Characterization of silicate monomer with sodium,calcium and strontium but not with lithium and magnesium ions by fast atom bombardment mass spectrometry

Fast atom bombardment mass spectrometry (FABMS) was applied to the direct detection of silica species dissolved in LiCl, NaCl, MgCl(2), CaCl(2) and SrCl(2) solutions in order to investigate its dissolution process in solution. Several species of dissolved silicate complexes in the solution were directly detected by FABMS. The peak intensities of [SiO(2)(OH)(2)Na](-), [SiO(3)(OH)Ca](-) and [SiO(3)(OH)Sr](-) increased with increasing concentrations of NaCl, CaCl(2) and SrCl(2), whereas the peak intensities of [SiO(2)(OH)(2)Li](-) and [SiO(3)(OH)Mg](-) did not increase with increasing concentrations of LiCl and MgCl(2). These results indicte that silicate and cation bind in the solution not after but before ionization. The isotope pattern of Sr(2+) confirmed the existence of the silicate-Sr complex not only with increase of the concentration of silica but also the mass numbers of Sr. The silicate complexes formed with Na(+), Ca(2+) and Sr(2+) showed high stability in chloride solution. This is in good accordance with the fact that Na(+), Ca(2+) and Sr(2+) accelerate the dissolution of silica to form complexes during solution equilibrium. Considering that the stability constant was examined and reported in other papers, this new findings that Mg(2+) does not form a complex with silicic acid (Si(OH)(4)) is very important.     

Quartz crystal microbalance with dissipation monitoring and surface plasmon resonance studies of carboxymethyl cellulose adsorption onto regenerated cellulose surfaces

Adsorption of anionic polyelectrolytes, sodium salts of carboxymethyl celluloses (CMCs) with different degrees of substitution (DS = 0.9 and 1.2), from aqueous electrolyte solutions onto regenerated cellulose surfaces was studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) experiments. The influence of both calcium chloride (CaCl(2)) and sodium chloride (NaCl) on CMC adsorption was examined. The QCM-D results demonstrated that CaCl(2) (divalent cation) caused significantly greater CMC adsorption onto regenerated cellulose surfaces than NaCl (monovalent cation) at the same ionic strength. The CMC layers adsorbed onto regenerated cellulose surfaces from CaCl(2) solutions exhibited greater stability upon exposure to flowing water than layers adsorbed from NaCl solutions. Both QCM-D and SPR results showed that CMC adsorption onto regenerated cellulose surfaces from CaCl(2) solutions increased with increasing CaCl(2) concentration up to the solubility limit (10 mM). Voigt-based viscoelastic modeling of the QCM-D data indicated that the CMC layers adsorbed onto regenerated cellulose surfaces had shear viscosities of η(f) ≈ 10(-3) N·s·m(-2) and elastic shear moduli of μ(f) ≈ 10(5) N·m(-2). Furthermore, the combination of SPR spectroscopy and QCM-D showed that the CMC layers contained 90-95% water. Adsorption isotherms for CMCs in CaCl(2) solutions were also obtained from QCM-D and were fit by Freundlich isotherms. This study demonstrated that CMC adsorption from CaCl(2) solutions is useful for the modification of cellulose surfaces.     

高温及超临界条件下 MgCl2与CaCl2水溶液中离子水化与缔合的量子化学计算

对NaCl等碱金属水溶液的研究表明,室温条件下,离子在溶液中以水合形式存在,而在高温及超临界时,阴阳离子将结合成为离子对．采用量子化学计算,研究了MgCl2与CaCl2水溶液中水化与缔合的情况．通过Gaussian98软件包计算了阳离子的水化自由能以及离子对的生成能,从而获得水合离子与离子对的热力学稳定性及其随温度、压力的变化情况．通过比较热力学稳定性,考察了两种溶液中水化与缔合的变化情况．研究结果表明,MgCl2与CaCl2水溶液中离子水化与缔合的变化趋势与碱金属溶液基本一致,但是存在一个过渡区域,该区域内离子对与水合离子共存,因此需要采用不同于碱金属溶液的方法处理MgCl2与CaCl2水溶液．     

Influence of natural organic matter on the deposition kinetics of extracellular polymeric substances (EPS) on silica

