Effect of some physical and chemical parameters on fluoride removal by nanofiltration

In natural waters, fluoride ions are necessary and beneficial for the human being. At higher level of F⁻ in water, it is toxic and detrimental to human health, leading to serious problems such as dental and skeleton fluorosis. According to the World Health Organization, the acceptable concentrations of fluoride in potable water are in the range of 0.7–1.5 mg L⁻¹. Various treatment technologies for fluoride removal from water have been used such as ion exchange, adsorption and membrane processes. In the present study, removal of fluoride ions from aqueous solutions was investigated using a polyamide thin film composite nanofiltration membrane denoted as HL 2514 T from Osmonics Company. Through this membrane, the mechanism of transport was investigated. The Kedem–Katchelsky model was applied in order to determine phenomenological parameters σ and P _s, respectively, the reflection coefficient of the membrane and the solute permeability of ions. The convective and diffusive parts of the mass transfer were quantified. The retention of monovalent and bivalent salts by this membrane shows that it is negatively charged. In the second part, retention of fluoride anions was investigated. Results show that the retention of fluoride by HL membrane exceeds 80%. The influence of the chemical parameters (feed concentration and ionic strength) and the physical parameters (applied pressure and recovery) on the elimination of fluoride was studied.     

Spectrofluorimetric Assessment of Chlorzoxazone and Ibuprofen in Pharmaceutical Formulations by using Eu-Tetracycline HCl Optical Sensor Doped in Sol–Gel Matrix

A novel, simple, sensitive and selective spectrofluorimetric method was developed for the determination of trace amounts of chlorzoxazone and Ibuprofen in pharmaceutical tablets using optical sensor Eu-Tetracycline HCl doped in sol–gel matrix. The chlorzoxazone or Ibuprofen can remarkably enhance the luminescence intensity of Eu-Tetracycline HCl complex doped in a sol–gel matrix in dimethylformamide (DMF) at pH 9.7 and 6.3, respectively, λ_ex = 400 nm. The enhancing of luminescence intensity peak of Eu-Tetracycline HCl complex at 617 nm is proportional to the concentration of chlorzoxazone or Ibuprofen a result that suggested profitable application as a simple optical sensor for chlorzoxazone or Ibuprofen assessment. The dynamic ranges found for the determination of chlorzoxazone and Ibuprofen concentration are 5 × 10⁻⁹–1 × 10⁻⁴ and 1 × 10⁻⁸–7 × 10⁻⁵ mol L⁻¹, and the limit of detection (LOD) and quantitation limit of detection (LOQ) are 3.1 × 10⁻¹⁰ , 9.6 × 10⁻¹⁰ and 5.6 × 10⁻¹⁰, 1.7 × 10⁻⁹ mol L⁻¹, respectively.     

The influence of hydrogen plasma pre-treatment on the structure of BDND electrode surface applied for phenol detection

The surface properties of boron-doped nanocrystalline diamond films treated with H₂ plasma was investigated in regard to their electrochemical response for phenol oxidation. The surface of these films is relatively flat formed by crystallites with sizes of about 40 nm. X-ray photoelectron spectroscopy analyses showed that electrode surface has a high amount of C–H bonds. This behavior is in agreement with Mott-Schottky plot measurements concerning the flat band potential that presented a value as expected for hydrogenated diamond surface. This electrode presented the phenol detection limit of 0.08 mg L⁻¹ for low phenol concentrations from 40 to 250 μmol L⁻¹.     

Ultrasonic assisted arsenate adsorption on solvothermally synthesized calcite modified by goethite, α-MnO2 and goethite/α-MnO2

A highly porous calcium carbonate (calcite; sorbent 1) was used as a support for modification with α-FeOOH (calcite/goethite; sorbent 2), α-MnO₂ (calcite/α-MnO₂; sorbent 3) and α-FeOOH/α-MnO₂ (calcite/goethite/α-MnO₂; sorbent 4) in order to obtain a cheap hybrid materials for simple and effective arsenate removal from aqueous solutions. The adsorption ability of synthesized adsorbents was studied as a function of functionalization methods, pH, contact time, temperature and ultrasonic treatment. Comparison of the adsorptive effectiveness of synthesized adsorbents for arsenate removal, under ultrasound treatment and classical stirring method, has shown better performance of the former one reaching maximum adsorption capacities of 1.73, 21.00, 10.36 and 41.94 mg g⁻¹, for sorbents 1–4, respectively. Visual MINTEQ equilibrium speciation modeling was used for prediction of pH and interfering ion influences on arsenate adsorption.     

