size effect and surface defects. Meanwhile, Ti 3 C 2 QDs demonstrate a high PL response induced by the deprotonation of the surface defects. Furthermore, combining the highly pH sensitive Ti 3 C 2 QDs with the pH insensitive [Ru(dpp) 3 ]Cl 2 , we developed a ratiometric pH sensor to quantitatively monitor the intracellular pH values. These novel MXene quantum dots can serve as a promising platform for developing practical fluorescent nanosensors.

Bluetooth technology for prevention of dental caries.

PubMed

Kolahi, Jafar; Fazilati, Mohamad

2009-12-01

Caries is caused when the pH at the tooth surface drops below 5.5. A miniaturized and autonomous pH monitoring nodes can be attached to the tooth surface, like a tooth jewel. This intelligent sensor includes three components: (a) digital micro pH meter, (b) power supply, (c) wireless communicating device. The micro pH meter facilitates long term tooth surface pH monitoring and providing real time feedback to the patients and dental experts. Power supply of this system will be microfabricated biocatalytic fuel cell (enzymatic micro-battery) using organic compounds (e.g. formate or glucose) as the fuel to generate electricity. When micro pH meter detects the pH lower than 5.5, wireless Bluetooth device sends a caution (e.g. "you are at risk of dental caries") to external monitoring equipment such as mobile phone or a hands-free heads. After reception of the caution, subjects should use routine brushing and flossing procedure or use a medicated chewing gum (e.g. chlorhexidine containing chewing gum) or rinse with a mouthwash.

Responses of microbial community to pH stress in bioleaching of low grade copper sulfide.

PubMed

Wang, Yuguang; Li, Kai; Chen, Xinhua; Zhou, Hongbo

2018-02-01

The microbial diversity and dynamics in the leachates and on the ore surfaces of different depth of the column were analyzed during bioleaching of low grade copper sulfide at different pH, after inoculation with the same inoculum containing mesophiles and moderate thermophiles. The results indicate that low pH was beneficial to enhance copper extraction. The highest copper extraction (86%) was obtained when pH was controlled at 1.0-1.5. The microbial structures on the ore surfaces were independent of community structures in the leachate, even at the top portion of column. Microbial richness and evenness increased with decreasing pH during bioleaching. pH had significant effects on microbial community structure in the leachate and on the mineral surface of different depth of the column. Leptospirillum ferriphilum accounted for the highest proportions of the community at most times when pH was operated during bioleaching, especially at the end of run. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Farmer, R.W.; Dussert, B.W.; Kovacic, S.L.

Laboratory studies have identified the cause of the pH rise, which occurs during water treatment with activated carbon, as an interaction between the naturally occurring anions and protons in the water and the carbon surface. The interaction can be described as an ion exchange type of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. These studies have shown that the anion sorption and resulting pH increase is independent of the raw material used for the activated carbon production, e.g. bituminous or subbituminous coal, peat, wood or coconut. Also, the pH excursions occurmore » with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of the wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface through controlled oxidation rather than the water chemistry or extended preprocessing at the treatment site.« less

Surface catalysis of uranium(VI) reduction by iron(II)

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

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

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

NONE

Many times the start up of granular activated carbon adsorption systems for the control of organic contaminants in wastewater cm exhibit unacceptable increases in the adscurber effluent pH. Experience shows that the duration of the pH increase ranges from several hours to several days, during which time several hundred bed volumes of water can be discharged with a pH in excess of 9. Laboratory studies have identified the cause of the pH rise as an interaction between the naturally occurring anions and protons ar the water and the carbon surface. The interaction can be described as an ion exchange typemore » of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. Capacities of the carbon for the anions range from 2 to 9 mg/g GAC, depending upon the water characteristics, the carbon type, the nature of the anion and its influent concentration. These studies have shown de the anion sorption and resulting pH increase is independent of the raw material used for die activated carbon production, e.g. bituminous or sub-bituminous coal, peat, wood or coconut. Also, the pH excursions occur with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface rather than the water chemistry. The change to the carbon surface is accomplished through a controlled oxidation process. This process provides a more acidic carbon surface with a reduced affinity for the anions in the waste water. As a result, the pH excursions above 9 are eliminated and the initial effluent from the adsorption system can be discharged without further treatment.« less

Fibronectin module FN(III)9 adsorption at contrasting solid model surfaces studied by atomistic molecular dynamics.

PubMed

Kubiak-Ossowska, Karina; Mulheran, Paul A; Nowak, Wieslaw

2014-08-21

The mechanism of human fibronectin adhesion synergy region (known as integrin binding region) in repeat 9 (FN(III)9) domain adsorption at pH 7 onto various and contrasting model surfaces has been studied using atomistic molecular dynamics simulations. We use an ionic model to mimic mica surface charge density but without a long-range electric field above the surface, a silica model with a long-range electric field similar to that found experimentally, and an Au {111} model with no partial charges or electric field. A detailed description of the adsorption processes and the contrasts between the various model surfaces is provided. In the case of our model silica surface with a long-range electrostatic field, the adsorption is rapid and primarily driven by electrostatics. Because it is negatively charged (-1e), FN(III)9 readily adsorbs to a positively charged surface. However, due to its partial charge distribution, FN(III)9 can also adsorb to the negatively charged mica model because of the absence of a long-range repulsive electric field. The protein dipole moment dictates its contrasting orientation at these surfaces, and the anchoring residues have opposite charges to the surface. Adsorption on the model Au {111} surface is possible, but less specific, and various protein regions might be involved in the interactions with the surface. Despite strongly influencing the protein mobility, adsorption at these model surfaces does not require wholesale FN(III)9 conformational changes, which suggests that the biological activity of the adsorbed protein might be preserved.

Predicting adhesion and biofilm formation boundaries on stainless steel surfaces by five Salmonella enterica strains belonging to different serovars as a function of pH, temperature and NaCl concentration.

PubMed

Moraes, Juliana O; Cruz, Ellen A; Souza, Enio G F; Oliveira, Tereza C M; Alvarenga, Verônica O; Peña, Wilmer E L; Sant'Ana, Anderson S; Magnani, Marciane

2018-05-26

This study aimed to assess the capability of 97 epidemic S. enterica strains belonging to 18 serovars to form biofilm. Five strains characterized as strong biofilm-producers, belonging to distinct serovars (S. Enteritidis 132, S. Infantis 176, S. Typhimurium 177, S. Heidelberg 281 and S. Corvallis 297) were assayed for adhesion/biofilm formation on stainless steel surfaces. The experiments were conducted in different combinations of NaCl (0, 2, 4, 5, 6, 8 and 10% w/v), pH (4, 5, 6 and 7) and temperatures (8 °C, 12 °C, 20 °C and 35 °C). Only adhesion was assumed to occur when S. enterica counts were ≥3 and <5 log CFU/cm 2 , whereas biofilm formation was defined as when the counts were ≥5 log CFU/cm 2 . The binary responses were used to develop models to predict the probability of adhesion/biofilm formation on stainless steel surfaces by five strains belonging to different S. enterica serovars. A total of 99% (96/97) of the tested S. enterica strains were characterized as biofilm-producers in the microtiter plate assays. The ability to form biofilm varied (P < 0.05) within and among the different serovars. Among the biofilm-producers, 21% (20/96), 45% (43/96), and 35% (34/96) were weak, moderate and strong biofilm-producers, respectively. The capability for adhesion/biofilm formation on stainless steel surfaces under the experimental conditions studied varied among the strains studied, and distinct secondary models were obtained to describe the behavior of the five S. enterica tested. All strains showed adhesion at pH 4 up to 4% of NaCl and at 20 °C and 35 °C. The probability of adhesion decreased when NaCl concentrations were >8% and at 8 °C, as well as in pH values ≤ 5 and NaCl concentrations > 6%, for all tested strains. At pH 7 and 6, biofilm formation for S. Enteritidis, S. Infantis, S. Typhimurium, S. Heidelberg was observed up to 6% of NaCl at 35 °C and 20 °C. The predicted boundaries for adhesion were pH values < 5 and NaCl ≥ 4% and at temperatures <20 °C. For biofilm formation, the predicted boundaries were pH values < 5 and NaCl concentrations ≥ 2% and at temperatures <20 °C for all strains. The secondary models obtained describe the variability in boundaries of adhesion and biofilm formation on stainless steel by five strains belonging to different S. enterica serovars. The boundary models can be used to predict adhesion and biofilm formation ability on stainless steel by S. enterica as affected by pH, NaCl and temperature. Copyright © 2018 Elsevier B.V. All rights reserved.

Kinetic multi-layer model of the epithelial lining fluid (KM-ELF): Reactions of ozone and OH with antioxidants and surfactant molecules

NASA Astrophysics Data System (ADS)

Lakey, Pascale; Pöschl, Ulrich; Shiraiwa, Manabu

2015-04-01

Oxidants cause damage to biosurfaces such as the lung epithelium unless they are effectively scavenged. The respiratory tract is covered in a thin layer of fluid which extends from the nasal cavity to the alveoli and contain species that scavenge ozone and other incoming oxidants. The kinetic multi-layer model of the epithelial lining fluid (KM-ELF) has been developed in order to investigate the reactions of ozone and OH with antioxidants (ascorbate, uric acid, glutathione and α-tocopherol) and surfactant lipids and proteins within the epithelial lining fluid (ELF). The model incorporates different processes: gas phase diffusion, adsorption and desorption from the surface, bulk phase diffusion and known reactions at the surface and in the bulk. The ELF is split into many layers: a sorption layer, a surfactant layer, a near surface bulk layer and several bulk layers. Initial results using KM-ELF indicate that at ELF thicknesses of 80 nm and 1 × 10-4cm the ELF would become rapidly saturated with ozone with saturation occurring in less than a second. However, at an ELF thickness of 1 × 10-3cm concentration gradients were observed throughout the ELF and the presence of antioxidants reduced the O3 reaching the lung cells and tissues by 40% after 1 hour of exposure. In contrast, the antioxidants were efficient scavengers of OH radicals, although the large rate constants of OH reacting with the antioxidants resulted in the antioxidants decaying away rapidly. The chemical half-lives of the antioxidants and surface species were also calculated using KM-ELF as a function of O3 and OH concentration and ELF thickness. Finally, the pH dependence of the products of reactions between antioxidants and O3 were investigated. The KM-ELF model predicted that a harmful ascorbate ozonide product would increase from 1.4 × 1011cm-3at pH 7.4 to 1.1 × 1014 cm-3 at pH 4after 1 hour although a uric acid ozonide product would decrease from 2.0 × 1015cm-3to 5.9 × 1012cm-3.

Competitive Adsorption between Nanoparticles and Surface Active Ions for the Oil-Water Interface.

PubMed

Hua, Xiaoqing; Bevan, Michael A; Frechette, Joelle

2018-04-24

Nanoparticles (NPs) can add functionality (e.g., catalytic, optical, rheological) to an oil-water interface. Adsorption of ∼10 nm NPs can be reversible; however, the mechanisms for adsorption and its effects on surface pressure remain poorly understood. Here we demonstrate how the competitive reversible adsorption of NPs and surfactants at fluid interfaces can lead to independent control of both the adsorbed amount and surface pressure. In contrast to prior work, both species investigated (NPs and surfactants) interact reversibly with the interface and without the surface active species binding to NPs. Independent measurements of the adsorption and surface pressure isotherms allow determination of the equation of state (EOS) of the interface under conditions where the NPs and surfactants are both in dynamic equilibrium with the bulk phase. The adsorption and surface pressure measurements are performed with gold NPs of two different sizes (5 and 10 nm), at two pH values, and across a wide concentration range of surfactant (tetrapentylammonium, TPeA + ) and NPs. We show that free surface active ions compete with NPs for the interface and give rise to larger surface pressures upon the adsorption of NPs. Through a competitive adsorption model, we decouple the contributions of NPs wetting at the interface and their surface activity on the measured surface pressure. We also demonstrate reversible control of adsorbed amount via changes in the surfactant concentration or the aqueous phase pH.

Electroless Cu Plating on Anodized Al Substrate for High Power LED.

PubMed

Rha, Sa-Kyun; Lee, Youn-Seoung

2015-03-01

Area-selective copper deposition on screen printed Ag pattern/anodized Al/Al substrate was attempted using a neutral electroless plating processes for printed circuit boards (PCBs), according to a range of variation of pH 6.5-pH 8 at 70 °C. The utilized basic electroless solution consisted of copper(II) sulfate pentahydrate, sodium phosphinate monohydrate, sodium citrate tribasic dihydrate, ammonium chloride, and nickel(II) sulfate hexahydrate. The pH of the copper plating solutions was adjusted from pH 6.5 to pH 8 using NH4OH. Using electroless plating in pH 6.5 and pH 7 baths, surface damage to the anodized Al layer hardly occurred; the structure of the plated Cu-rich films was a typical fcc-Cu, but a small Ni component was co-deposited. In electroless plating at pH 8, the surface of the anodized Al layer was damaged and the Cu film was composed of a lot of Ni and P which were co-deposited with Cu. Finally, in a pH 7 bath, we can make a selectively electroless plated Cu film on a PCB without any lithography and without surface damage to the anodized Al layer.

Engineering of acidic O/W emulsions with pectin.

PubMed

Alba, K; Sagis, L M C; Kontogiorgos, V

2016-09-01

Pectins with distinct molecular design were isolated by aqueous extraction at pH 2.0 or 6.0 and were examined in terms of their formation and stabilisation capacity of model n-alkane-in-water emulsions at acidic pH (pH 2.0). The properties and stability of the resulting emulsions were examined by means of droplet size distribution analysis, Lifshitz-Slyozov-Wagner modelling, bulk rheology, interfacial composition analysis, large-amplitude oscillatory surface dilatational rheology, electrokinetic analysis and fluorescence microscopy. Both pectin preparations were able to emulsify alkanes in water but exhibited distinct ageing characteristics. Emulsions prepared using pectin isolated at pH 6.0 were remarkably stable with respect to droplet growth after thirty days of ageing, while those prepared with pectin isolated at pH 2.0 destabilised rapidly. Examination of chemical composition of interfacial layers indicated multi-layered adsorption of pectins at the oil-water interface. The higher long-term stability of emulsions prepared with pectin isolated at high pH is attributed to mechanically stronger interfaces, the highly branched nature and the low hydrodynamic volume of the chains that result in effective steric stabilisation whereas acetyl and methyl contents do not contribute to the long-term stability. The present work shows that it is possible by tailoring the fine structure of pectin to engineer emulsions that operate in acidic environments. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of Soft Drinks with Low pH on Different Ni-Ti Orthodontic Archwire Surface Patterns

NASA Astrophysics Data System (ADS)

Abalos, C.; Paul, A.; Mendoza, A.; Solano, E.; Palazon, C.; Gil, F. J.

2013-03-01

The aim of this study was to determine the influence of soft drinks on the surface of Ni-Ti archwires and their corrosion behavior. Archwires with different patterns (smooth, scratch, dimple, and crack) were selected and characterized by scanning electron microscopy and laser confocal microscopy. Immersion tests were performed in artificial saliva (pH 6.7) with a soft drink with a pH of 2.5 for 28 days. The results showed an increase in the surface defects and/or roughness of the dimple, crack and scratch patterns with the immersion times, and a decrease in corrosion resistance. A relationship between the surface pattern and the extent of the corrosion in Ni-Ti archwires with soft drinks at low pH has been demonstrated. Pattern should be taken into account in future studies, and manufacturing processes that produce surface defects (especially cracks) should be avoided.

Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Bourcier, W. L.; Gooding, J. L.

1988-01-01

Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.

Modification by protons of frog skeletal muscle KATP channels: effects on ion conduction and nucleotide inhibition.

PubMed Central

Vivaudou, M; Forestier, C

1995-01-01

1. The molecular mechanisms underlying pH regulation of skeletal muscle ATP-sensitive K+ (KATP) channels were studied using the patch clamp technique in the inside-out configuration. Two effects of intracellular protons were studied in detail: the decrease in magnitude of single-channel currents and the increase in open probability (Po) of nucleotide-inhibited channels. 2. The pH dependence of inward unit currents under different ionic conditions was in poor agreement with either a direct block of the pore by protons or an indirect proton-induced conformational change, but was compatible with the protonation of surface charges located near the cytoplasmic entrance of the pore. This latter electrostatic mechanism was modelled using Gouy-Chapman-Stern theory, which predicted the data accurately with a surface charge density of about 0.1 negative elementary charges per square nanometre and a pK (pH value for 50% effect) value for protonation of these charges of 6.25. The same mechanism, i.e. neutralization of negative surface charges by cation binding, could also account for the previously reported reduction of inward unit currents by Mg2+. 3. Intracellular alkalization did not affect Po of the KATP channels. Acidification increased Po. In the presence of 0.1 mM ATP (no Mg2+), the channel activation vs. pH relationship could be fitted with a sigmoid curve with a Hill coefficient slightly above 2 and a pK value of 6. This latter value was dependent on the ATP concentration, decreasing from 6.3 in 30 microM ATP to 5.3 in 1 microM ATP. 4. Conversely, the channel inhibition vs. ATP concentration curve was shifted to the right when the pH was lowered. At pH 7.1, the ATP concentration causing half-maximal inhibition was about 10 microM. At pH 5.4, it was about 400 microM. The Hill coefficient values remained slightly below 2. Similar effects were observed when ADP was used as the inhibitory nucleotide. 5. These results confirm that a reciprocal competitive link exists between proton and nucleotide binding sites. Quantitatively, they are in full agreement with a steady-state model of a KATP channel possessing four identical protonation sites (microscopic pK, 6) allosterically connected to the channel open state and two identical nucleotide sites (microscopic ATP dissociation constant, approximately 30 microM) connected to the closed state. Images Figure 13 PMID:7473225

Phosphorus doping of Si and Si1 - xGex grown by ultrahigh vacuum chemical vapor deposition using Si2H6 and GeH4

NASA Astrophysics Data System (ADS)

Chen, L. P.; Huang, G. W.; Chang, C. Y.