The influence of humic acid and alginate, two major components of natural organic matter (NOM), on deposition kinetics of extracellular polymeric substances (EPS) on silica was examined in both NaCl and CaCl(2) solutions over a wide range of environmentally relevant ionic strengths utilizing a quartz crystal microbalance with dissipation. Deposition kinetics of both soluble EPS and bound EPS extracted from four bacterial strains with different characteristics was investigated. EPS deposition on humic acid-coated silica surfaces was found to be much lower than that on bare silica surfaces under all examined conditions. In contrast, pre-coating the silica surfaces with alginate enhanced EPS deposition in both NaCl and CaCl(2) solutions. More repulsive electrostatic interaction between EPS and surface contributed to the reduced EPS deposition on humic acid-coated silica surface. The trapping effect induced by the rough alginate layer resulted in the greater EPS deposition on alginate-coated surfaces in NaCl solutions, whereas surface heterogeneities on alginate layer facilitated favorable interactions with EPS in CaCl(2) solutions. The presence of dissolved background humic acid and alginate in solutions both significantly retarded EPS deposition on silica surfaces due to the greater steric and electrostatics repulsion.     

Effect of water hardness on surface tension and dilational visco-elasticity of sodium dodecyl sulphate solutions

The complementary drop and bubble profile analysis and maximum bubble pressure tensiometry are used to measure the dynamic surface tension of aqueous SDS solutions in the presence of hardness salts (CaCl(2) and MgCl(2) in the ratio of 2:1 at concentrations of 6 and 40FH). The presence of hardness salts results in an essential increase of the SDS adsorption activity, which indicates the formation of Ca(DS)(2) and Mg(DS)(2) in the SDS solutions. The surface tension isotherms of SDS in presence of Ca(DS)(2) and Mg(DS)(2) are described using the generalised Frumkin model. The presence of hardness salts accelerates the ageing of SDS solutions as compared with the addition of 0.01 M NaCl due to a faster hydrolysis and hence formation of dodecanol. These results are used to estimate the possible concentration of dodecanol in the studied SDS solutions. The buoyant bubble profile method with harmonic surface oscillations is used to measure the dilational rheology of SDS solutions in presence of hardness salts in the frequency range between 0.005 Hz and 0.2 Hz. The visco-elasticity modulus in the presence of hardness salts is higher as compared with its values in the presence of 0.01 M NaCl additions. The ageing of SDS solutions leads to an essential increase of the visco-elastic modulus.     

Influence of humic acid on the aggregation kinetics of fullerene (C60) nanoparticles in monovalent and divalent electrolyte solutions

The early stage aggregation kinetics of fullerene C60 nanoparticles were investigated in the presence of Suwannee River humic acid and common monovalent and divalent electrolytes through time-resolved dynamic light scattering (DLS). In the absence of humic acid, the aggregation behavior of the fullerene nanoparticles in the presence of NaCl, MgCl2, and CaCl2 was found to be consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability. In the presence of humic acid and NaCl or MgCl2 electrolytes, the adsorbed humic acid on the fullerene nanoparticles led to steric repulsion, which effectively stabilized the nanoparticle suspension. This behavior manifested in a dramatic drop in the rate of aggregation, an increase in the critical coagulation concentration (CCC), and an attained value of less than unity for the inverse stability ratio (or attachment efficiency) at high MgCl2 concentrations. While the increase in the nanoparticle stability was similarly observed in the presence of humic acid at low CaCl2 concentrations, enhanced aggregation occurred at higher CaCl2 concentrations. Measurement of scattered light intensities over time indicated significant aggregation of the humic acid macromolecules in solutions of high CaCl2 concentrations. Transmission electron microscopy (TEM) imaging of the fullerene aggregate structures in the presence of humic acid revealed that bridging of the fullerene nanoparticles and aggregates by the humic acid aggregates is the likely mechanism for the enhanced aggregation at high CaCl2 concentrations.     