Cilostazol determination by the enhancement of the green emission of Tb3+ optical sensor

The efficiency of excited-state interaction between Tb³⁺ and the industrial product Cilostazol (CIL) has been studied in different solvents. High luminescence intensity peak at 545 nm of terbium complex in acetonitrile was obtained. The photophysical properties of the green emissive Tb³⁺ complex have been elucidated, the terbium was used as optical sensor for the assessment of CIL in the pharmaceutical tablets and body fluids at pH 3.1 and λ_ex = 320 nm with a concentration range 1.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹ of CIL, correlation coefficient of 0.998 and detection limit of 7.5 × 10⁻¹⁰ mol L⁻¹.     

Preparation of amino-modified titanate nanotubes and its striking adsorption ability to duplex DNA

In this study, amino-modified titanate nanotubes (NH₂-TNs) were prepared and used to adsorb duplex DNA. Macroscopic complexes between DNA and NH₂-TNs were observed. The uptake of DNA by NH₂-TNs was very fast; equilibrium was reached within 10 min at pH 3.6–5.0. The equilibrium capacity in the adsorption isotherm of NH₂-TNs was 240 mg g⁻¹, and further increase of the adsorption capacity was obtained with the addition of Ca²⁺ in solution. The adsorbed DNA could be released with phosphate buffer saline (PBS) solution without damage of the DNA strands. NH₂-TNs could protect DNA from cleavage efficiently in the presence of DNase I.     

Spectrofluorimetric Assessment of Doxycycline Hydrochloride in Pharmaceutical Tablets and Serum Sample Based on the Enhancement of the Luminescence Intensity of the Optical Sensor Sm<Superscript>3+</Superscript> Ion

A simple and sensitive spectrofluorimetric method for determination of trace amount of doxycycline hydrochloride (DC) in pharmaceutical tablets and serum samples was developed. In ammonia buffer solution of pH 8.9 the doxycycline hydrochloride can remarkably enhance the luminescence intensity of the Sm³⁺ ion in Sm³⁺- DC complex at λ_ex = 400 nm. The produced luminescence intensity of Sm³⁺- DC complex in DMSO is in proportion to the concentration of DC and used as optical sensor for its determination. The dynamic range for the determination of DC is 1 × 10⁻⁸ – 5 × 10⁻⁶ mol L⁻¹ and in case of quantum yield calculations is 7 × 10⁻⁹ – 5 × 10⁻⁶ mol L⁻¹ with detection limit of 6.5 × 10⁻¹⁰ mol L⁻¹. The enhancement mechanism of the luminescence intensity in the Sm³⁺- DC system has been also discussed. A comparison with other spectrofluorimetric methods for tetracycline derivatives in which Eu³⁺ ion is used instead of Sm³⁺ ion is also studied.     

Synthesis,characterization and role of zero-valent iron nanoparticle in removal of hexavalent chromium from chromium-spiked soil

Chromium is an important industrial metal used in various products/processes. Remediation of Cr contaminated sites present both technological and economic challenges, as conventional methods are often too expensive and difficult to operate. In the present investigation, Zero-valent iron (Fe⁰) nanoparticles were synthesized, characterized, and were tested for removal of Cr(VI) from the soil spiked with Cr(VI). Fe⁰ nanoparticles were synthesized by the reduction of ferric chloride with sodium borohydride and were characterized by UV–Vis (Ultra violet–Visible) and FTIR (Fourier transform infrared) spectroscopy. The UV–Vis spectrum of Fe⁰ nanoparticles suspended in 0.8% Carboxymethyl cellulose showed its absorption maxima at 235 nm. The presence of one band at 3,421 cm⁻¹ ascribed to OH stretching vibration and the second at 1,641 cm⁻¹ to OH bending vibration of surface-adsorbed water indicates the formation of ferrioxyhydroxide (FeOOH) layer on Fe⁰ nanoparticles. The mean crystalline dimension of Fe⁰ nanoparticles calculated by XRD (X-ray diffraction) using Scherer equation was 15.9 nm. Average size of Fe⁰ nanoparticles calculated from TEM (Transmission electron microscopy) images was found around 26 nm. Dynamic Light Scattering (DLS) also showed approximately the same size. Batch experiments were performed using various concentration of Fe⁰ nanoparticles for reduction of soil spiked with 100 mg kg⁻¹ Cr(VI). The reduction potential of Fe⁰ nanoparticles at a concentration of 0.27 g L⁻¹ was found to be 100% in 3 h. Reaction kinetics revealed a pseudo-first order kinetics. Factors like pH, contact time, stabilizer, and humic acid facilitates the reduction of Cr(VI).     