1996-03-01

100 ppm PH3 diluted in hydrogen is used as the n-type dopant gas in Si and Si1-xGex epilayers grown by ultrahigh vacuum chemical vapor deposition (UHVCVD) using Si2H6 and GeH4. The phosphorus concentration in Si increases linearly at a small PH3 flow rate and becomes nearly saturated at higher flow rates, while the phosphorus concentration in Si1-xGex only shows a nearly linear behavior with PH3 flow rate. The growth rates of Si and Si1-xGex epilayers decrease seriously (˜50%) and slightly (˜10%) with the increase of PH3 flow rate, respectively. These results can be explained by a model based on the enhancement of hydrogen desorption rate at smaller PH3 flow rates and different levels of the effects of phosphorus blocking of surface-activated sites between Si and Si1-xGex epilayers at higher PH3 flow rates.

Response surface optimization of pH and ionic strength for emulsion characteristics of egg yolk.

PubMed

Kurt, S; Zorba, O

2009-11-01

Effects of pH (3.5, 4.5, 6.0, 7.5, and 8.5) and ionic strength (0.05, 0.15, 0.30, 0.45, and 0.55 M NaCl) on emulsion capacity, emulsion stability (ES), apparent yield stress of emulsion (AYS), and emulsion density (ED) of egg yolk were studied by using a model system. Ionic strength and pH had significant (P < 0.01) effects on the emulsion characteristics of egg yolk. Their interaction effects also have been found significant on ES, AYS, and ED. Predicted solutions of ES, emulsion capacity, and ED were minimum. The critical point of ES was determined to be at pH 6.08 and an ionic strength of 0.49 (M NaCl). Predicted solution for AYS was a maximum, which was determined to be at pH 6.04 and an ionic strength of 0.29 (M NaCl). Optimum values of pH and ionic strenght were 4.61 to 7.43 and 0.10 to 0.47, respectively.

An ectromelia virus profilin homolog interacts with cellular tropomyosin and viral A-type inclusion protein.

PubMed

Butler-Cole, Christine; Wagner, Mary J; Da Silva, Melissa; Brown, Gordon D; Burke, Robert D; Upton, Chris

2007-07-24

Profilins are critical to cytoskeletal dynamics in eukaryotes; however, little is known about their viral counterparts. In this study, a poxviral profilin homolog, ectromelia virus strain Moscow gene 141 (ECTV-PH), was investigated by a variety of experimental and bioinformatics techniques to characterize its interactions with cellular and viral proteins. Profilin-like proteins are encoded by all orthopoxviruses sequenced to date, and share over 90% amino acid (aa) identity. Sequence comparisons show highest similarity to mammalian type 1 profilins; however, a conserved 3 aa deletion in mammalian type 3 and poxviral profilins suggests that these homologs may be more closely related. Structural analysis shows that ECTV-PH can be successfully modelled onto both the profilin 1 crystal structure and profilin 3 homology model, though few of the surface residues thought to be required for binding actin, poly(L-proline), and PIP2 are conserved. Immunoprecipitation and mass spectrometry identified two proteins that interact with ECTV-PH within infected cells: alpha-tropomyosin, a 38 kDa cellular actin-binding protein, and the 84 kDa product of vaccinia virus strain Western Reserve (VACV-WR) 148, which is the truncated VACV counterpart of the orthopoxvirus A-type inclusion (ATI) protein. Western and far-western blots demonstrated that the interaction with alpha-tropomyosin is direct, and immunofluorescence experiments suggest that ECTV-PH and alpha-tropomyosin may colocalize to structures that resemble actin tails and cellular protrusions. Sequence comparisons of the poxviral ATI proteins show that although full-length orthologs are only present in cowpox and ectromelia viruses, an ~ 700 aa truncated ATI protein is conserved in over 90% of sequenced orthopoxviruses. Immunofluorescence studies indicate that ECTV-PH localizes to cytoplasmic inclusion bodies formed by both truncated and full-length versions of the viral ATI protein. Furthermore, colocalization of ECTV-PH and truncated ATI protein to protrusions from the cell surface was observed. These results suggest a role for ECTV-PH in intracellular transport of viral proteins or intercellular spread of the virus. Broader implications include better understanding of the virus-host relationship and mechanisms by which cells organize and control the actin cytoskeleton.

Mechanism of Phosphine Dissociation on the Si(001) Surface

NASA Astrophysics Data System (ADS)

Warschkow, Oliver; Schofield, Steven R.; Smith, Phil V.

2005-03-01

The continued down-scaling of electronic devices to the atomic scale increasingly requires an atomic-level understanding of the elementary processes of semiconductor doping. We present a combined experimental and theoretical investigation into the dissociation mechanism of phosphine (PH3) on the Si(001) surface. As reported by us elsewhere in this conference, a number of prominent intermediate species of PH3 dissociation observed in STM experiments have been structurally characterized as PH2+H, PH+2H and P+3H species respectively. In this poster we present detailed quantum chemical calculations of these and other short-lived intermediates as well as the transition (kinetic) barriers between them. This leads us to formulate a step-by-step mechanism for the complete dissociation of PH3 on the Si(001) surface.

Atomic force microscopy of adsorbed proteoglycan mimetic nanoparticles: Toward new glycocalyx-mimetic model surfaces.

PubMed

Hedayati, Mohammadhasan; Kipper, Matt J

2018-06-15

Blood vessels present a dense, non-uniform, polysaccharide-rich layer, called the endothelial glycocalyx. The polysaccharides in the glycocalyx include polyanionic glycosaminoglycans (GAGs). This polysaccharide-rich surface has excellent and unique blood compatibility. We report new methods for preparing and characterizing dense GAG surfaces that can serve as models of the vascular endothelial glycocalyx. The GAG-rich surfaces are prepared by adsorbing heparin or chondroitin sulfate-containing polyelectrolyte complex nanoparticles (PCNs) to chitosan-hyaluronan polyelectrolyte multilayers (PEMs). The surfaces are characterized by PeakForce tapping atomic force microscopy, both in air and in aqueous pH 7.4 buffer, and by PeakForce quantitative nanomechanics (PF-QNM) mode with high spatial resolution. These new surfaces provide access to heparin-rich or chondroitin sulfate-rich coatings that mimic both composition and nanoscale structural features of the vascular endothelial glycocalyx. Copyright © 2018. Published by Elsevier Ltd.

The effect of surface charge on photocatalytic degradation of methylene blue dye using chargeable titania nanoparticles.

PubMed

Azeez, Fadhel; Al-Hetlani, Entesar; Arafa, Mona; Abdelmonem, Yasser; Nazeer, Ahmed Abdel; Amin, Mohamed O; Madkour, Metwally

2018-05-08

Herein, a simple approach based on tailoring the surface charge of nanoparticles, NPs, during the preparation to boost the electrostatic attraction between NPs and the organic pollutant was investigated. In this study, chargeable titania nanoparticles (TiΟ 2 NPs) were synthesized via a hydrothermal route under different pH conditions (pH = 1.6, 7.0 and 10). The prepared TiΟ 2 NPs were fully characterized via various techniques including; transmission electron microscopy (TEM), X-ray diffraction (XRD), N 2 adsorption/desorption, X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible spectroscopy (UV-Vis) and dynamic light scattering (DLS). The influence of the preparation pH on the particle size, surface area and band gap was investigated and showed pH-dependent behavior. The results revealed that upon increasing the pH value, the particle size decreases and lead to larger surface area with less particles agglomeration. Additionally, the effect of pH on the surface charge was monitored by XPS to determine the amount of hydroxyl groups on the TiO 2 NPs surface. Furthermore, the photocatalytic activity of the prepared TiΟ 2 NPs towards methylene blue (MB) photodegradation was manifested. The variation in the preparation pH affected the point of zero charge (pH PZC ) of TiO 2 NPs, subsequently, different photocatalytic activities based on electrostatic interactions were observed. The optimum efficiency obtained was 97% at a degradation rate of 0.018 min -1 using TiO 2 NPs prepared at pH 10.

Optimization of diesel oil biodegradation in seawater using statistical experimental methodology.

PubMed

Xia, Wenxiang; Li, Jincheng; Xia, Yan; Song, Zhiwen; Zhou, Jihong

2012-01-01

Petroleum hydrocarbons released into the environment can be harmful to higher organisms, but they can be utilized by microorganisms as the sole source of energy for metabolism. To investigate the optimal conditions of diesel oil biodegradation, the Plackett-Burman (PB) design was used for the optimization in the first step, and N source (NaNO₃), P source (KH₂PO₄) and pH were found to be significant factors affecting oil degradation. Then the response surface methodology (RSM) using a central composite design (CCD) was adopted for the augmentation of diesel oil biodegradation and a fitted quadratic model was obtained. The model F-value of 27.25 and the low probability value (<0.0001) indicate that the model is significant and that the concentration of NaNO₃N, KH₂PO₄ and pH had significant effects on oil removal during the study. Three-dimensional response surface plots were constructed by plotting the response (oil degradation efficiency) on the z-axis against any two independent variables, and the optimal biodegradation conditions of diesel oil (original total petroleum hydrocarbons 125 mg/L) were determined as follows: NaNO₃ 0.143 g, KH₂PO₄ 0.022 g and pH 7.4. These results fit quite well with the C, N and P ratio in biological cells. Results from the present study might provide a new method to estimate the optimal nitrogen and phosphorus concentration in advance for oil biodegradation according to the composition of petroleum.

Chemical reaction mechanisms between Y2O3 stabilized ZrO2 and Gd doped CeO2 with PH3 in coal syngas

NASA Astrophysics Data System (ADS)

Chen, Gang; Kishimoto, Haruo; Yamaji, Katsuhiko; Kuramoto, Koji; Gong, Mingyang; Liu, Xingbo; Hackett, Gregory; Gerdes, Kirk; Horita, Teruhisa

2014-12-01

To clarify the chemical stability of the key materials exposed to coal syngas (CSG) containing PH3 contaminant atmosphere, exposure tests of Y2O3 8 mol.% stabilized ZrO2 (YSZ) and Gd doped CeO2 (GDC) are carried out in simulated CSG with different concentrations of PH3. Significant reaction between YSZ and 10 ppm PH3 in CSG atmosphere is confirmed, and no obvious reaction is detected on the surface of YSZ after exposed in CSG with 1 ppm PH3. YPO4, Zr2.25(PO4)3 and monoclinic Y partial stabilized ZrO2 (m-PSZ) are identified on the YSZ pellet surface after exposed in CSG with 10 ppm PH3. GDC reacted with PH3 even at 1 ppm concentration. A (Ce0.9Gd0.1)PO4 layer is formed on the surface of GDC pellet after exposure in CSG with 10 ppm PH3. Possible reaction mechanisms between YSZ and GDC with PH3 in CSG are clarified. Compared with GDC, YSZ exhibits sufficient phosphorus resistance for devices directly exposed to a coal syngas atmosphere containing low concentration of PH3.

Reactive transport modelling of a high-pH infiltration test in concrete

NASA Astrophysics Data System (ADS)

Chaparro, M. Carme; Soler, Josep M.; Saaltink, Maarten W.; Mäder, Urs K.

2017-06-01

A laboratory-scale tracer test was carried out to characterize the transport properties of concrete from the Radioactive Waste Disposal Facility at El Cabril (Spain). A hyperalkaline solution (K-Ca-OH, pH = 13.2) was injected into a concrete sample under a high entry pressure in order to perform the experiment within a reasonable time span, obtaining a decrease of permeability by a factor of 1000. The concentrations of the tracers, major elements (Ca2+, SO4 2 - , K+ and Na+) and pH were measured at the outlet of the concrete sample. A reactive transport model was built based on a double porosity conceptual model, which considers diffusion between a mobile zone, where water can flow, and an immobile zone without any advective transport. The numerical model assumed that all reactions took place in the immobile zone. The cement paste consists of C-S-H gel, portlandite, ettringite, calcite and gypsum, together with residual alite and belite. Two different models were compared, one with portlandite in equilibrium (high initial surface area) and another one with portlandite reaction controlled by kinetics (low initial surface area). Overall the results show dissolution of alite, belite, gypsum, quartz, C-S-H gel and ettringite and precipitation of portlandite and calcite. Permeability could have decreased due to mineral precipitation.

Citrobacter amalonaticus Phytase on the Cell Surface of Pichia pastoris Exhibits High pH Stability as a Promising Potential Feed Supplement

PubMed Central

Li, Cheng; Lin, Ying; Huang, Yuanyuan; Liu, Xiaoxiao; Liang, Shuli

2014-01-01

Phytase expressed and anchored on the cell surface of Pichia pastoris avoids the expensive and time-consuming steps of protein purification and separation. Furthermore, yeast cells with anchored phytase can be used as a whole-cell biocatalyst. In this study, the phytase gene of Citrobacter amalonaticus was fused with the Pichia pastoris glycosylphosphatidylinositol (GPI)-anchored glycoprotein homologue GCW61. Phytase exposed on the cell surface exhibits a high activity of 6413.5 U/g, with an optimal temperature of 60°C. In contrast to secreted phytase, which has an optimal pH of 5.0, phytase presented on the cell surface is characterized by an optimal pH of 3.0. Moreover, our data demonstrate that phytase anchored on the cell surface exhibits higher pH stability than its secreted counterpart. Interestingly, our in vitro digestion experiments demonstrate that phytase attached to the cell surface is a more efficient enzyme than secreted phytase. PMID:25490768

Citrobacter amalonaticus phytase on the cell surface of Pichia pastoris exhibits high pH stability as a promising potential feed supplement.

PubMed

Li, Cheng; Lin, Ying; Huang, Yuanyuan; Liu, Xiaoxiao; Liang, Shuli

2014-01-01

Phytase expressed and anchored on the cell surface of Pichia pastoris avoids the expensive and time-consuming steps of protein purification and separation. Furthermore, yeast cells with anchored phytase can be used as a whole-cell biocatalyst. In this study, the phytase gene of Citrobacter amalonaticus was fused with the Pichia pastoris glycosylphosphatidylinositol (GPI)-anchored glycoprotein homologue GCW61. Phytase exposed on the cell surface exhibits a high activity of 6413.5 U/g, with an optimal temperature of 60°C. In contrast to secreted phytase, which has an optimal pH of 5.0, phytase presented on the cell surface is characterized by an optimal pH of 3.0. Moreover, our data demonstrate that phytase anchored on the cell surface exhibits higher pH stability than its secreted counterpart. Interestingly, our in vitro digestion experiments demonstrate that phytase attached to the cell surface is a more efficient enzyme than secreted phytase.

First-principles study of low Miller index Ni3S2 surfaces in hydrotreating conditions.

PubMed

Aray, Yosslen; Vega, David; Rodriguez, Jesus; Vidal, Alba B; Grillo, Maria Elena; Coll, Santiago

2009-03-12

Density functional theory (DFT) calculations combined with surface thermodynamic arguments and the Gibbs-Curie-Wulff equilibrium morphology formalism have been employed to explore the effect of the reaction conditions, temperature (T), and gas-phase partial pressures (PH2 and PH2S) on the stability of nickel sulfide (Ni3S2) surfaces. Furthermore, the strength and nature of chemical bonds for selected Ni3S2 surface cuts were investigated with the quantum theory of atoms in molecules methodology. A particular analysis of the electrostatic potential within this theoretical framework is performed to study the potential activity of nickel sulfide nanoparticles as hydrodesulfurization (HDS) catalysts. The calculated thermodynamic surface stabilities and the resulting equilibrium morphology model suggest that unsupported Ni3S2 nanoparticles mainly expose (111) and (111) type surface faces in HDS conditions. Analysis of the electrostatic potential mapped onto a selected electron density isocontour (0.001 au) on those expose surface reveals a poor potential reactivity toward electron-donating reagents (i.e., low Lewis acidity). Consequently, a very low attraction between coordinatively unsaturated active sites (Lewis sites) exposed at the catalytic particles and the S atoms coming from reagent polluting molecules does inactive these kinds of particles for HDS.