STUDY ON THE DESALINATION BEHAVIORS OF PA/PSF THIN FILM COMPOSITE

1. INTRODUCTION Nanofiltration (NF) membranes have been known for having properties between those of ultrafiltration (UF) membranes and reverse osmosis (RO) membranes and thus have found applications in many areas especially in rejecting multivalent ions for water softening and charged organic pollutants for wastewater treatment. Because of their advantages, such as low operating pressure, high permeate flux, high retention to multivalent ions and organic molecules with molecular weight …     

STUDY ON THE DESALINATION BEHAVIORS OF PA/PSF THIN FILM COMPOSITE

A polypiperazine amide (PA)/polysulfone (PSF) thin film composite (TFC) was prepared by interfacial polymerization (IP) using a trimesoyl chloride hexane solution as the oil phase and a piperazine aqueous solution as the water phase on a porous polysulfone hollow fiber substrate. Its separating behaviors were investigated systematically to various salts such as NaCl, KCI, Na2SO4,MgCl2, CaCl2 and MgSO4, showing the highest rejection rate to Na2SO4, the second to MgSO4, the third to MgCl2 and CaCl2, and the lowest to KCI, NaCl, being 99%, 98%, 70%, 60%, 15% and 10% respectively. Under an increasing pressure or with time, the rejection rate of the TFC rises to a plateau. To various concentration of the feed, the rejection rate reduced gradually with the higher concentration.     

Characteristics of the series resonant-frequency shift of a quartz crystal microbalance in electrolyte solutions

We report the novel characteristics of the series resonant-frequency shift, DeltaF, of a one-face sealed quartz crystal microbalance (QCM) in solutions of monovalent electrolytes and divalent electrolytes. In the present study, we used NaCl, KCl, LiCl, NaNO3 and CH3COONa as monovalent electrolytes, and MgCl2, CaCl2, MgSO4 and Na2SO4 as divalent electrolytes. These experiments reveal that, in all the solutions, the DeltaF values vary linearly with an increase in the square root of the density-viscosity product of the solutions, and the immersion angle dependence of DeltaF appears. Moreover, we have found that the intercept values of DeltaF are dependent only on the cation species, and that the slope values of DeltaF with the viscosity and density of the solutions are related only to the valence of ions. We also suggest that the DeltaF values are independent of anion species, conductivity and permittivity of the solutions.     

Influence of solution chemistry on the deposition and detachment kinetics of RNA on silica surfaces

The deposition kinetics of RNA extracted from both virus and bacteria on silica surfaces were examined in both monovalent (NaCl) and divalent (CaCl(2)) solutions under a wide range of environmentally relevant ionic strength and pH conditions by utilizing a quartz crystal microbalance with dissipation (QCM-D). To better understand the RNA deposition mechanisms, QCM-D data were complemented by diffusion coefficients and zeta potentials of RNA as a function of examined solution chemistry conditions. Favorable deposition of RNA on poly-l-lysine-coated (positively charged) silica surfaces was governed by the convective-diffusive transport of RNA to the surfaces. The deposition kinetics of RNA on bare silica surfaces were controlled by classic Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions. The presence of divalent cations (Ca(2+)) in solutions greatly enhanced the deposition kinetics of RNA on silica surfaces. Solution pH also affected the deposition behavior of RNA on silica surfaces. Release experiments showed that detachment of RNA from silica surfaces was significant in NaCl solutions, whereas, the deposited RNA on silica surfaces in CaCl(2) solutions was more likely to be irreversible.     

Salt effects on the protonation and on alkali and alkaline earth metal complex formation of 1,2,3-propanetricarboxylate in aqueous solution

The protonation of 1,2,3-propanetricarboxylate (tricarballylate, tca) was studied in LiCl, NaCl, KCl, MgCl(2), CaCl(2) and tetraethylammonium iodide (Et(4)NI) aqueous solutions, at 25 degrees C, in the ionic strength range 0 < I < 1M, using the pH-metric technique. The differences between protonation constants determined in Et(4)NI and those determined in the other background salts were interpreted in terms of complex formations. Least squares calculations are consistent with the formation of MLH(j) (j = 0,1.2), M(2)LH(i) (i = 0,1,2), M(2)L species, when M = Mg(2+), Ca(2+). Potentiometric measurements performed in mixed NaClKCl, NaClCaCl(2) and MgCl(2)CaCl(2) solutions showed the formation of mixed metal complexes NaKL, NaKHL, NaCaL and CaMgL. The dependence on ionic strength of protonation and complex formation constants was evaluated using a simple Debye-Hückel type equation.     