Effect of amino acid sequence and pH on nanofiber formation of self-assembling peptides EAK16-II and EAK16-IV.

PubMed

Hong, Yooseong; Legge, Raymond L; Zhang, S; Chen, P

2003-01-01

Atomic force microscopy (AFM) and axisymmetric drop shape analysis-profile (ASDA-P) were used to investigate the mechanism of self-assembly of peptides. The peptides chosen consisted of 16 alternating hydrophobic and hydrophilic amino acids, where the hydrophilic residues possess alternating negative and positive charges. Two types of peptides, AEAEAKAKAEAEAKAK (EAK16-II) and AEAEAEAEAKAKAKAK (EAK16-IV), were investigated in terms of nanostructure formation through self-assembly. The experimental results, which focused on the effects of the amino acid sequence and pH, show that the nanostructures formed by the peptides are dependent on the amino acid sequence and the pH of the solution. For pH conditions around neutrality, one of the peptides used in this study, EAK16-IV, forms globular assemblies and has lower surface tension at air-water interfaces than another peptide, EAK16-II, which forms fibrillar assemblies at the same pH. When the pH is lowered below 6.5 or raised above 7.5, there is a transition from globular to fibrillar structures for EAK16-IV, but EAK16-II does not show any structural transition. Surface tension measurements using ADSA-P showed different surface activities of peptides at air-water interfaces. EAK16-II does not show a significant difference in surface tension for the pH range between 4 and 9. However, EAK16-IV shows a noticeable decrease in surface tension at pH around neutrality, indicating that the formation of globular assemblies is related to the molecular hydrophobicity.

Surface charge effects in protein adsorption on nanodiamonds

NASA Astrophysics Data System (ADS)

Aramesh, M.; Shimoni, O.; Ostrikov, K.; Prawer, S.; Cervenka, J.

2015-03-01

Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids.Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids. Electronic supplementary information (ESI) available: The FTIR spectrum of nanodiamonds, QCM-D profiles of 50 nm nanodiamond adsorption on silica surfaces, QCM-D profiles of protein desorption after rinsing with water (rinsing experiment) and the full FTIR spectrum of proteins before and after adsorption on ND particles. See DOI: 10.1039/c5nr00250h

Utilization of surface mine ponds in East Tennessee by breeding amphibians

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

Turner, L.J.; Fowler, D.K.

1981-06-01

Of 24 ponds examined on Ollis Creek Surface Mine, Campbell County, Tennessee, 21 contained breeding amphibians. Twelve species of amphibians were identified in ponds that ranged from 4.0 to 8.0 in pH. Although ponds with low pH values were used by breeding amphibians, significantly more amphibian species were found in ponds with higher pH values. The average pH of ponds occupied by each amphibian species varied. Spring peepers (Hyla crucifer) occupied ponds with the lowest average pH (5.22) while upland chorus frogs (Pseudacris triseriata feriarum) utilized ponds with the highest average pH (6.33). Findings indicated high biological productivity in surfacemore » mine ponds. Aquatic vegetation was present in 20 of the 24 ponds. Aquatic insects and a diverse wildlife fauna utilized the study ponds. Large mammals (3 species), waterbirds (17 species), and snakes (2 species) were among those species observed. Surface mine ponds were found to supply an important habitat component for a variety of wildlife species and therefore improve the quality of wildlife habitat on the surface mines. In some areas, mine ponds are the only source of surface water available for wildlife use. 23 references, 9 figures, 5 tables.« less

Projections of Ocean Acidification Under the U.N. Framework Convention of Climate Change Using a Reduced-Form Climate Carbon-Cycle Model

NASA Astrophysics Data System (ADS)

Hartin, C.

2016-02-01

Ocean chemistry is quickly changing in response to continued anthropogenic emissions of carbon to the atmosphere. Mean surface ocean pH has already decreased by 0.1 units relative to the preindustrial era. We use an open-source, simple climate and carbon cycle model ("Hector") to investigate future changes in ocean acidification (pH and calcium carbonate saturations) under the climate agreement from the United Nations Convention on Climate Change Conference (UNFCCC) of Parties in Paris 2015 (COP 21). Hector is a reduced-form, very fast-executing model that can emulate the global mean climate of the CMIP5 models, as well as the inorganic carbon cycle in the upper ocean, allowing us to investigate future changes in ocean acidification. We ran Hector under three different emissions trajectories, using a sensitivity analysis approach to quantify model uncertainty and capture a range of possible ocean acidification changes. The first trajectory is a business-as-usual scenario comparable to a Representative Concentration Pathway (RCP) 8.5, the second a scenario with the COP 21 commitments enacted, and the third an idealized scenario keeping global temperature change to 2°C, comparable to a RCP 2.6. Preliminary results suggest that under the COP 21 agreements ocean pH at 2100 will decrease by 0.2 units and surface saturations of aragonite (calcite) will decrease by 0.9 (1.4) units relative to 1850. Under the COP 21 agreement the world's oceans will be committed to a degree of ocean acidification, however, these changes may be within the range of natural variability evident in some paleo records.

Designing pH induced fold switch in proteins

NASA Astrophysics Data System (ADS)

Baruah, Anupaul; Biswas, Parbati

2015-05-01

This work investigates the computational design of a pH induced protein fold switch based on a self-consistent mean-field approach by identifying the ensemble averaged characteristics of sequences that encode a fold switch. The primary challenge to balance the alternative sets of interactions present in both target structures is overcome by simultaneously optimizing two foldability criteria corresponding to two target structures. The change in pH is modeled by altering the residual charge on the amino acids. The energy landscape of the fold switch protein is found to be double funneled. The fold switch sequences stabilize the interactions of the sites with similar relative surface accessibility in both target structures. Fold switch sequences have low sequence complexity and hence lower sequence entropy. The pH induced fold switch is mediated by attractive electrostatic interactions rather than hydrophobic-hydrophobic contacts. This study may provide valuable insights to the design of fold switch proteins.

Electrokinetics of the silica and aqueous electrolyte solution interface: Viscoelectric effects.

PubMed

Hsu, Wei-Lun; Daiguji, Hirofumi; Dunstan, David E; Davidson, Malcolm R; Harvie, Dalton J E

2016-08-01

The manipulation of biomolecules, fluid and ionic current in a new breed of integrated nanofluidic devices requires a quantitative understanding of electrokinetics at the silica/water interface. The conventional capacitor-based electrokinetic Electric Double Layer (EDL) models for this interface have some known shortcomings, as evidenced by a lack of consistency within the literature for the (i) equilibrium constants of surface silanol groups, (ii) Stern layer capacitance, (iii) zeta (ζ) potential measured by various electrokinetic methods, and (iv) surface conductivity. In this study, we consider how the experimentally observable viscoelectric effect - that is, the increase of the local viscosity due to the polarisation of polar solvents - affects electrokinetcs at the silica/water interface. Specifically we consider how a model that considers viscoelectric effects (the VE model) performs against two conventional electrokinetic models, namely the Gouy-Chapman (GC) and Basic Stern capacitance (BS) models, in predicting four fundamental electrokinetic phenomena: electrophoresis, electroosmosis, streaming current and streaming potential. It is found that at moderate to high salt concentrations (>5×10(-3)M) predictions from the VE model are in quantitative agreement with experimental electrokinetic measurements when the sole additional adjustable parameter, the viscoelectric coefficient, is set equal to a value given by a previous independent measurement. In contrast neither the GS nor BS models is able to reproduce all experimental data over the same concentration range using a single, robust set of parameters. Significantly, we also show that the streaming current and potential in the moderate to high surface charge range are insensitive to surface charge behaviour (including capacitances) when viscoelectric effects are considered, in difference to models that do not consider these effects. This strongly questions the validity of using pressure based electrokinetic experiments to measure surface charge characteristics within this experimentally relevant high pH and moderate to high salt concentration range. At low salt concentrations (<5×10(-3)M) we find that there is a lack of consistency in previously measured channel conductivities conducted under similar solution conditions (pH, salt concentration), preventing a conclusive assessment of any model suitability in this regime. Copyright © 2016 Elsevier B.V. All rights reserved.

Efficient Bioconjugation of Protein Capture Agents to Biosensor Surfaces Using Aniline-Catalyzed Hydrazone Ligation

PubMed Central

Byeon, Ji-Yeon; Limpoco, F. T.; Bailey, Ryan C.

2010-01-01

Aniline-catalyzed hydrazone ligation between surface immobilized hydrazines and aldehyde-modified antibodies is shown to be an efficient method for attaching protein capture agents to model oxide-coated biosensor substrates. Silicon photonic microring resonators are used to directly evaluate the efficiency of this surface bioconjugate reaction at various pHs and in the presence or absence of aniline as a nucleophilic catalyst. It is found that aniline significantly increases the net antibody loading for surfaces functionalized over a pH range from 4.5 to 7.4, allowing derivatization of substrates with reduced incubation time and sample consumption. This increase in antibody loading directly results in more sensitive antigen detection when functionalized microrings are employed in a label-free immunoassay. Furthermore, these experiments also reveal an interesting pH dependent non-covalent binding trend that plays an important role in dictating the amount of antibody attached onto the substrate, highlighting the competing contributions of the bioconjugate reaction rate and the dynamic interactions that control opportunities for a solution-phase biomolecule to react with a substrate-bound reagent. PMID:20809595

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

USGS Publications Warehouse

Brown, J.G.; Bassett, R.L.; Glynn, P.D.

2000-01-01

A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

A pH dependent Raman and surface enhanced Raman spectroscopic studies of citrazinic acid aided by theoretical calculations

NASA Astrophysics Data System (ADS)

Sarkar, Sougata; Chowdhury, Joydeep; Dutta, Soumen; Pal, Tarasankar

2016-12-01

A pH dependent normal Raman scattering (NRS) and surface enhanced Raman scattering (SERS) spectral patterns of citrazinic acid (CZA), a biologically important molecule, have been investigated. The acid, with different pKa values ( 4 and 11) for the two different functional groups (-COOH and -OH groups), shows interesting range of color changes (yellow at pH 14 and brown at pH 2) with the variation in solution pH. Thus, depending upon the pH of the medium, CZA molecule can exist in various protonated and/or deprotonated forms. Here we have prescribed the existence different possible forms of CZA at different pH (Forms ;C;, ;H; and ;Dprot; at pH 14 and Forms ;A;, ;D;, and ;P; at pH 2 respectively). The NRS spectra of these solutions and their respective SERS spectra over gold nanoparticles were recorded. The spectra clearly differ in their spectral profiles. For example the SERS spectra recorded with the CZA solution at pH 2 shows blue shift for different bands compared to its NRS window e.g. 406 to 450 cm- 1, 616 to 632 cm- 1, 1332 to 1343 cm- 1 etc. Again, the most enhanced peak at 1548 cm- 1 in NRS while in the SERS window this appears at 1580 cm- 1. Similar observation was also made for CZA at pH 14. For example, the 423 cm- 1 band in the NRS profile experience a blue shift and appears at 447 cm- 1 in the SERS spectrum as well as other bands at 850, 1067 and 1214 cm- 1 in the SERS window are markedly enhanced. It is also worth noting that the SERS spectra at the different pH also differ from each other. These spectral differences indicate the existence of various adsorptive forms of the CZA molecule depending upon the pH of the solution. Therefore based on the experimental findings we propose different possible molecular forms of CZA at different pH (acidic and alkaline) conditions. For example forms 'A', 'D' and 'P' existing in acidic pH (pH 2) and three other deprotonated forms 'C', 'H' and 'Dprot' in alkaline pH (pH 14). The DFT calculations for these prescribed model systems were also carried out to have a plausible understanding of their equilibrium geometries and the vibrational wavenumbers. An idea about the molecular orientation of the adsorbate over nanocolloidal gold substrate is also documented.

A pH dependent Raman and surface enhanced Raman spectroscopic studies of citrazinic acid aided by theoretical calculations.

PubMed

Sarkar, Sougata; Chowdhury, Joydeep; Dutta, Soumen; Pal, Tarasankar

2016-12-05

A pH dependent normal Raman scattering (NRS) and surface enhanced Raman scattering (SERS) spectral patterns of citrazinic acid (CZA), a biologically important molecule, have been investigated. The acid, with different pKa values (~4 and ~11) for the two different functional groups (-COOH and -OH groups), shows interesting range of color changes (yellow at pH~14 and brown at pH~2) with the variation in solution pH. Thus, depending upon the pH of the medium, CZA molecule can exist in various protonated and/or deprotonated forms. Here we have prescribed the existence different possible forms of CZA at different pH (Forms "C", "H" and "Dprot" at pH~14 and Forms "A", "D", and "P" at pH~2 respectively). The NRS spectra of these solutions and their respective SERS spectra over gold nanoparticles were recorded. The spectra clearly differ in their spectral profiles. For example the SERS spectra recorded with the CZA solution at pH~2 shows blue shift for different bands compared to its NRS window e.g. 406 to 450cm(-1), 616 to 632cm(-1), 1332 to 1343cm(-1) etc. Again, the most enhanced peak at ~1548cm(-1) in NRS while in the SERS window this appears at ~1580cm(-1). Similar observation was also made for CZA at pH~14. For example, the 423cm(-1) band in the NRS profile experience a blue shift and appears at ~447cm(-1) in the SERS spectrum as well as other bands at ~850, ~1067 and ~1214cm(-1) in the SERS window are markedly enhanced. It is also worth noting that the SERS spectra at the different pH also differ from each other. These spectral differences indicate the existence of various adsorptive forms of the CZA molecule depending upon the pH of the solution. Therefore based on the experimental findings we propose different possible molecular forms of CZA at different pH (acidic and alkaline) conditions. For example forms 'A', 'D' and 'P' existing in acidic pH (pH~2) and three other deprotonated forms 'C', 'H' and 'Dprot' in alkaline pH (pH~14). The DFT calculations for these prescribed model systems were also carried out to have a plausible understanding of their equilibrium geometries and the vibrational wavenumbers. An idea about the molecular orientation of the adsorbate over nanocolloidal gold substrate is also documented. Copyright © 2016 Elsevier B.V. All rights reserved.

Depth matters: Soil pH and dilution effects in the northern Great Plains

USDA-ARS?s Scientific Manuscript database

In the northern Great Plans (NGP), surface sampling depths of 0-15.2 cm or 0-20.3 cm are suggested for testing soil characteristics such as pH. However, acidification is often most pronounced near-surface (e.g., <10 cm). Thus, sampling deeper can potentially dilute (increase) pH measurements and the...

Use of gold nanoparticles as crosslink agent to form chitosan nanocapsules: study of the direct interaction in aqueous solutions.

PubMed

Prado-Gotor, R; López-Pérez, G; Martín, M J; Cabrera-Escribano, F; Franconetti, A

2014-06-01

A systematic study of the interaction between free anionic gold nanoparticles and chitosan in a solution is presented. A spectroscopic study of the interaction between 10nm gold nanoparticles and low molecular weight chitosan is reported as a function of the concentration and pH of the polymer in a solution. Zeta potential measurements and TEM images indicate the effective aggregation of the nanoparticles in the presence of chitosan. At the same time, anionic gold nanoparticles act as crosslink agents to form chitosan nanocapsules with an average molecular size of 260nm. The changes of the surface plasmon band due to the adsorption of the polymer on the nanoparticle surface allow using of the citrate gold nanoparticles as sensors of the polymer for analytical purposes. The limit of detection for chitosan biopolymer is 69nM. The optimum pH for the interaction between the biopolymer and the nanoparticles is found at a value of 6.4, obtained from spectrophotometric measurements and applying a deconvolution analysis of the experimental data. A simple model based on molecular surface electrostatic interactions is proposed to understand the pH dependence of the investigated system. Copyright © 2014 Elsevier Inc. All rights reserved.

Adsorption of hyaluronic acid on solid supports: role of pH and surface chemistry in thin film self-assembly.

PubMed

Choi, Jae-Hyeok; Kim, Seong-Oh; Linardy, Eric; Dreaden, Erik C; Zhdanov, Vladimir P; Hammond, Paula T; Cho, Nam-Joon

2015-06-15

Owing to its biocompatibility, resistance to biofouling, and desirable physicochemical and biological properties, hyaluronic acid (HA) has been widely used to modify the surface of various materials. The role of various physicochemical factors in HA adsorption remains, however, to be clarified. Herein, we employed quartz crystal microbalance with dissipation (QCM-D) in order to investigate HA adsorption at different pH conditions onto three substrates-silicon oxide, amine-terminated self-assembled monolayer (SAM) on gold, and carboxylic acid-terminated SAM on gold. The QCM-D experiments indicated specific pH conditions where either strong or weak HA adsorption occurs. The morphology of the adsorbed HA layers was investigated by atomic force microscopy (AFM), and we identified that strong HA adsorption produced a complete, homogenous and smooth HA layer, while weak HA adsorption resulted in rough and inhomogeneous HA layers. The observed specifics of the kinetics of HA adsorption, including a short initial linear phase and subsequent long non-linear phase, were described by using a mean-field kinetic model taking HA diffusion limitations and reconfiguration in the adsorbed state into account. The findings extend the physicochemical background of design strategies for improving the use of passive HA adsorption for surface modification applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Soil and water characteristics of a young surface mine wetland

NASA Astrophysics Data System (ADS)

Andrew Cole, C.; Lefebvre, Eugene A.

1991-05-01

Coal companies are reluctant to include wetland development in reclamation plans partly due to a lack of information on the resulting characteristics of such sites. It is easier for coal companies to recreate terrestrial habitats than to attempt experimental methods and possibly face significant regulatory disapproval. Therefore, we studied a young (10 years) wetland on a reclaimed surface coal mine in southern Illinois so as to ascertain soil and water characteristics such that the site might serve as a model for wetland development on surface mines. Water pH was not measured because of equipment problems, but evidence (plant life, fish, herpetofauna) suggests suitable pH levels. Other water parameters (conductivity, salinity, alkalinity, chloride, copper, total hardness, iron, manganese, nitrate, nitrite, phosphate, and sulfate) were measured, and only copper was seen in potentially high concentrations (but with no obvious toxic effects). Soil variables measured included pH, nitrate, nitrite, ammonia, potassium, calcium, magnesium, manganese, aluminum, iron, sulfate, chloride, and percent organic matter. Soils were slightly alkaline and most parameters fell within levels reported for other studies on both natural and manmade wetlands. Aluminum was high, but this might be indicative more of large amounts complexed with soils and therefore unavailable, than amounts actually accessible to plants. Organic matter was moderate, somewhat surprising given the age of the system.

Calcium-Phosphate-Osteopontin Particles Reduce Biofilm Formation and pH Drops in in situ Grown Dental Biofilms.

PubMed

Schlafer, Sebastian; Ibsen, Casper J S; Birkedal, Henrik; Nyvad, Bente

2017-01-01

This 2-period crossover study investigated the effect of calcium-phosphate-osteopontin particles on biofilm formation and pH in 48-h biofilms grown in situ. Bovine milk osteopontin is a highly phosphorylated glycoprotein that has been shown to interfere with bacterial adhesion to salivary-coated surfaces. Calcium-phosphate-osteopontin particles have been shown to reduce biofilm formation and pH drops in a 5-species laboratory model of dental biofilm without affecting bacterial viability. Here, smooth surface biofilms from 10 individuals were treated ex vivo 6 times/day for 30 min with either calcium-phosphate-osteopontin particles or sterile saline. After growth, the amount of biofilm formed was determined by confocal microscopy, and pH drops upon exposure to glucose were monitored using confocal-microscopy-based pH ratiometry. A total of 160 biofilms were analysed. No adverse effects of repeated ex vivo treatment with calcium-phosphate-osteopontin particles were observed. Particle treatment resulted in a 32% lower amount of biofilm formed (p < 0.05), but large inter-individual differences could be observed. Biofilm pH was significantly higher upon particle treatment, both shortly after the addition of glucose and after 30 min of incubation with glucose (p < 0.05). Calcium-phosphate-osteopontin particles may represent a new therapeutic approach to caries control and aim at directly targeting virulence factors involved in the caries process. Further studies are required to determine the effect of particle treatment on more acidogenic/aciduric biofilms as well as the remineralizing potential of the particles. © 2016 S. Karger AG, Basel.

Surface laser alloying of 17-4PH stainless steel steam turbine blades

NASA Astrophysics Data System (ADS)

Yao, Jianhua; Wang, Liang; Zhang, Qunli; Kong, Fanzhi; Lou, Chenghua; Chen, Zhijun

2008-09-01

As a known high-quality precipitation hardening stainless steel with high strength, high antifatigue, excellent corrosion resistance and good weldability, 17-4PH has been widely used to produce steam turbine blades. However, under the impact of high-speed steam and water droplets, the blades are prone to cavitation, which could lead to lower efficiency, shorter life time, and even accidents. In this article, the 17-4PH blade's surface was alloyed using a high power CO 2 laser. The microstructure and microhardness of hardened 17-4PH were tested by scanning electronic microscope (SEM), X-ray diffraction (XRD), energy disperse spectroscopy (EDS) and a microhardness tester. After laser alloying, the surface layer was denser and the grain refined, while the microhardness of the surface (average 610HV 0.2) was about one times higher than that of the substrate material (330HV 0.2). The friction coefficient of the laser-alloyed 17-4PH layer was much lower than that of the substrate.

Activity, conformation and dynamics of cutinase adsorbed on poly(methyl methacrylate) latex particles.

PubMed

Baptista, R P; Santos, A M; Fedorov, A; Martinho, J M G; Pichot, C; Elaïssari, A; Cabral, J M S; Taipa, M A

2003-05-08

The adsorption of a recombinant cutinase from Fusarium solani pisi onto the surface of 100 nm diameter poly(methyl methacrylate) (PMMA) latex particles was evaluated. Adsorption of cutinase is a fast process since more than 70% of protein molecules are adsorbed onto PMMA at time zero of experiment, irrespective of the tested conditions. A Langmuir-type model fitted both protein and enzyme activity isotherms at 25 degrees C. Gamma(max) increased from 1.1 to 1.7 mg m(-2) and U(max) increased from 365 to 982 U m(-2) as the pH was raised from 4.5 to 9.2, respectively. A decrease (up to 50%) in specific activity retention was observed at acidic pH values (pH 4.5 and 5.2) while almost no inactivation (eta(act) congruent with 87-94%) was detected upon adsorption at pH 7.0 and 9.2. Concomitantly, far-UV circular dichroism (CD) spectra evidenced a reduction in the alpha-helical content of adsorbed protein at acidic pH values while at neutral and alkaline pH the secondary structure of adsorbed cutinase was similar to that of native protein. Fluorescence anisotropy decays showed the release of some constraints to the local motion of the Trp69 upon protein adsorption at pH 8.0, probably due to the disruption of the tryptophan-alanine hydrogen bond when the tryptophan interacts with the PMMA surface. Structural data associated with activity measurements at pH 7.0 and 9.2 showed that cutinase adsorbs onto PMMA particles in an end-on orientation with active site exposed to solvent and full integrity of cutinase secondary structure. Hydrophobic interactions are likely the major contribution to the adsorption mechanism at neutral and alkaline pH values, and a higher amount of protein is adsorbed to PMMA particles with increasing temperature at pH 9.2. The maximum adsorption increased from 88 to 140 mg cutinase per g PMMA with temperature raising from 25 to 50 degrees C, at pH 9.2.

Cation effects on phosphatidic acid monolayers at various pH conditions.

PubMed

Zhang, Ting; Cathcart, Matthew G; Vidalis, Andrew S; Allen, Heather C

2016-10-01

The impact of pH and cations on phase behavior, stability, and surface morphology for dipalmitoylphosphatidic acid (DPPA) monolayers was investigated. At pH<10, DPPA monolayers on water are predominantly populated by neutral species and display the highest packing density. Cations are found to expand and stabilize the monolayer in the following order of increasing magnitude at pH 5.6: Na + >K + ∼Mg 2+ >Ca 2+ . Additionally, cation complexation is tied to the pH and protonation state of DPPA, which are the primary factors controlling the monolayer surface behavior. The binding affinity of cations to the headgroup and thus deprotonation capability of the cation, ranked in the order of Ca 2+ >Mg 2+ >Na + >K + , is found to be well explained by the law of matching water affinities. Nucleation of surface 3D lipid structures is observed from Ca 2+ , Mg 2+ , and Na + , but not from K + , consistent with the lowest binding affinity of K + . Unraveling cation and pH effects on DPPA monolayers is useful in further understanding the surface properties of complex systems such as organic-coated marine aerosols where organic films are directly influenced by the pH and ionic composition of the underlying aqueous phase. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Development of luminescent pH sensor films for monitoring bacterial growth through tissue.

PubMed

Wang, Fenglin; Raval, Yash; Chen, Hongyu; Tzeng, Tzuen-Rong J; DesJardins, John D; Anker, Jeffrey N

2014-02-01

Although implanted medical devices (IMDs) offer many benefits, they are susceptible to bacterial colonization and infections. Such infections are difficult to treat because bacteria could form biofilms on the implant surface, which reduce antibiotics penetration and generate local dormant regions with low pH and low oxygen. In addition, these infections are hard to detect early because biofilms are often localized on the surface. Herein, an optical sensor film is developed to detect local acidosis on an implanted surface. The film contains both upconverting particles (UCPs) that serve as a light source and a pH indicator that alters the luminescence spectrum. When irradiated with 980 nm light, the UCPs produce deeply penetrating red light emission, while generating negligible autofluorescence in the tissue. The basic form of the pH indicator absorbs more of upconversion luminescence at 661 nm than at 671 nm and consequently the spectral ratio indicates pH. Implanting this pH sensor film beneath 6-7 mm of porcine tissue does not substantially affect the calibration curve because the peaks are closely spaced. Furthermore, growth of Staphylococcus epidermidis on the sensor surface causes a local pH decrease that can be detected non-invasively through the tissue. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders

The activity and selectivity for CO 2/CO reduction over copper electrodes is strongly dependent on the local surface structure of the catalyst and the pH of the electrolyte. Here we investigate a unique, copper nanocube surface (CuCube) as a CO reduction electrode under neutral and basic pH, using online electrochemical mass spectroscopy (OLEMS) to determine the onset potentials and relative intensities of methane and ethylene production. To relate the unique selectivity to the surface structure, the CuCube surface reactivity is compared to polycrystalline copper and three single crystals under the same reaction conditions. Here, we find that the high selectivitymore » for ethylene over the CuCube surface is most comparable to the Cu(100) surface, which has the cubic unit cell. However, the suppression of methane production over CuCube is unique to that particular surface. Basic pH is also shown to enhance ethylene selectivity on all surfaces, again with the CuCube surface being unique.« less

Dispersion of phyllosilicates in aqueous suspensions: role of the nature and amount of surfactant.

PubMed

Houta, Nadia; Lecomte-Nana, Gisèle-Laure; Tessier-Doyen, Nicolas; Peyratout, Claire

2014-07-01

The present work aims at investigating the effect of pH values and additives on the dispersion of two 1:1 dioctahedral phyllosilicates in the presence of water. Two model clays are used for this purpose, BIP kaolin and NZCC halloysite, presenting the same surface chemistry but different morphologies. The effect of sodium hexametaphosphate, sodium silicate and sodium carbonate is discussed. Kaolin and halloysite powders were first characterized using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Subsequently, suspensions containing 8 mass% of each clay were prepared with or without additives. Experimental measurements regarding the pH values, the zeta potential and the rheological behavior were performed to determine the most suitable additive. Results show that the conformation of halloysite particles changes regarding pH values of suspensions and is strongly related to the surface charges of these particles. At their natural pH values, halloysite and kaolin suspensions exhibit zeta potentials equal to -50 and -20 mV respectively. This trend indicates that halloysite-based suspensions are well dispersed compared to kaolin-based suspensions. Sodium hexametaphosphate is the most suitable dispersant for both clays. The rheological characterization regarding further applications in casting process indicates a shear-thinning behavior for all studied compositions. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils.

PubMed

Ertli, Tímea; Marton, Aurél; Földényi, Rita

2004-11-01

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

NASA Astrophysics Data System (ADS)

Chaïrat, Claire; Schott, Jacques; Oelkers, Eric H.; Lartigue, Jean-Eric; Harouiya, Najatte

2007-12-01

The dissolution rates of natural fluorapatite (FAP), Ca 10(PO 4) 6F 2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ⩽ pH ⩽ 7, FAP dissolution rates are pH independent at 7 ⩽ pH ⩽ 10, and FAP dissolution rates again decrease with increasing pH at pH ⩾ 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10. Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using r+(molms)=6.61×10-6{aK}/{1+aK+aCa4aF1.4aOH0.6aH6K}+3.69×10-8[tbnd CaOH2+] where ai refers to the activity of the ith aqueous species, [tbnd CaOH2+] denotes the concentration of hydrated calcium sites at the surface of the leached layer (mol m -2), and Kex and Kads stand for the apparent stability constants of the Ca 2+/H + exchange and adsorption/penetration reactions, respectively.

Adsorption of virus-like particles on ion exchange surface: Conformational changes at different pH detected by dual polarization interferometry.

PubMed

Yang, Yanli; Mengran Yu; Zhang, Songping; Ma, Guanghui; Su, Zhiguo

2015-08-21

Disassembling of virus-like particles (VLPs) like hepatitis B virus surface antigen (HB-VLPs) during chromatographic process has been identified as a major cause of loss of antigen activity. In this study, dual polarization interferometry (DPI) measurement, together with chromatography experiments, were performed to study the adsorption and conformational change of HB-VLPs on ion exchange surface at three different pHs. Changes in pH values of buffer solution showed only minimal effect on the HB-VLPs assembly and antigen activity, while significantly different degree of HB-VLPs disassembling was observed after ion exchange chromatography (IEC) at different pHs, indicating the conformational change of HB-VLPs caused mainly by its interactions with the adsorbent surface. By creating an ion exchange surface on chip surface, the conformational changes of HB-VLPs during adsorption to the surface were monitored in real time by DPI for the first time. As pH increased from 7.0 to 9.0, strong electrostatic interactions between oppositely charged HB-VLPs and the ion exchange surface make the HB-VLPs spread thinly or even adsorbed in disassembled formation on the surface as revealed by significant decrease in thickness of the adsorbed layer measured by DPI. Such findings were consistent with the results of IEC experiments operated at different pHs, that more disassembled HB-VLPs were detected in the eluted proteins at pH 9.0. At low pH like pH 5.0, however, possible bi-layer adsorption was involved as evidenced by an adsorbed layer thickness higher than average diameter of the HB-VLPs. The "lateral" protein-protein interactions might be unfavorable and would make additional contribution to the disassembling of HB-VLPs besides the primary mechanism related to the protein-surface interactions; therefore, the lowest antigen activity was observed after IEC at pH 5.0. Such real-time information on conformational change of VLPs is helpful for better understanding the real mechanism for the disassembling of VLPs on the solid-liquid interface. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimization of hydrolysis conditions for the production of glucomanno-oligosaccharides from konjac using β-mannanase by response surface methodology.

PubMed

Chen, Junfan; Liu, Desheng; Shi, Bo; Wang, Hai; Cheng, Yongqiang; Zhang, Wenjing

2013-03-01

Glucomanno-oligosaccharides (GMO), usually produced from hydrolysis of konjac tubers with a high content of glucomannan, have a positive effect on Bifidobacterium as well as a variety of other physiological activities. Response surface methodology (RSM) was employed to optimize the hydrolysis time, hydrolysis temperature, pH and enzyme to substrate ratio (E/S) to obtain a high GMO yield from konjac tubers. From the signal-factor experiments, it was concluded that the change in the direct reducing sugar (DRS) is consistent with total reducing sugar (TRS) but contrary to the degree of polymerization (DP). DRS was used as an indicator of the content of GMO in the RSM study. The optimum RSM operating conditions were: reaction time of 3.4 h, reaction temperature of 41.0°C, pH of 7.1 and E/S of 0.49. The results suggested that the enzymatic hydrolysis was enhanced by temperature, pH and incubation time. Model validation showed good agreement between experimental results and the predicted responses. Copyright © 2012 Elsevier Ltd. All rights reserved.

Distribution and interactions of pentachlorophenol in soils: The roles of soil iron oxides and organic matter.

PubMed

Diagboya, Paul N; Olu-Owolabi, Bamidele I; Adebowale, Kayode O

2016-08-01

Soil iron oxides (IOs) and organic matter (OM) play varying roles in pentachlorophenol (PCP) retention and mobility, but the extent and mechanism are still unknown. Therefore, in order to have a better understanding of the adsorption of PCP on soils, batch sorption studies were carried out on whole soils and soils selectively treated to remove IOs (IOR) and OM (OMR). The effects of pH, time, and temperature were investigated. Results showed that PCP sorption was temperature and pH dependent; sorption decreased as both temperature and pH increased. Sorption was partly surface adsorption and partly partitioning within voids of IOs components as revealed by the kinetics models. The surface adsorption was multi-layer in nature. Equilibria were faster in the IOR soils than the untreated and OMR soils. IOs played greater roles in PCP sorption than OM. Removal of soil components, especially the IOs, as experienced in soils plagued by soil erosion, may lead to increased risks of PCP pollution of environmental media especially the aquifer. Copyright © 2016 Elsevier B.V. All rights reserved.

Fe-Mn binary oxide incorporated into diatomite as an adsorbent for arsenite removal: preparation and evaluation.