Adsorption of guar gum onto quartz from dilute mixed electrolyte solutions

The effect of potassium, sodium, calcium, magnesium, and hydrogen cations on adsorption of guar gum onto quartz was investigated at natural pH. The role of the background ions was analyzed in terms of their water-structure making or breaking capabilities. In dilute solutions (0.01 mol/L) of structure-makers (NaCl, HCl, CaCl2, and MgCl2), the guar gum adsorption density did not change compared to the adsorption densities obtained in distilled water. Potassium, the only structure-breaking ion (chaotrope) among the tested cations, significantly enhanced guar gum adsorption. The results obtained in mixed electrolytes demonstrate that the strong structure-breaking properties of K+ overcome any contributions from weak structure making ions (kosmotropes), and guar gum adsorption remains at the levels observed in KCl alone. Only when strongly hydrated Mg2+ ions are mixed with KCl, the overall effect becomes additive and the influence of potassium is proportionally reduced by increasing concentrations of magnesium cations. In this approach, guar gum adsorption on quartz is viewed as a competition between polysaccharide and water molecules for silanol surface sites. The hydration of the quartz surface inhibits the adsorption process but the competition equilibrium, and hence polysaccharide adsorption, can be affected by the presence of chaotropes or kosmotropes.     

A spectroscopic study of the fluorescence quenching interactions between biomedically important salts and the fluorescent probe merocyanine 540

The effects of several biologically important inorganic salts, including NaCl, NaI, NaBr, KCl, MgCl2, MgSO4 and CaCl2 on the electronic absorption and fluorescence spectra of Merocyanine 540 (MC-540) have been investigated in aqueous media at 25 degrees C. Depending on both the MC-540 concentration and the nature of salt, a new absorption band appears at about 515 nm, above the critical salt concentration (CSC), corresponding to salt-induced MC-540 aggregation. Several types of MC-540 fluorescence quenching by the salts are observed, according to their cationic charge and the nature of anion: in the case of monovalent ions (Na+, K+), a non-linear Stern-Volmer behaviour is observed, indicating variable contributions of dynamic and static quenching mechanisms, whereas for divalent alkaline-earth (Mg2+, Ca2+) ions, linear Stern-Volmer relationships are obtained. Using these results, an analytical quenchofluorimetric approach is proposed for the determination of magnesium ions.     

Electrothermal vaporization on a tungsten filament for the determination of arsenic in chloride solutions by low-pressure helium ICP-MS.

A combined method of electrothermal vaporization and low-pressure helium ICP-MS was developed for the determination of traces of arsenic in chloride solutions, because serious spectral interference occurred in conventional argon ICP-MS. On a tungsten filament was placed 5 microl of a sample and heated electrothermally to remove the solvent. The resulting residue on the filament was covered with a vaporization chamber, and after reducing the pressure to ca. 5 Torr, it was rapidly heated by discharging a high-capacity condenser (0.22 F). The vapor of arsenic was transferred to a helium plasma with a stream of carrier gas for the determination. The background was not observed at m/z of 75, which allowed the determination of arsenic at ng/ml levels in chloride solutions. Sodium chloride significantly enhanced the intensity of the arsenic signal, whereas other chlorides, including KCl, MgCl2, CaCl2 and NH4Cl, suppressed the analytical signals. This enhancement due to sodium ions seems to be a peculiar phenomenon to the helium ICP. The proposed method can be applied to direct determinations of as low as 0.9 ng/ml of arsenic in seawater.     

H2 and Cl2 production in the radiolysis of calcium and magnesium chlorides and hydroxides

The production of H2 has been examined in the gamma-ray and 5 MeV He ion radiolysis of CaCl2.2H2O, CaCl2.6H2O, Ca(OH)2, MgCl2.2H2O, MgCl2.6H2O, and Mg(OH)2. The highest yield for the formation of H2 is observed in the gamma-radiolysis of MgCl2.2H2O (0.72 molecule/(100 eV), 75 nmol/J), but the yield decreases with dose due to the relative instability of the dihydrate. The H2 yields with the other compounds range from 0.04 to 0.2 molecule/(100 eV) (4.2-21 nmol/J), which is lower than that from pure water or 2 M chloride solutions. There appears to be no relationship between the results for H2 from waters of hydration with that from aqueous salt brines. No particular trend is observed in the radiation chemical yields of H2 with respect to the cation or the degree of hydration. The production of Cl2 is found only in the gamma-radiolysis of CaCl2 with a few weight percent of excess water. No Cl2 was found in the 5 MeV He ion radiolysis of identical systems. None of the other compounds examined here showed detectable amounts of Cl2 formation.     