PubMed

Chang, Fangfang; Qu, Jiuhui; Liu, Huijuan; Liu, Ruiping; Zhao, Xu

2009-10-15

Fe-Mn binary oxide incorporated into diatomite (FMBO-diatomite) was prepared by a simple coating method, and exhibited high oxidation and adsorption ability for arsenite [As(III)]. After being incorporated by Fe-Mn binary oxide, the surface area of diatomite increased 36%, and the pore volume increased five times. The pHzpc of FMBO-diatomite was determined to be 8.1. These characteristics are responsible for the increased As(III) adsorption efficiency. The adsorption equilibria of As(III) on FMBO-diatomite were described well by a Langmuir isotherm model due to the homogeneous distribution of Fe-Mn binary oxide on a diatomite surface. As(III) was oxidized into As(V), and then adsorbed by FMBO-diatomite. The oxidation and adsorption efficiencies for As(III) depended deeply on the pH of solution. When the pH was raised to 8.1, the As(III) adsorption efficiency of FMBO-diatomite was almost equal to the As(III) oxidation efficiency. Silicate and phosphate had negative effects on As(III) adsorption. Also the influence of silicate and phosphate with the pH variation was different.

Distribution and interactions of pentachlorophenol in soils: The roles of soil iron oxides and organic matter

NASA Astrophysics Data System (ADS)

Diagboya, Paul N.; Olu-Owolabi, Bamidele I.; Adebowale, Kayode O.

2016-08-01

Soil iron oxides (IOs) and organic matter (OM) play varying roles in pentachlorophenol (PCP) retention and mobility, but the extent and mechanism are still unknown. Therefore, in order to have a better understanding of the adsorption of PCP on soils, batch sorption studies were carried out on whole soils and soils selectively treated to remove IOs (IOR) and OM (OMR). The effects of pH, time, and temperature were investigated. Results showed that PCP sorption was temperature and pH dependent; sorption decreased as both temperature and pH increased. Sorption was partly surface adsorption and partly partitioning within voids of IOs components as revealed by the kinetics models. The surface adsorption was multi-layer in nature. Equilibria were faster in the IOR soils than the untreated and OMR soils. IOs played greater roles in PCP sorption than OM. Removal of soil components, especially the IOs, as experienced in soils plagued by soil erosion, may lead to increased risks of PCP pollution of environmental media especially the aquifer.

Properties of purified cytosolic isoenzyme I of Cu,Zn-superoxide dismutase from Nicotiana plumbaginifolia leaves.

PubMed

Ragusa, S; Cambria, M T; Scarpa, M; Di Paolo, M L; Falconi, M; Rigo, A; Cambria, A

2001-11-01

The isoenzyme I of cytosolic Cu,Zn-superoxide dismutase (SOD) from Nicotiana plumbaginifolia (tobacco) leaves has been purified to apparent homogeneity. The relative molecular mass of the native isoenzyme, determined by gel filtration chromatography, is about 33.2 kDa. SDS-polyacrylamide gel electrophoresis shows that the enzyme is composed of two equal subunits of 16.6 kDa The isolectric point, assayed by isoelectric focusing, in the pH range of 3.5-6.5, is 4.3. The enzyme stability was tested at different temperatures, pH, and concentration of inhibitors (KCN and H(2)O(2)). The catalytic constant (k(cat)) was 1.17 +/- 0.14 x 10(9) M(-1) s(-1) at pH 9.9 and 0.1 M ionic strength. The activation energy of the thermal denaturation process is 263 kJ mol(-1). The electrostatic surface potential of the modeled tobacco Cu,Zn-SOD I was calculated showing that the functional spatial network of charges on the protein surface has been maintained, independently of the amino acid substitution around the active sites. Copyright 2001 Academic Press.

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.

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

PubMed

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

Smooth model surfaces from lignin derivatives. II. Adsorption of polyelectrolytes and PECs monitored by QCM-D.

PubMed

Norgren, Magnus; Gärdlund, Linda; Notley, Shannon M; Htun, Myat; Wågberg, Lars

2007-03-27

For the first time to the knowledge of the authors, well-defined and stable lignin model surfaces have been utilized as substrates in polyelectrolyte adsorption studies. The adsorption of polyallylamine (PAH), poly(acrylic acid) (PAA), and polyelectrolyte complexes (PECs) was monitored using quartz crystal microgravimetry with dissipation (QCM-D). The PECs were prepared by mixing PAH and PAA at different ratios and sequences, creating both cationic and anionic PECs with different charge levels. The adsorption experiments were performed in 1 and 10 mM sodium chloride solutions at pH 5 and 7.5. The highest adsorption of PAH and cationic PECs was found at pH 7.5, where the slightly negatively charged nature of the lignin substrate is more pronounced, governing electrostatic attraction of oppositely charged polymeric substances. An increase in the adsorption was further found when the electrolyte concentration was increased. In comparison, both PAA and the anionic PEC showed remarkably high adsorption to the lignin model film. The adsorption of PAA was further studied on silica and was found to be relatively low even at high electrolyte concentrations. This indicated that the high PAA adsorption on the lignin films was not induced by a decreased solubility of the anionic polyelectrolyte. The high levels of adsorption on lignin model surfaces found both for PAA and the anionic PAA-PAH polyelectrolyte complex points to the presence of strong nonionic interactions in these systems.

Ultrasound-assisted extraction of pectins from grape pomace using citric acid: a response surface methodology approach.

PubMed

Minjares-Fuentes, R; Femenia, A; Garau, M C; Meza-Velázquez, J A; Simal, S; Rosselló, C

2014-06-15

An ultrasound-assisted procedure for the extraction of pectins from grape pomace with citric acid as the extracting agent was established. A Box-Behnken design (BBD) was employed to optimize the extraction temperature (X1: 35-75°C), extraction time (X2: 20-60 min) and pH (X3: 1.0-2.0) to obtain a high yield of pectins with high average molecular weight (MW) and degree of esterification (DE) from grape pomace. Analysis of variance showed that the contribution of a quadratic model was significant for the pectin extraction yield and for pectin MW whereas the DE of pectins was more influenced by a linear model. An optimization study using response surface methodology was performed and 3D response surfaces were plotted from the mathematical model. According to the RSM model, the highest pectin yield (∼32.3%) can be achieved when the UAE process is carried out at 75°C for 60 min using a citric acid solution of pH 2.0. These pectic polysaccharides, composed mainly by galacturonic acid units (<97% of total sugars), have an average MW of 163.9 kDa and a DE of 55.2%. Close agreement between experimental and predicted values was found. These results suggest that ultrasound-assisted extraction could be a good option for the extraction of functional pectins with citric acid from grape pomace at industrial level. Copyright © 2014 Elsevier Ltd. All rights reserved.

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater

PubMed Central

Kim, Ja-Myung; Baars, Oliver

2016-01-01

A poorly studied but potentially important consequence of the CO2-induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis, demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035261

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater.

PubMed

Kim, Ja-Myung; Baars, Oliver; Morel, François M M

2016-11-28

A poorly studied but potentially important consequence of the CO 2 -induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis , demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

Mechanisms of antimony adsorption onto soybean stover-derived biochar in aqueous solutions.

PubMed

Vithanage, Meththika; Rajapaksha, Anushka Upamali; Ahmad, Mahtab; Uchimiya, Minori; Dou, Xiaomin; Alessi, Daniel S; Ok, Yong Sik

2015-03-15

Limited mechanistic knowledge is available on the interaction of biochar with trace elements (Sb and As) that exist predominantly as oxoanions. Soybean stover biochars were produced at 300 °C (SBC300) and 700 °C (SBC700), and characterized by BET, Boehm titration, FT-IR, NMR and Raman spectroscopy. Bound protons were quantified by potentiometric titration, and two acidic sites were used to model biochar by the surface complexation modeling based on Boehm titration and NMR observations. The zero point of charge was observed at pH 7.20 and 7.75 for SBC300 and SBC700, respectively. Neither antimonate (Sb(V)) nor antimonite (Sb(III)) showed ionic strength dependency (0.1, 0.01 and 0.001 M NaNO3), indicating inner sphere complexation. Greater adsorption of Sb(III) and Sb(V) was observed for SBC300 having higher -OH content than SBC700. Sb(III) removal (85%) was greater than Sb(V) removal (68%). Maximum adsorption density for Sb(III) was calculated as 1.88 × 10(-6) mol m(-2). The Triple Layer Model (TLM) successfully described surface complexation of Sb onto soybean stover-derived biochar at pH 4-9, and suggested the formation of monodentate mononuclear and binuclear complexes. Spectroscopic investigations by Raman, FT-IR and XPS further confirmed strong chemisorptive binding of Sb to biochar surfaces. Copyright © 2014 Elsevier Ltd. All rights reserved.

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

"Artificial lymphatic system": a new approach to reduce interstitial hypertension and increase blood flow, pH and pO2 in solid tumors.

PubMed

DiResta, G R; Lee, J; Healey, J H; Levchenko, A; Larson, S M; Arbit, E

2000-05-01

A mechanical drainage system, the "artificial lymphatic system" (ALS), consisting of a vacuum source and drain, is evaluated for its ability to aspirate the interstitial fluids responsible for the elevated interstitial fluid pressure (IFP) observed in solid tumors. IFP, pH, and pO2 radial profiles were measured before and after aspiration using wick-in-needle (WIN) probes, needle pH and oxygen electrodes, respectively. Laser Doppler flowmetry measured temporal changes in blood flow rate (BFR) at the tumor surface during aspiration. The WIN probe and IFP profile data were analyzed using numerical simulation and distributed mathematical models, respectively. The model parameter, P(E), reflecting central tumor IFP, was reduced from 15.3 to 5.7 mm Hg in neuroblastoma and from 13.3 to 12.1 mm Hg in Walker 256, respectively, following aspiration. The simulation demonstrated that spatial averaging inherent in WIN measurements reduced the calculated magnitude of the model parameter changes. IFP was significantly lower (p<0.05), especially in regions surrounding the drain, and BFR was significantly higher (p<0.05) following 25 and 45 min of aspiration, respectively; pH and pO2 profiles increased following aspiration. The experimental and mathematical findings suggest that ALS aspiration may be a viable way of reducing IFP and increasing BFR, pO2, and pH and should enhance solid tumor chemo and radiation therapy.

Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures.

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

Palmer, Donald; Machesky, Michael L.; Benezeth, Pascale

2009-07-01

Surface titrations were carried out on suspensions of monoclinic ZrO{sub 2} from 25 to 290 C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol {center_dot} kg{sup -1}(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li{sup +}, Na{sup +}, K{sup +} and (CH{sub 3}){sub 4}N{sup +}, and the magnitude of their association with the surface. The combined results were treated with a 1-pK{sub a} MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at eachmore » temperature. The pH of zero-point-charge, pH{sub zpc}, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250 C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO{sub 2} particles from 200 to 360 C. At 350 and 360 C, Li{sup +} and OH{sup -} ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO{sub 2} surfaces at near-neutral pH conditions as indicated in earlier publications.« less

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

PubMed

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Impact of anthropogenic atmospheric nitrogen and sulfur deposition on ocean acidification and the inorganic carbon system.

PubMed

Doney, Scott C; Mahowald, Natalie; Lima, Ivan; Feely, Richard A; Mackenzie, Fred T; Lamarque, Jean-Francois; Rasch, Phil J

2007-09-11

Fossil fuel combustion and agriculture result in atmospheric deposition of 0.8 Tmol/yr reactive sulfur and 2.7 Tmol/yr nitrogen to the coastal and open ocean near major source regions in North America, Europe, and South and East Asia. Atmospheric inputs of dissociation products of strong acids (HNO(3) and H2SO(4)) and bases (NH(3)) alter surface seawater alkalinity, pH, and inorganic carbon storage. We quantify the biogeochemical impacts by using atmosphere and ocean models. The direct acid/base flux to the ocean is predominately acidic (reducing total alkalinity) in the temperate Northern Hemisphere and alkaline in the tropics because of ammonia inputs. However, because most of the excess ammonia is nitrified to nitrate (NO(3)(-)) in the upper ocean, the effective net atmospheric input is acidic almost everywhere. The decrease in surface alkalinity drives a net air-sea efflux of CO(2), reducing surface dissolved inorganic carbon (DIC); the alkalinity and DIC changes mostly offset each other, and the decline in surface pH is small. Additional impacts arise from nitrogen fertilization, leading to elevated primary production and biological DIC drawdown that reverses in some places the sign of the surface pH and air-sea CO(2) flux perturbations. On a global scale, the alterations in surface water chemistry from anthropogenic nitrogen and sulfur deposition are a few percent of the acidification and DIC increases due to the oceanic uptake of anthropogenic CO(2). However, the impacts are more substantial in coastal waters, where the ecosystem responses to ocean acidification could have the most severe implications for mankind.

A cell-surface-anchored ratiometric fluorescent probe for extracellular pH sensing.

PubMed

Ke, Guoliang; Zhu, Zhi; Wang, Wei; Zou, Yuan; Guan, Zhichao; Jia, Shasha; Zhang, Huimin; Wu, Xuemeng; Yang, Chaoyong James

2014-09-10

Accurate sensing of the extracellular pH is a very important yet challenging task in biological and clinical applications. This paper describes the development of an amphiphilic lipid-DNA molecule as a simple yet useful cell-surface-anchored ratiometric fluorescent probe for extracellular pH sensing. The lipid-DNA probe, which consists of a hydrophobic diacyllipid tail and a hydrophilic DNA strand, is modified with two fluorescent dyes; one is pH-sensitive as pH indicator and the other is pH-insensitive as an internal reference. The lipid-DNA probe showed sensitive and reversible response to pH change in the range of 6.0-8.0, which is suitable for most extracellular studies. In addition, based on simple hydrophobic interactions with the cell membrane, the lipid-DNA probe can be easily anchored on the cell surface with negligible cytotoxicity, excellent stability, and unique ratiometric readout, thus ensuring its accurate sensing of extracellular pH. Finally, this lipid-DNA-based ratiometric pH indicator was successfully used for extracellular pH sensing of cells in 3D culture environment, demonstrating the potential applications of the sensor in biological and medical studies.

Quantifying Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction.

PubMed

Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh

2018-05-15

We quantify changes in the interfacial pH local to the electrochemical double layer during electrocatalysis, using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with a selectivity that is linearly dependent on the bulk solution pH. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH within molecular length scales of the surface. We use the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and find that the local pH can vary dramatically, > 3 units, relative to the bulk value even at modest current densities in well-buffered electrolytes. This work highlights the key role that interfacial pH variation plays in modulating inner-sphere electrocatalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Basic Research in Electronics (JSEP).

DTIC Science & Technology

1981-09-30

These antennas can have a low profile or be flush-mounted, are inherently rugged, are simple to fabricate , and can be made conformal to the surface...made in. the " light flash" radiated by the plasma in front of the metal surface. D. High-Power Microwave-Atmosphere Interactions The original model...Scintillation," Ph.D. Thesis , Poly- technic Institute of New York (August 1980); also POLY-MRI Report No. 80-1410. 7. S.R. Barone, "Angular Momentum of Particles

Iridium Oxide pH Sensor Based on Stainless Steel Wire for pH Mapping on Metal Surface

NASA Astrophysics Data System (ADS)

Shahrestani, S.; Ismail, M. C.; Kakooei, S.; Beheshti, M.; Zabihiazadboni, M.; Zavareh, M. A.

2018-03-01

A simple technique to fabricate the iridium oxide pH sensor is useful in several applications such as medical, food processing and engineering material where it is able to detect the changes of pH. Generally, the fabrication technique can be classified into three types: electro-deposition iridium oxide film (EIrOF), activated iridium oxide film (AIROF) and sputtering iridium oxide film (SIROF). This study focuses on fabricating electrode, calibration and test. Electro-deposition iridium oxide film is a simple and effective method of fabricating this kind of sensor via cyclic voltammetry process. The iridium oxide thick film was successfully electrodeposited on the surface of stainless steel wire with 500 cycles of sweep potential. A further analysis under FESEM shows detailed image of iridium oxide film which has cauliflower-liked microstructure. EDX analysis shows the highest element present are iridium and oxygen which concluded that the process is successful. The iridium oxide based pH sensor has shown a good performance in comparison to conventional glass pH sensor when it is being calibrated in buffer solutions with 2, 4, 7 and 9 pH values. The iridium oxide pH sensor is specifically designed to measure the pH on the surface of metal plate.

Effect of pH values on surface modification and solubility of phosphate bioglass-ceramics in the CaO-P 2O 5-Na 2O-SrO-ZnO system

NASA Astrophysics Data System (ADS)

Li, Xudong; Cai, Shu; Zhang, Wenjuang; Xu, Guohua; Zhou, Wei

2009-08-01

The bioactive glass-ceramics in the CaO-P 2O 5-Na 2O-SrO-ZnO system were synthesized by the sol-gel technique, and then chemically treated at different pH values to study the solubility and surface modification. Samples sintered at 650 °C for 4 h consisted of the crystalline phase β-Ca 2P 2O 7 and the glass matrix. After soaking in the solution at pH 1.0, the residual glass matrix on the surface appeared entirely dissolved and no new phase could be detected. Whereas at pH 3.0, web-like layer exhibiting peaks corresponding to CaP 2O 6 was formed and covered the entire surface of the sample. When conducted at pH 10.0, only part of the glass matrix was dissolved and a new phase Ca 4P 6O 19 was precipitated, forming the petaline layer. The chemical treatment can easily change the surface morphologies and phase composition of this bioactive glass-ceramics. The higher level of surface roughness resulting from the new-formed layer would improve the interface bonding and benefit for cell adhesion.

Solution and surface effects on plasma fibronectin structure

PubMed Central

1983-01-01

As assessed by electron microscopy, the reported shape of the plasma fibronectin molecule ranges from that of a compact particle to an elongated, rod-like structure. In this study, we evaluated the effects of solution and surface conditions on fibronectin shape. Freeze-dried, unstained human plasma fibronectin molecules deposited at pH 7.0-7.4 onto carbon films and examined by scanning transmission electron microscopy appeared relatively compact and pleiomorphic, with approximate average dimensions of 24 nm X 16 nm. Negatively stained molecules also had a similar shape but revealed greater detail in that we observed irregular, yarn-like structures. Glutaraldehyde-induced intramolecular cross-linking did not alter the appearance of plasma fibronectin. Molecules deposited at pH 2.8, pH 9.3, or after succinylation were less compact than those deposited at neutral pH. In contrast, fibronectin molecules sprayed onto mica surfaces at pH 7, rotary shadowed, and examined by transmission electron microscopy were elongated and nodular with a contour length of 120-130 nm. Sedimentation velocity experiments and electron microscopic observations indicate that fibronectin unfolds when it is succinylated, when the ionic strength is raised at pH 7, or when the pH is adjusted to 9.3 or 2.8. Greater unfolding is observed at pH 2.8 at low ionic strength (less than 0.01) compared with material at that pH in 0.15 M NaCl solution. We conclude that (a) the shape assumed by the fibronectin molecule can be strongly affected by solution conditions and by deposition onto certain surfaces; and that (b) the images of fibronectin seen by scanning transmission electron microscopy at neutral pH on carbon film are representative of molecules in physiologic solution. PMID:6417145

Surface charge control for zwitterionic polymer brushes: Tailoring surface properties to antifouling applications.

PubMed

Guo, Shanshan; Jańczewski, Dominik; Zhu, Xiaoying; Quintana, Robert; He, Tao; Neoh, Koon Gee

2015-08-15

Electrostatic interactions play an important role in adhesion phenomena particularly for biomacromolecules and microorganisms. Zero charge valence of zwitterions has been claimed as the key to their antifouling properties. However, due to the differences in the relative strength of their acid and base components, zwitterionic materials may not be charge neutral in aqueous environments. Thus, their charge on surfaces should be further adjusted for a specific pH environment, e.g. physiological pH typical in biomedical applications. Surface zeta potential for thin polymeric films composed of polysulfobetaine methacrylate (pSBMA) brushes is controlled through copolymerizing zwitterionic SBMA and cationic methacryloyloxyethyltrimethyl ammonium chloride (METAC) via surface-initiated atom transfer polymerization. Surface properties including zeta potential, roughness, free energy and thickness are measured and the antifouling performance of these surfaces is assessed. The zeta potential of pSBMA brushes is -40 mV across a broad pH range. By adding 2% METAC, the zeta potential of pSBMA can be tuned to zero at physiological pH while minimally affecting other physicochemical properties including dry brush thickness, surface free energy and surface roughness. Surfaces with zero and negative zeta potential best resist fouling by bovine serum albumin, Escherichia coli and Staphylococcus aureus. Surfaces with zero zeta potential also reduce fouling by lysozyme more effectively than surfaces with negative and positive zeta potential. Copyright © 2015 Elsevier Inc. All rights reserved.

Adsorption of Ni(II) onto Chemically Modified Spent Grated Coconut (Cocos Nucifera)

NASA Astrophysics Data System (ADS)

Hamzah, F. I.; Khalid, K.; Hanafiah, M. A. K. M.

2017-06-01

A new adsorbent of plant waste origin from coconut processing food factory was explored for removing Ni(II) from aqueous solutions. Several parameters such as pH, dosage, concentration and contact time were studied to obtain optimum conditions for treatment of Ni(II) contaminated wastewater. Spent grated coconut (Cocos nucifera) treated with sulfuric acid (SSGC) showed good adsorption capacity for Ni(II) ion. The amount adsorbed was affected by solution pH with the highest value achieved at pH 5. Other optimum conditions found were; dosage of 0.02 g, and 60 min of equilibrium time. Ni(II) adsorption obeyed the pseudo-second order kinetic model which suggested that chemisorption mechanism occurred in the adsorption process. The equilibrium data presented a better fitting to the Langmuir isotherm model, an indication that monolayer adsorption occurred onto a homogeneous surface. The maximum adsorption capacity, qmax was 97.09 mg g-1, thus SSGC can be classified as good and comparable with other plant waste adsorbents.

Monitoring and assessment of ocean acidification in the Arctic Ocean-A scoping paper

USGS Publications Warehouse

Robbins, Lisa L.; Yates, Kimberly K.; Feely, Richard; Fabry, Victoria

2010-01-01

Carbon dioxide (CO2) in the atmosphere is absorbed at the ocean surface by reacting with seawater to form a weak, naturally occurring acid called carbonic acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution. Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats. The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

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

USGS Publications Warehouse

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

1987-01-01

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

Earth system responses to cumulative carbon emissions

NASA Astrophysics Data System (ADS)

Steinacher, M.; Joos, F.

2015-07-01

Information on the relationship between cumulative fossil carbon emissions and multiple climate targets are essential to design emission mitigation and climate adaptation strategies. In this study, the transient responses in different climate variables are quantified for a large set of multi-forcing scenarios extended to year 2300 towards stabilization and in idealized experiments using the Bern3D-LPJ carbon-climate model. The model outcomes are constrained by 26 physical and biogeochemical observational data sets in a Bayesian, Monte-Carlo type framework. Cumulative fossil emissions of 1000 Gt C result in a global mean surface air temperature change of 1.88 °C (68 % confidence interval (c.i.): 1.28 to 2.69 °C), a decrease in surface ocean pH of 0.19 (0.18 to 0.22), and in steric sea level rise of 20 cm (13 to 27 cm until 2300). Linearity between cumulative emissions and transient response is high for pH and reasonably high for surface air and sea surface temperatures, but less pronounced for changes in Atlantic Meridional Overturning, Southern Ocean and tropical surface water saturation with respect to biogenic structures of calcium carbonate, and carbon stocks in soils. The slopes of the relationships change when CO2 is stabilized. The Transient Climate Response is constrained, primarily by long-term ocean heat observations, to 1.7 °C (68 % c.i.: 1.3 to 2.2 °C) and the Equilibrium Climate Sensitivity to 2.9 °C (2.0 to 4.2 °C). This is consistent with results by CMIP5 models, but inconsistent with recent studies that relied on short-term air temperature data affected by natural climate variability.

In situ spectroscopic evidence for neptunium(V)-carbonate inner-sphere and outer-sphere ternary surface complexes on hematite surfaces.

PubMed

Arai, Yuji; Moran, P B; Honeyman, B D; Davis, J A

2007-06-01

Np(V) surface speciation on hematite surfaces at pH 7-9 under pC2 = 10(-3.45) atm was investigated using X-ray absorption spectroscopy (XAS). In situ XAS analyses suggest that bis-carbonato inner-sphere and tris-carbonato outer-sphere ternary surface species coexist at the hematite-water interface at pH 7-8.8, and the fraction of outer-sphere species gradually increases from 27 to 54% with increasing pH from 7 to 8.8. The results suggest that the heretofore unknown Np(V)-carbonato ternary surface species may be important in predicting the fate and transport of Np(V) in the subsurface environment down gradient of high-level nuclear waste respositories.

Response surface methodology modeling to improve degradation of Chlorpyrifos in agriculture runoff using TiO2 solar photocatalytic in a raceway pond reactor.

PubMed

Amiri, Hoda; Nabizadeh, Ramin; Silva Martinez, Susana; Jamaleddin Shahtaheri, Seyed; Yaghmaeian, Kamyar; Badiei, Alireza; Nazmara, Shahrokh; Naddafi, Kazem

2018-01-01

This paper deals with the use of a raceway pond reactor (RPR) as an alternative photoreactor for solar photocatalytic applications. Raceway pond reactors are common low-cost reactors which can treat large volumes of water. The experiments were carried out with TiO 2 in the agriculture effluent spiked with Chlorpyrifos (CPF) at circumneutral pH. The Response Surface Methodology (RSM) was used to find the optimum process parameters to maximize CPF oxidation from the mathematical model equations developed in this study using R software. By ANOVA, p-value of lack of fit > 0.05 indicated that, the equation was well-fitted. The theoretical efficiency of CPF removal, under the optimum oxidation conditions with UV solar energy of around 697 ± 5.33 lux, was 84.01%, which is in close agreement with the mean experimental value (80 ± 1.42%) confirming that the response model was suitable for the optimization. As far as the authors know, this is the first study of CPF removal using RPR in agriculture runoff at circumneutral pH. Copyright © 2017. Published by Elsevier Inc.

Application of response surface methodology and semi-mechanistic model to optimize fluoride removal using crushed concrete in a fixed-bed column.

PubMed

Gu, Bon-Wun; Lee, Chang-Gu; Park, Seong-Jik

2018-03-01

The aim of this study was to investigate the removal of fluoride from aqueous solutions by using crushed concrete fines as a filter medium under varying conditions of pH 3-7, flow rate of 0.3-0.7 mL/min, and filter depth of 10-20 cm. The performance of fixed-bed columns was evaluated on the basis of the removal ratio (Re), uptake capacity (qe), degree of sorbent used (DoSU), and sorbent usage rate (SUR) obtained from breakthrough curves (BTCs). Three widely used semi-mechanistic models, that is, Bohart-Adams, Thomas, and Yoon-Nelson models, were applied to simulate the BTCs and to derive the design parameters. The Box-Behnken design of response surface methodology (RSM) was used to elucidate the individual and interactive effects of the three operational parameters on the column performance and to optimize these parameters. The results demonstrated that pH is the most important factor in the performance of fluoride removal by a fixed-bed column. The flow rate had a significant negative influence on Re and DoSU, and the effect of filter depth was observed only in the regression model for DoSU. Statistical analysis indicated that the model attained from the RSM study is suitable for describing the semi-mechanistic model parameters.

The surface characteristics of hyperbranched polyamide modified corncob and its adsorption property for Cr(VI)

NASA Astrophysics Data System (ADS)

Lin, Hai; Han, Shaoke; Dong, Yingbo; He, Yinhai

2017-08-01

A low-cost anion adsorbent for Cr(VI) effectively removing was synthesized by hyperbranched polyamide modified corncob (HPMC). Samples were characterized by Brunauer-Emmett-Teller (BET) surface area analysis, field-emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray spectroscopy, Fourier transform infrared (FTIR) and zeta potential analysis. Kinetics, isotherms and thermodynamics studies of HPMC for Cr(VI) adsorption were investigated in batch static experiments, in the temperature range of 25-45 °C, pH = 2.0. Results showed that the adsorption was rapid and stable, with the uptake capacity higher than 80% after 30 min. Adsorption behavior and rate-controlling mechanisms were analyzed using three kinetic models (pseudo-first order, pseudo-second order, intra-particle kinetic model). Kinetic studies showed that the adsorption of HPMC to Cr(VI) relied the pseudo-second-order model, and controlled both by the intra-particle diffusion and film diffusion. Equilibrium data was tested by Langmuir and Freundlich adsorption isotherm models. Langmuir model was more suitable to indicate a homogeneous distribution of active sites on HPMC and monolayer adsorption. The maximum adsorption capacity from the Langmuir model, qmax, was 131.6 mg/g at pH 2.0 and 45 °C for HPMC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto HPMC.

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

[Analyze nanofiltration separation rule of chlorogenic acid from low concentration ethanol by Donnan effect and solution-diffusion effect].

PubMed

Li, Cun-Yu; Liu, Li-Cheng; Jin, Li-Yang; Li, Hong-Yang; Peng, Guo-Ping

2017-07-01

To separate chlorogenic acid from low concentration ethanol and explore the influence of Donnan effect and solution-diffusion effect on the nanofiltration separation rule. The experiment showed that solution pH and ethanol volume percent had influences on the separation of chlorogenic acid. Within the pH values from 3 to 7 for chlorogenic acid in 30% ethanol, the rejection rate of chlorogenic acid was changed by 70.27%. Through the response surface method for quadratic regression model, an interaction had been found in molecule weight cut-off, pH and ethanol volume percent. In fixed nanofiltration apparatus, the existence states of chlorogenic acid determinedits separation rules. With the increase of ethanol concentration, the free form chlorogenic acid was easily adsorbed, dissolved on membrane surface and then caused high transmittance due to the solution-diffusion effect. However, at the same time, due to the double effects of Donnan effect and solution-diffusion effect, the ionic state of chlorogenic acid was hard to be adsorbed in membrane surface and thus caused high rejection rate. The combination of Box-Behnken design and response surface analysis can well optimize the concentrate process by nanofiltration, and the results showed that nanofiltration had several big advantages over the traditional vacuum concentrate technology, meanwhile, and solved the problems of low efficiency and serious component lossesin the Chinese medicines separation process for low concentration organic solvent-water solution. Copyright© by the Chinese Pharmaceutical Association.

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.

Novel computational approach for studying ph effects, excluded volume and ion-ion correlations in electrical double layers around polyelectrolytes and nanoparticles

NASA Astrophysics Data System (ADS)

Ovanesyan, Zaven

Highly charged cylindrical and spherical objects (macroions) are probably the simplest structures for modeling nucleic acids, proteins and nanoparticles. Their ubiquitous presence within biophysical systems ensures that Coulomb forces are among the most important interactions that regulate the behavior of these systems. In these systems, ions position themselves in a strongly correlated manner near the surface of a macroion and form electrical double layers (EDLs). These EDLs play an important role in many biophysical and biochemical processes. For instance, the macroion's net charge can change due to the binding of many multivalent ions to its surface. Thus, proper description of EDLs near the surface of a macroion may reveal a counter-intuitive charge inversion behavior, which can generate attraction between like-charged objects. This is relevant for the variety of fields such as self-assembly of DNA and RNA folding, as well as for protein aggregation and neurodegenerative diseases. Certainly, the key factors that contribute to these phenomena cannot be properly understood without an accurate solvation model. With recent advancements in computer technologies, the possibility to use computational tools for fundamental understanding of the role of EDLs around biomolecules and nanoparticles on their physical and chemical properties is becoming more feasible. Establishing the impact of the excluded volume and ion-ion correlations, ionic strength and pH of the electrolyte on the EDL around biomolecules and nanoparticles, and how changes in these properties consequently affect the Zeta potential and surface charge density are still not well understood. Thus, modeling and understanding the role of these properties on EDLs will provide more insights on the stability, adsorption, binding and function of biomolecules and nanoparticles. Existing mean-field theories such as Poisson Boltzmann (PB) often neglect the ion-ion correlations, solvent and ion excluded volume effects, which are important details for proper description of EDL properties. In this thesis, we implement an efficient and accurate classical solvation density functional theory (CDSFT) for EDLs of spherical macroions and cylindrical polyelectrolytes embedded in aqueous electrolytes. This approach extends the capabilities of mean field approximations by taking into account electrostatic ion-ion correlations, size asymmetry and excluded volume effects without compromising the computational cost. We apply the computational tool to study the structural and thermodynamic properties of the ionic atmosphere around B-DNA and spherical nanoparticles. We demonstrate that the presence of solvent molecules at experimental concentration and size values has a significant impact on the layering of ions. This layering directly influences the integrated charge and mean electrostatic potential in the diffuse region of the spherical electrical double layer (SEDL) and have a noticeable impact on the behavior of zeta potential (ZP). Recently, we have extended the aforementioned CSDFT to account for the charge-regulated mechanisms of the macroion surface on the structural and thermodynamic properties of spherical EDLs. In the approach, the CSDFT is combined with a surface complexation model to account for ion correlation and excluded volume effects on the surface titration of spherical macroions. We apply the proposed computational approach to describe the role that the ion size and solvent excluded volume play on the surface titration properties of silica nanoparticles. We analyze the effects of the nanoparticle size, pH and salt concentration of the aqueous solution on the nanoparticle's surface charge and zeta potential. The results reveal that surface charge density and zeta potential significantly depend on excluded volume and ion-ion correlation effects as well as on pH for monovalent ion species at high salt concentrations. Overall, our results are in good agreement with Monte Carlo simulations and available experimental data. We discuss future directions of this work, which includes extension of the solvation model for studying the flexibility properties of rigid peptides and globular proteins, and describes benefits that this research can potentially bring to scientific and non scientific communities.

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1994-01-01

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO4, 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer.The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H+ by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO2 to Fe(III), which then precipitated as Fe(OH)3. Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH)3 at pH < 4.7 and as AlOHSO4 at pH < 4.7. Aqueous Ca and SO4were close to equilibrium with gypsum.After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO4concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H+ desorbed from Fe(OH)3, pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO4 and elevated aqueous Al.