Effects of atmospherically important solvated ions on organic acid adsorption at the surface of aqueous solutions

The effects of salts on the solubility of amphiphilic organic molecules are of importance to numerous atmospheric, environmental, and biological systems. A detailed picture of the influence of dissolved atmospheric salts, NaCl and Na(2)SO(4), on the adsorption of hexanoic acid at the vapor/water interface is developed using vibrational sum-frequency spectroscopy and surface tension measurements as a function of time, organic concentration, and solution pH. We have found that for hexanoic acid adsorption at the vapor/water interface, a fast initial adsorption is followed by two considerably slower processes: a reorientation of the polar headgroup and a restructuring of the headgroup solvation shell. The addition of salts affects this restructuring by reducing the range of water--headgroup interactions immediately upon surface adsorption for ion containing solutions. Reorientation of the organic headgroup with time occurs at the surface of both salt-containing and salt-free solutions, but the most stable orientation differs with the added ions. The dissolved salts also enhance the interfacial concentration of hexanoic acid, consistent with the known salting-out behavior of Cl(-) and SO(4)(2-) anions.     

A NOVEL NANOFILTRATION MEMBRANE PREPARED WITH PAMAM AND TMC (I)

A series of nanofiltration (NF) membranes were prepared with poly(amido-amine) (PAMAM) and trimesoyl chloride (TMC) viu in situ interfacial polymerization.The effects of the generation number and concentration of PAMAM on the properties of NF membranes were discussed.Fourier transform infrared spectroscopy (FTIR-ATR),atomic force microscopy (AFM),scanning electron microscopy (SEM) and contact angle measurements were employed to characterize the resulting membranes.The nanofiltration performances were evaluated with solutions of NaCl,Na2SO4,MgCl2 and MgSO4,respectively.FTIR-ATR spectra indicated that TMC reacted more sufficiently with the higher generation PAMAM.The salts rejection of the resulting membranes increased with increasing the generation number of PAMAM,which was mainly attributed to the concentration difference of terminal amino-groups among the different generation PAMAM.The MgCl2 (2000 mg/L) rejection of NF-G5 reached 90.3% under the pressure of 0.6 Mpa in a cross-flow method measurement.The rejection of MgCl2 increased with increasing concentration of PAMAM.The salts rejection order of NF membranes with high rejection is MgCl2>MgSO4>Na2SO4>NaCI.It was also found that the NF-Gx (x=4,5,6,7) membranes became more hydrophilic with increasing the generation number of PAMAM.     

Study on hydration layers near nanoscale silica dispersed in aqueous solutions through viscosity measurement

On the basis of the Einstein theory of viscosity of dispersion, a parameter, termed as solvation factor, is presented to evaluate the solvation degree of nanoscale particles dispersed in a liquid in this work. The value of the parameter is obtained through the measurements of relative viscosity of the dispersions as a function of the volume fraction of dry particles. The solvation factor has been used to study the hydration layers near nanoscale silica particles dispersed in water and aqueous electrolyte (NaCl and CaCl2) solutions in this work. The experimental results have shown that a strong hydration indeed applied to the silica surfaces in aqueous solutions, leaving a large volume of hydration layers on the surfaces. Also, it has been found that the hydration of the nanoscale silica particles could be greatly enhanced if they were dispersed in aqueous NaCl or CaCl2 solutions, which might be attributed to that the hydrated cations (Na+ or Ca2+) bind onto the silica/ water interface and thus increase the volume of the hydration layers.     

Interfacial interactions between amphiphilic cyclodextrins and physiologically relevant cations

The compression isotherms of a series of amphiphilic cyclodextrins, formed (a) by acylation at the secondary hydroxyl face and (b) by acylation accompanied by varying degrees of sulfatation (DS) at the primary hydroxyl face (DS=0, 4, and 7), have been studied on subphases of pure water and of water containing NaCl, KCl, MgCl(2), and CaCl(2) at inter- and extracellular concentrations. The formation of solid lipid nanoparticles (SLNs) by two of the molecules has been observed, while these do not aggregate at concentrations of monovalent salts up to 150 mM for the sulfated derivative. In the presence of divalent salts one of these with a DS=0 for sulfatation degree flocculates at divalent salt concentrations below 0.1 mM while the other with a DS=4 flocculates at Mg(2+) concentration above 5 mM and a Ca(2+) concentration above 3 mM. AFM noncontact mode imaging has been carried out, in air, for the SLNs deposited on mica.