Influence of the water molecules near surface of viral protein on virus activation process

NASA Astrophysics Data System (ADS)

Shepelenko, S. O.; Salnikov, A. S.; Rak, S. V.; Goncharova, E. P.; Ryzhikov, A. B.

2009-06-01

The infection of a cell with influenza virus comprises the stages of receptor binding to the cell membrane, endocytosis of virus particle, and fusion of the virus envelope and cell endosome membrane, which is determined by the conformational changes in hemagglutinin, a virus envelope protein, caused by pH decrease within the endosome. The pH value that induces conformation rearrangements of hemagglutinin molecule considerably varies for different influenza virus strains, first and foremost, due to the differences in amino acid structure of the corresponding proteins. The main goal of this study was to construct a model making it possible to assess the critical pH value characterizing the fusogenic activity of influenza virus hemagglutinin from the data on hemagglutinin structure and experimental verification of this model. Under this model, we assume that when the electrostatic force between interacting hemagglutinin molecules in the virus envelop exceeds a certain value, the hemagglutinin HA1 subunits are arranged so that they form a cavity sufficient for penetration of water molecules. This event leads to an irreversible hydration of the inner fragments of hemagglutinin molecule in a trimer and to the completion of conformational changes. The geometry of electrostatic field in hemagglutinin trimer was calculated taking into account the polarization effects near the interface of two dielectrics, aqueous medium and protein macromolecule. The critical pH values for the conformational changes in hemagglutinin were measured by the erythrocyte hemolysis induced by influenza virus particles when decreasing pH. The critical pH value conditionally separating the pH range into the regions with and without the conformational changes was calculated for several influenza virus H1N1 and H3N2 strains based on the data on the amino acid structure of the corresponding hemagglutinin molecules. Comparison of the theoretical and experimental values of critical pH values for influenza virus strains suggests that the proposed model of the interaction between water molecules and influenza virus envelope proteins has a high prediction efficiency.

Reverse micelle-mediated synthesis of calcium phosphate nanocarriers for controlled release of bovine serum albumin.

PubMed

Dasgupta, Sudip; Bandyopadhyay, Amit; Bose, Susmita

2009-10-01

Calcium phosphate (CaP) nanoparticles with a calcium to phosphorus (Ca:P) molar ratio of 1.5:1 were synthesized using reverse microemulsion. Ca(NO(3))(2).4H(2)O and H(3)PO(4) were used as the aqueous phase, cyclohexane as the organic phase and poly(oxyethylene)(12) nonylphenol ether (NP-12) as the surfactant. Depending on the calcination temperature between 600 and 800 degrees C, CaP nanoparticle showed different phases of calcium-deficient hydroxyapatite (CDHA) and beta-tricalcium phosphate (beta-TCP), particle size between 48 and 69 nm, and a BET specific average surface area between 73 and 57 m(2)g(-1). Bovine serum albumin (BSA) was used as a model protein to study loading and release behavior. The adsorptive property of BSA was investigated by the change in BET surface area of these nanoparticles and the pH of the suspension. At pH 7.5, the maximum amount of BSA was adsorbed onto CaP nanoparticle. The release kinetics of BSA showed a gradual time-dependent increase in pH 4.0 and 6.0 buffer solutions. However, the amount of protein released was significantly smaller at pH 7.2. The BSA release rate also varied depending on the presence of different phases of CaPs in the system, beta-TCP or CDHA. These results suggest that the BSA protein release rate can be controlled by changing the particle size, surface area and phase composition of the CaP nanocarriers.

Understanding Potential Exposure Sources of Perfluorinated Carboxylic Acids in the Workplace

PubMed Central

Kaiser, Mary A.; Dawson, Barbara J.; Barton, Catherine A.; Botelho, Miguel A.

2010-01-01

This paper integrates perspectives from analytical chemistry, environmental engineering, and industrial hygiene to better understand how workers may be exposed to perfluorinated carboxylic acids when handling them in the workplace in order to identify appropriate exposure controls. Due to the dramatic difference in physical properties of the protonated acid form and the anionic form, this family of chemicals provides unique industrial hygiene challenges. Workplace monitoring, experimental data, and modeling results were used to ascertain the most probable workplace exposure sources and transport mechanisms for perfluorooctanoic acid (PFOA) and its ammonium salt (APFO). PFOA is biopersistent and its measurement in the blood has been used to assess human exposure since it integrates exposure from all routes of entry. Monitoring suggests that inhalation of airborne material may be an important exposure route. Transport studies indicated that, under low pH conditions, PFOA, the undissociated (acid) species, actively partitions from water into air. In addition, solid-phase PFOA and APFO may also sublime into the air. Modeling studies determined that contributions from surface sublimation and loss from low pH aqueous solutions can be significant potential sources of workplace exposure. These findings suggest that keeping surfaces clean, preventing accumulation of material in unventilated areas, removing solids from waste trenches and sumps, and maintaining neutral pH in sumps can lower workplace exposures. PMID:20974675

Simulated effect of calcification feedback on atmospheric CO2 and ocean acidification

PubMed Central

Zhang, Han; Cao, Long

2016-01-01

Ocean uptake of anthropogenic CO2 reduces pH and saturation state of calcium carbonate materials of seawater, which could reduce the calcification rate of some marine organisms, triggering a negative feedback on the growth of atmospheric CO2. We quantify the effect of this CO2-calcification feedback by conducting a series of Earth system model simulations that incorporate different parameterization schemes describing the dependence of calcification rate on saturation state of CaCO3. In a scenario with SRES A2 CO2 emission until 2100 and zero emission afterwards, by year 3500, in the simulation without CO2-calcification feedback, model projects an accumulated ocean CO2 uptake of 1462 PgC, atmospheric CO2 of 612 ppm, and surface pH of 7.9. Inclusion of CO2-calcification feedback increases ocean CO2 uptake by 9 to 285 PgC, reduces atmospheric CO2 by 4 to 70 ppm, and mitigates the reduction in surface pH by 0.003 to 0.06, depending on the form of parameterization scheme used. It is also found that the effect of CO2-calcification feedback on ocean carbon uptake is comparable and could be much larger than the effect from CO2-induced warming. Our results highlight the potentially important role CO2-calcification feedback plays in ocean carbon cycle and projections of future atmospheric CO2 concentrations. PMID:26838480

Fluorapatite crystal growth from modified seawater solutions

NASA Astrophysics Data System (ADS)

Van Cappellen, Philippe; Berner, Robert A.

Seeded precipitation experiments were conducted in a pH/fluoride-stat system to study the crystal growth of fluorapatite ( FAP ) in carbonate-free NaCl-CaCl 2-NaF-Na 2HPO 4 solutions, at seawater calcium concentration, chlorinity, and pH. With increasing supersaturation, the dependence of the growth rate on the relative supersaturation changes from parabolic to exponential. This is interpreted as reflecting a transition in the crystal growth mechanism from growth at dislocation-induced surface steps to surface nucleation-controlled growth. The analysis of the kinetic data leads to a mineral-aqueous solution interfacial tension for FAP of 289 mJ/m 2. The Arrhenius activation energy of the growth reaction in the temperature range 12 to 35°C is 47 kJ/mol. The inhibition of FAP growth by Mg 2+ ions was investigated over a range of total dissolved Mg of 0 to 60 mM. At dissolved magnesium concentrations typical of marine pore waters (40-60 mM), the rate of FAP growth is 15 to 20 times slower than in the absence of Mg 2+, for the same degree of supersaturation, at 25 °C and pH = 8. The inhibitory effect can be explained by the blocking of growth sites at the surface of FAP crystals by adsorbed Mg 2+ ions. A simple Langmuir adsorption model for the retardation effect of Mg 2+ is supported by the results. The effect of pH on FAP growth was tested for pH values from 7 to 8.5. In this range, growth of FAP is catalyzed by hydrogen ions. The apparent growth rate constant is proportional to ( aH+) m where m, the rate order with respect to H +, is a non-integral number which depends on pH. At identical degrees of supersaturation, the growth rate of FAP at pH = 7 is nearly twice that at pH = 8. When corrected for bottom water temperatures, pore water pH, and the retardation of Mg 2+, the experimental growth rates predict that during burial in modern phosphatic sediments, apatite particles grow to sizes on the order of 0.1-10 μrn. The relatively slow growth kinetics of FAP are consistent with the observed small particle sizes of marine sedimentary apatite.

Role of direct electron-phonon coupling across metal-semiconductor interfaces in thermal transport via molecular dynamics.

PubMed

Lin, Keng-Hua; Strachan, Alejandro

2015-07-21

Motivated by significant interest in metal-semiconductor and metal-insulator interfaces and superlattices for energy conversion applications, we developed a molecular dynamics-based model that captures the thermal transport role of conduction electrons in metals and heat transport across these types of interface. Key features of our model, denoted eleDID (electronic version of dynamics with implicit degrees of freedom), are the natural description of interfaces and free surfaces and the ability to control the spatial extent of electron-phonon (e-ph) coupling. Non-local e-ph coupling enables the energy of conduction electrons to be transferred directly to the semiconductor/insulator phonons (as opposed to having to first couple to the phonons in the metal). We characterize the effect of the spatial e-ph coupling range on interface resistance by simulating heat transport through a metal-semiconductor interface to mimic the conditions of ultrafast laser heating experiments. Direct energy transfer from the conduction electrons to the semiconductor phonons not only decreases interfacial resistance but also increases the ballistic transport behavior in the semiconductor layer. These results provide new insight for experiments designed to characterize e-ph coupling and thermal transport at the metal-semiconductor/insulator interfaces.

Experimental investigation and modeling of dissolved organic carbon removal by coagulation from seawater.

PubMed

Jeong, Sanghyun; Sathasivan, Arumugam; Kastl, George; Shim, Wang Geun; Vigneswaran, Saravanamuthu

2014-01-01

Coagulation removes colloidal matters and dissolved organic carbon (DOC) which can cause irreversible membrane fouling. However, how DOC is removed by coagulant is not well-known. Jar test was used to study the removal of hydrophobic and hydrophilic DOC fractions at various doses (0.5-8.0 mg-Fe(+3) L(-1)) of ferric chloride (FeCl3) and pH (5.0-9.0). Natural organic matter (NOM) in seawater and treated seawater were fractionated by liquid chromatography-organic carbon detector (LC-OCD). Compared to surface water, the removal of DOC in seawater by coagulation was remarkably different. Majority of DOC could be easily removed with very low coagulant dose (<5.0 mg-Fe(+3) L(-1)) and the removal efficiency did not vary with pH, but the DOC composition in treated water had significantly changed. Hydrophobic fraction (HB) was better removed at high pH while hydrophilic fraction (HF) was better removed at low pH. A modified model of Kastl et al. (2004) which assumed that the removal occurred by adsorption of un-dissociated compounds onto ferric hydroxide was formulated and successfully validated against the jar test data. Copyright © 2013 Elsevier Ltd. All rights reserved.

Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

NASA Astrophysics Data System (ADS)

Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

1998-02-01

The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

NASA Astrophysics Data System (ADS)

Davis, James A.; Meece, David E.; Kohler, Matthias; Curtis, Gary P.

2004-09-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 -8 to 1 · 10 -5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+, Mg 2+, HCO 3-, SO 42-, H 4SiO 4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

USGS Publications Warehouse

Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.

2004-01-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca2+, Mg2+, HCO3-, SO42-, H4SiO4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters. ?? 2004 Elsevier Ltd.

Experimental design based response surface methodology optimization of ultrasonic assisted adsorption of safaranin O by tin sulfide nanoparticle loaded on activated carbon

NASA Astrophysics Data System (ADS)

Roosta, M.; Ghaedi, M.; Daneshfar, A.; Sahraei, R.

2014-03-01

In this research, the adsorption rate of safranine O (SO) onto tin sulfide nanoparticle loaded on activated carbon (SnS-NPAC) was accelerated by the ultrasound. SnS-NP-AC was characterized by different techniques such as SEM, XRD and UV-Vis measurements. The present results confirm that the ultrasound assisted adsorption method has remarkable ability to improve the adsorption efficiency. The influence of parameters such as the sonication time, adsorbent dosage, pH and initial SO concentration was examined and evaluated by central composite design (CCD) combined with response surface methodology (RSM) and desirability function (DF). Conducting adsorption experiments at optimal conditions set as 4 min of sonication time, 0.024 g of adsorbent, pH 7 and 18 mg L-1 SO make admit to achieve high removal percentage (98%) and high adsorption capacity (50.25 mg g-1). A good agreement between experimental and predicted data in this study was observed. The experimental equilibrium data fitting to Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich models show that the Langmuir model is a good and suitable model for evaluation and the actual behavior of adsorption. Kinetic evaluation of experimental data showed that the adsorption processes followed well pseudo-second-order and intraparticle diffusion models.

Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

PubMed

Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Enriquez-Victorero, Carlos; Montero-Alejo, Ana Lilian; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

2016-04-01

Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions. Copyright © 2016 Elsevier Inc. All rights reserved.

Response surface methodology as an approach to determine optimal activities of lipase entrapped in sol-gel matrix using different vegetable oils.

PubMed

Pinheiro, Rubiane C; Soares, Cleide M F; de Castro, Heizir F; Moraes, Flavio F; Zanin, Gisella M

2008-03-01

The conditions for maximization of the enzymatic activity of lipase entrapped in sol-gel matrix were determined for different vegetable oils using an experimental design. The effects of pH, temperature, and biocatalyst loading on lipase activity were verified using a central composite experimental design leading to a set of 13 assays and the surface response analysis. For canola oil and entrapped lipase, statistical analyses showed significant effects for pH and temperature and also the interactions between pH and temperature and temperature and biocatalyst loading. For the olive oil and entrapped lipase, it was verified that the pH was the only variable statistically significant. This study demonstrated that response surface analysis is a methodology appropriate for the maximization of the percentage of hydrolysis, as a function of pH, temperature, and lipase loading.

Investigation of passive films on nickel Alloy 690 in lead-containing environments

NASA Astrophysics Data System (ADS)

Peng, B.; Lu, B. T.; Luo, J. L.; Lu, Y. C.; Ma, H. Y.

2008-09-01

Passive films formed on Alloy UNS N06690 were investigated in simulated crevice chemistries. It was found the role of lead in corrosion processes is strongly dependent on the pH value of the testing solutions. At pH 1.5 the effect of lead is narrowly noticeable; while at pH 12.7, lead has a significant influence on the electrochemical performance of alloy UNS N06690. The lead alters the surface morphologies at both pH and account for higher hydroxide content in the surface film at pH 12.7. The lead incorporation hinders the formation of spinel oxides during the passivation in alkaline solution. Nanoindentation tests indicate a significant lead-induced degradation in the mechanical properties of passive films. The passivation degradation is attributed to detrimental effects of lead via interrupting the dehydration process and hindering the formation of protective layers on the alloy surface.

Improvement of GaN light-emitting diodes with surface-treated Al-doped ZnO transparent Ohmic contacts by holographic photonic crystal

NASA Astrophysics Data System (ADS)

Yang, W. F.; Liu, Z. G.; Xie, Y. N.; Cai, J. F.; Liu, S.; Gong, H.; Wu, Z. Y.

2012-06-01

This letter presents a holographic photonic crystal (H-PhC) Al-doped ZnO (AZO) transparent Ohmic contact layer on p-GaN to increase the light output of GaN-based LEDs without destroying the p-GaN. The operating voltage of the PhC LEDs at 20 mA was almost the same as that of the typical planar AZO LEDs. While the resultant PhC LED devices exhibited significant improvements in light extraction, up to 1.22 times that of planar AZO LEDs without PhC integration. Temperature dependence of the integrated photoluminescence intensity indicates that this improvement can be attributed to the increased extraction efficiency due to the surface modification. These results demonstrate that the surface-treated AZO layer by H-PhCs is suitable for fabricating high-brightness GaN-based LEDs.

Modeling pH-Responsive Adsorption of Polyelectrolytes at Oil-Water Interfaces

NASA Astrophysics Data System (ADS)

Qin, Shiyi; Yong, Xin

We use dissipative particle dynamics (DPD) to discover the interfacial adsorption of pH-responsive polyelectrolytes in oil-water binary systems under different pH values. The electrostatic interactions between charged beads and the dielectric discontinuity across the interface are modeled by exploiting a modified Particle-Particle-Particle-Mesh (PPPM) method, which uses an iterative method to solve the Poisson equation on a uniform grid. We first model the adsorption behavior of a single linear polyelectrolyte from the aqueous phase. The Henderson-Hasselbalch equation describes the relation between pH and the degree of ionization of the modeled polyelectrolytes. Through changing the degree of ionization, we explore the influence of pH on the adsorption behavior and show that the electrostatic interactions significantly modulate the adsorption. Time evolutions of the position and conformation of the polyelectrolytes and the variation in the oil-water surface tension will be measured to characterize the adsorption behavior. Furthermore, we model the pH-dependent adsorption behavior of polyelectrolytes with more complicated structures, namely, branched polyelectrolytes with hydrophobic backbones and hydrophilic side chains. We also find that the addition of salts in the medium and the lengths of the backbone and ionized side chain affect the adsorption. This research supported by the American Chemical Society Petroleum Research Fund (Award 56884-DNI9).

A pH-responsive emulsion stabilized by alginate-grafted anisotropic silica and its application in the controlled release of λ-cyhalothrin.

PubMed

Chen, Kai; Yu, Gaobo; He, Furui; Zhou, Qingfeng; Xiao, Dunchao; Li, Jiacheng; Feng, Yuhong

2017-11-15

Alginate (Alg) was grafted on the surface of anisotropic silica (SiO 2 -x) via the Ugi reaction (Alg-SiO 2 -1, Alg-SiO 2 -2, and Alg-SiO 2 -4). Compared with pristine SiO 2 -x, modified SiO 2 -x is more sensitive to pH. Three stable liquid paraffin-in-water emulsions were prepared with Alg-SiO2-1, Alg-SiO2-2, and Alg-SiO2-4. Alg-SiO 2 -2 exhibited satisfactory emulsification ability. The emulsions became more stable as emulsion pH varied from 2.0 to 6.2 because of polymer chain interactions that led to the formation of a three-dimensional network. When the emulsion pH varied from 6.2 to 8.0, the particle charge increased, in turn increasing interparticle the electrostatic interactions that increased emulsion stability. When the emulsion pH was 9.0, the subsequent decrease in particle charge, decreased the emulsion stability. The model drug λ-cyhalothrin was embedded in the emulsions. A sustained-release assay demonstrated that increasing emulsion pH from 3.0 to 8.0 decreased cumulative drug release from the emulsion from 99.7% to 13.5%. This result indicated that the emulsion is a pH triggered drug delivery system. The sustained-release curves of λ-cyhalothrin are describable by the Weibull model. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical design of pH-sensitive nanovalves on the outer surface of mesoporous silicas for controlled storage and release of aromatic amino acid

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

Roik, N.V., E-mail: roik_nadya@ukr.net; Belyakova, L.A.

2014-07-01

Mesoporous silicas with hexagonally arranged pore channels were synthesized in water–ethanol-ammonia solution using cetyltrimethylammonium bromide as template. Directed modification of silica surface with N-[N′-(N′-phenyl)-2-aminophenyl]-3-aminopropyl groups was realized by postsynthetic activation of halogenoalkylsilicas, which have surface uniformly or selectively distributed 3-chloropropyl groups, with 2-aminodiphenylamine in the liquid phase. Chemical composition of silica materials was estimated by IR spectroscopy and chemical analysis of the surface products of reactions. Characteristics of porous structure of MCM-41-type silicas were determined from X-ray and low-temperature nitrogen ad-desorption measurements. Release ability of synthesized silica carriers was established on encapsulation of 4-aminobenzoic acid in pore channels and subsequentmore » delivery at pH=6.86 and pH=1.00. It was found that N-[N′-(N′-phenyl)-2-aminophenyl]-3-aminopropyl groups block pore entrances at neutral pH preventing 4-aminobenzoic acid release. At pH=1.00 repulsion of positively charged surface aromatic amino groups localized near pore orifices provides unhindered liberation of aromatic amino acid from mesoporous channels. - Graphical abstract: Blocking of pores with N-[N′-(N′-phenyl)-2-aminophenyl]-3-aminopropyl groups at pH=6.86 for storage of ABA and opening of pore entrances at pH=1.00 for unhindered ABA liberation. - Highlights: • Modification of MCM-41 with N-[N′-(N′-phenyl)-2-aminophenyl]-3-aminopropyl groups. • Study of release ability of synthesized silica carriers in relation to amino acid. • Controlled blocking and opening of pores by amino groups at pH change were performed. • Retention of amino acid at pH=6.86 and its liberation at pH=1.00 was proved.« less

Adsorption of cadmium by activated carbon cloth: influence of surface oxidation and solution pH.

PubMed

Rangel-Mendez, J R; Streat, M

2002-03-01

The surface of activated carbon cloth (ACC), based on polyacrylonitrile fibre as a precursor, was oxidised using nitric acid, ozone and electrochemical oxidation to enhance cadmium ion exchange capacity. Modified adsorbents were physically and chemically characterised by pH titration, direct titration, X-ray photoelectron spectroscopy, elemental analysis, surface area and porosimetry, and scanning electron microscopy. BET surface area decreased after oxidation, however, the total ion exchange capacity increased by a factor of approximately 3.5 compared to the commercial as-received ACC. A very significant increase in cadmium uptake, by a factor of 13, was observed for the electrochemically oxidised ACC. Equilibrium sorption isotherms were determined at pH 4, 5 and 6 and these showed that cadmium uptake increased with increasing pH. There was clear evidence of physical damage to ozone-oxidised fibre, however, acid and electrochemically oxidised samples were completely stable.

Aggregation behaviors of PEO-PPO-ph-PPO-PEO and PPO-PEO-ph-PEO-PPO at an air/water interface: experimental study and molecular dynamics simulation.

PubMed

Gong, Houjian; Xu, Guiying; Liu, Teng; Xu, Long; Zhai, Xueru; Zhang, Jian; Lv, Xin

2012-09-25

The block polyethers PEO-PPO-ph-PPO-PEO (BPE) and PPO-PEO-ph-PEO-PPO (BEP) are synthesized by anionic polymerization using bisphenol A as initiator. Compared with Pluronic P123, the aggregation behaviors of BPE and BEP at an air/water interface are investigated by the surface tension and dilational viscoelasticity. The molecular construction can influence the efficiency and effectiveness of block polyethers in decreasing surface tension. BPE has the most efficient ability to decrease surface tension of water among the three block polyethers. The maximum surface excess concentration (Γ(max)) of BPE is larger than that of BEP or P123. Moreover, the dilational modulus of BPE is almost the same as that of P123, but much larger than that of BEP. The molecular dynamics simulation provides the conformational variations of block polyethers at the air/water interface.

Interplay of charge distribution and conformation in peptides: comparison of theory and experiment.

PubMed

Makowska, Joanna; Bagińska, Katarzyna; Kasprzykowski, F; Vila, Jorge A; Jagielska, Anna; Liwo, Adam; Chmurzyński, Lech; Scheraga, Harold A

2005-01-01

We assessed the correlation between charge distribution and conformation of flexible peptides by comparing the theoretically calculated potentiometric-titration curves of two model peptides, Ac-Lys5-NHMe (a model of poly-L-lysine) and Ac-Lys-Ala11-Lys-Gly2-Tyr-NH2 (P1) in water and methanol, with the experimental curves. The calculation procedure consisted of three steps: (i) global conformational search of the peptide under study using the electrostatically driven Monte Carlo (EDMC) method with the empirical conformational energy program for peptides (ECEPP)/3 force field plus the surface-hydration (SRFOPT) or the generalized Born surface area (GBSA) solvation model as well as a molecular dynamics method with the assisted model building and energy refinement (AMBER)99/GBSA force field; (ii) reevaluation of the energy in the pH range considered by using the modified Poisson-Boltzmann approach and taking into account all possible protonation microstates of each conformation, and (iii) calculation of the average degree of protonation of the peptide at a given pH value by Boltzmann averaging over conformations. For Ac-Lys5-NHMe, the computed titration curve agrees qualitatively with the experimental curve of poly-L-lysine in 95% methanol. The experimental titration curves of peptide P1 in water and methanol indicate a remarkable downshift of the first pK(a) value compared to the values for reference compounds (n-butylamine and phenol, respectively), suggesting the presence of a hydrogen bond between the tyrosine hydroxyl oxygen and the H(epsilon) proton of a protonated lysine side chain. The theoretical titration curves agree well with the experimental curves, if conformations with such hydrogen bonds constitute a significant part of the ensemble; otherwise, the theory predicts too small a downward pH shift. Copyright 2005 Wiley Periodicals, Inc

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

PubMed Central

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-01-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter’s L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R2) for their absorbance, Hunter’s L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter’s b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter’s b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine. PMID:28401086

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

PubMed

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-03-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

2018-02-01

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum.

Influence of citric acid on the surface texture of glass ionomer restorative materials

PubMed Central

Reddy, Dappili Swami Ranga; Kumar, Ramachandran Anil; Venkatesan, Sokkalingam Mothilal; Narayan, Gopal Shankar; Duraivel, Dasarathan; Indra, Rajamani

2014-01-01

Aim: This study determined the effectiveness of G-coat plus surface protective agent over petroleum jelly on the surface texture of conventional Glass ionomer restorative materials. Materials and Methods: Three chemically cured conventional glass ionomer restorative materials type II, type IX and ketac molar were evaluated in this study. Sixty specimens were made for each restorative material. They were divided into two groups of thirty specimens each. Of the sixty specimens, thirty were coated with G-coat plus (a nano-filler coating) and the rest with petroleum jelly. Thirty samples of both protective coating agents were randomly divided into six groups of five specimens and conditioned in citric acid solutions of differing pH (pH 2, 3, 4, 5, 6 & 7). Each specimen was kept in citric acid for three hours a day, and the rest of time stored in salivary substitute. This procedure was repeated for 8 days. After conditioning, the surface roughness (Ra, μm) of each specimen was measured using a surface profilometer (Taylor & Habson, UK). Data was analyzed using one-way analysis of variance (ANOVA) and Tukey's HSD test at a significance level of 0.05. Results: The surface textures of all the tested glass ionomer restorative materials protected with G-coat plus were not significantly affected by acids at low pH. The surface textures of all the tested glass ionomer restorative materials protected with petroleum jelly coating were significantly affected by acids at low pH. Conclusion: The effects of pH on the surface texture of glass ionomer restoratives are material dependent. Among all the materials tested the surface texture of Type II GIC (Group I) revealed marked deterioration when conditioned in solutions of low pH and was statistically significant. Hence, a protective coating either with G-coat plus or with light polymerized low viscosity unfilled resin adhesives is mandatory for all the glass ionomer restorations to increase the wear resistance of the restorative materials. PMID:25298643

Influence of citric acid on the surface texture of glass ionomer restorative materials.

PubMed

Reddy, Dappili Swami Ranga; Kumar, Ramachandran Anil; Venkatesan, Sokkalingam Mothilal; Narayan, Gopal Shankar; Duraivel, Dasarathan; Indra, Rajamani

2014-09-01

This study determined the effectiveness of G-coat plus surface protective agent over petroleum jelly on the surface texture of conventional Glass ionomer restorative materials. Three chemically cured conventional glass ionomer restorative materials type II, type IX and ketac molar were evaluated in this study. Sixty specimens were made for each restorative material. They were divided into two groups of thirty specimens each. Of the sixty specimens, thirty were coated with G-coat plus (a nano-filler coating) and the rest with petroleum jelly. Thirty samples of both protective coating agents were randomly divided into six groups of five specimens and conditioned in citric acid solutions of differing pH (pH 2, 3, 4, 5, 6 & 7). Each specimen was kept in citric acid for three hours a day, and the rest of time stored in salivary substitute. This procedure was repeated for 8 days. After conditioning, the surface roughness (Ra, μm) of each specimen was measured using a surface profilometer (Taylor & Habson, UK). Data was analyzed using one-way analysis of variance (ANOVA) and Tukey's HSD test at a significance level of 0.05. The surface textures of all the tested glass ionomer restorative materials protected with G-coat plus were not significantly affected by acids at low pH. The surface textures of all the tested glass ionomer restorative materials protected with petroleum jelly coating were significantly affected by acids at low pH. The effects of pH on the surface texture of glass ionomer restoratives are material dependent. Among all the materials tested the surface texture of Type II GIC (Group I) revealed marked deterioration when conditioned in solutions of low pH and was statistically significant. Hence, a protective coating either with G-coat plus or with light polymerized low viscosity unfilled resin adhesives is mandatory for all the glass ionomer restorations to increase the wear resistance of the restorative materials.

Stream Water Quality Modeling in the Great Smoky Mountains National Park

NASA Astrophysics Data System (ADS)

Barnett, T. W.; Robinson, R. B.

2003-12-01

The purpose of this study was to examine water quality in the acid-impacted Great Smoky Mountains National Park (GRSM). Water samples have been collected roughly quarterly at ninety sampling sites throughout the Park from October, 1993 to November, 2002.. These samples were analyzed for pH, acid neutralizing capacity (ANC), conductivity, major cations, and major anions. The trout fisheries of the GRSM are considered some of the best in the eastern United States. However, fisheries biologists at the GRSM believe that some of the streams that once supported trout populations twenty or thirty years ago, no longer do. This study outlines and quantifies surface water quality conditions that might be harmful to trout populations through a literature review. This study identifies 71 sites (79 percent of total sampling sites) that currently have a median pH of greater than 6.0, above which, is unlikely to be harmful to trout species unless a high runoff of acid, Al-rich water creates a mixing zone where Al(OH)3 precipitates. The precipitate can accumulate on the gills and impede normal diffusion of O2, CO2, and nutrients. There are 17 sites (18 percent) that have median pH values in the 5.0 to 6.0 range. This range of pH values is likely to be harmful to trout species when aluminum concentrations exceed about 0.2 mg/l. The lower end of this range is probably harmful to the eggs and fry of trout and also to non-acclimated trout especially when calcium, sodium, and chloride concentrations are low. Only two sampling sites have median pH values in the 4.5 to 5.0 range. This pH range is likely harmful to eggs, fry and adult trout, particularly in the soft water conditions prevalent in the GRSM. The mechanisms adversely affecting trout in these ranges are ionoregulatory dysfunction, respiratory stress, and circulatory stress. Currently, there are no sampling sites with median pH values less than 4.5, although pH values could be lowered by more than one pH unit during high-flow episodic events depending on the ANC in the stream. Stepwise multiple linear regression was used to model pH, ANC, nitrate and sulfate. This study incorporates basin characteristics, time, acid deposition data, USGS stream flow data as surrogate hydrologic data, and precipitation data, e.g., inches of rain on preceding days, to determine whether these variables are associated with water quality. Acid deposition data came from biweekly wet only and throughfall monitoring at the Noland Divide, which is a high elevation acid deposition monitoring site within the Park. Precipitation data is collected at five National Weather Service monitoring sites within the Park. Each of the above variables were found to be statistically significant (p<0.05) influencing factors to water quality, particularly pH. Water quality conditions were adversely (decreasing pH and ANC and increasing sulfate and nitrate) affected by increased stream flows, acid deposition and precipitation. Models for pH and ANC produced R-square values around 0.71 and 0.86, respectively. Nitrate and sulfate modeling produced R-square values around 0.30. This study also analyzes temporal trends in pH. Modeling reveals statistically significant decreasing trends in pH with time. If conditions remain the same and past trends continue, models suggest that 30.0 percent of the sampling sites will reach pH values less than 6.0 in less than 10 years, 63.3 percent of the sites will reach pH values less than 6.0 in less than 25 years, and 96.7 percent of the sites will reach pH values less than 6.0 in less than 50 years. The models used to predict future pH values explain around 70 percent of the variability in the data.

Subtle charge balance controls surface-nucleated self-assembly of designed biopolymers.

PubMed

Charbonneau, Céline; Kleijn, J Mieke; Cohen Stuart, Martien A

2014-03-25

We report the surface-nucleated self-assembly into fibrils of a biosynthetic amino acid polymer synthesized by the yeast Pichia pastoris. This polymer has a block-like architecture, with a central silk-like block labeled SH, responsible for the self-assembly into fibrils, and two collagen-like random coil end blocks (C) that colloidally stabilize the fibers in aqueous solution. The silk-like block contains histidine residues (pKa≈6) that are positively charged in the low pH region, which hinders self-assembly. In aqueous solution, CSHC self-assembles into fibers above a pH-dependent critical nucleation concentration Ccb. Below Ccb, where no self-assembly occurs in solution, fibril formation can be induced by a negatively charged surface (silica) in the pH range of 3.5-7. The density of the fibers at the surface and their length are controlled by a subtle balance in charge between the protein polymer and the silica surface, which is evidenced from the dependence on pH. With increasing number density of the fibers at the surface, their average length decreases. The results can be explained on the basis of a nucleation-and-growth mechanism: the surface density of fibers depends on the rate of nucleation, while their growth rate is limited by transport of proteins from solution. Screening of the charges on the surface and histidine units by adding NaCl influences the nucleation-and-growth process in a complicated fashion: at low pH, the growth is improved, while at high pH, the nucleation is limited. Under conditions where nucleation in the bulk solution is not possible, growth of the surface-nucleated fibers into the solution--away from the surface--can still occur.

VALUING ACID MINE DRAINAGE REMEDIATION OF IMPAIRED WATERWAYS IN WEST VIRGINIA: A HEDONIC MODELING APPROACH

EPA Science Inventory

States with active and abandoned mines face large private and public costs to remediate damage to streams and rivers from acid mine drainage (AMD), the metal rich runoff flowing primarily from abandoned mines and surface deposits of mine waste. AMD can lower stream and river pH ...