Spectrofluorimetric Assessment of Hydrochlorothiazide Using Optical Sensor Nano-Composite Terbium Ion Doped in Sol-Gel Matrix

A new, simple, sensitive and selective spectrofluorimetric method for the determination of Hydrochlorothiazide was developed in acetonitrile at pH 6.2. The Hydrochlorothiazide can remarkably enhance the luminescence intensity of the Tb³⁺ ion doped in sol–gel matrix at λ_ex = 370 nm. The intensity of the emission band of Tb³⁺ ion doped in sol–gel matrix was increased due to the energy transfer from the triplet excited state of Hydrochlorothiazide to (⁵D₄) excited energy state of Tb³ ion. The enhancement of the emission band of Tb³⁺ ion doped in sol–gel matrix at (⁵D₄→⁷ F₅) 545 nm was directly proportion to the concentration of Hydrochlorothiazide with a dynamic ranges of 5.0 × 10⁻¹⁰—5.0 × 10⁻⁶ mol L⁻¹ and detection limit of 2.2 × 10⁻¹¹ mol L⁻¹.     

Chemical composition of surface-functionalized gold nanoparticles

The composition of surface-functionalized gold nanoparticles (diameter of the metallic core: 17–20 nm) was determined by elemental analysis (C, H, N, S, Au, Na) after preparation of a larger batch. Gold nanoparticles were prepared and functionalized with citrate according to the classical Turkevich method. The citrate-functionalized nanoparticles contained about 3.1 wt% of organic material (135 ng cm⁻² or 3.1 molecules nm⁻²). A partial exchange of citrate was accomplished by tris(sodium-m-sulfonato-phenyl)phosphine (TPPTS) which led to 2.1 wt% of citrate (90 ng cm⁻² or 2.1 molecules nm⁻²) and 1.4 wt% TPPTS (61 ng cm⁻² or 0.6 molecules nm⁻²). The citrate coating was quantitatively exchanged by poly(N-vinyl pyrrolidone) (PVP) after immersion in solutions with concentrations of 33, 66 and 128 mg L^-1, respectively, leading to contents of 4 to 6 wt% of PVP (171–271 ng cm⁻² or 9–15 PVP monomer units nm⁻²).     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Diazepam Fluorimetric Monitoring Upon Photo-Degradation in an Automatic Miniaturized Flow System

The present work describes the fully integration in line of a photo-degradation unit, comprising a low pressure UV lamp, in a Multipumping Flow System (MPFS), for the fluorimetric chemical control of commercially available pharmaceutical formulations containing diazepam. The utilization of an organized micellar medium provided enhanced fluorescence emission. The results allowed to obtain a linear working range for diazepam concentrations of up to 40 mg L⁻¹ (r = 0.9998) and the detection limit was about 0.97 mg L⁻¹. The results obtained by the miniaturized and automatic flow system were in agreement with those furnished by the reference procedure, with relative deviations comprised between −2.09% and 2.13%.     

Fluorescence Enhancement Effect for the Determination of Polychlorinated Biphenyls with Bovine Serum Albumin

A sensitive and selective method for the trace determination of 3, 3’, 4, 4’-tetrachlorobiphenyl (PCB77) by using bovine serum albumin (BSA) as a fluorescence probe was introduced. Under optimum conditions, the enhanced fluorescence intensity was proportional to the concentration of polychlorinated biphenyls in the range of 8.9 × 10⁻⁸–5.0 × 10⁻⁶ mol L⁻¹ for PCB77, and 5.0 × 10⁻⁷–5.0 × 10⁻⁶ mol L⁻¹ for 2, 2’, 5, 5’-tetrachlorbiphenyl (PCB52). The detection limits (S/N = 3) of PCB77 and PCB52 were 2.6 × 10⁻⁸ mol L⁻¹ and 2.9 × 10⁻⁷ mol L⁻¹, respectively. Furthermore, the fluorescence enhancement mechanism was discussed in detail. Results indicated that fluorescence enhancement of the system originated from the formation of BSA-PCBs complexes. In addition, PCBs were mainly bound to the tyrosine residues in BSA molecules.     

Nanofibrous membrane of polyacrylonitrile with efficient adsorption capacity for cadmium ions from aqueous solution: Isotherm and kinetic studies

The nanofibrous membrane of polyacrylonitrile (NMP) was successfully synthesized after NaOH and NaHCO₃ treatment aiming its functionalization using electrospinning for cadmium ion (Cd²⁺) adsorption. Field emission scanning electron microscopy (FE-SEM) revealed that small particles attached to the surface of functionalized PAN nanofibers. Equilibrium was attained after 60 min following a rapid uptake of Cd²⁺ with maximum adsorption capacity and percentage removal at an optimum solution pH of 7.0. The adsorbent dose of 0.3 g and 90 mg L⁻¹ of initial Cd²⁺ concentration yielded the maximum adsorption capacity. The pseudo-second-order kinetic model was the best fitted to the adsorption data, indicating that the chemisorption is the controlling mechanism of adsorption. The physisorption was proposed based on the calculated values of the mean free energy of adsorption from the D–R isotherm (E < 8 kJ mol⁻¹). Furthermore, three-parameter isotherm models indicated the homogeneous and heterogeneous Cd²⁺ adsorption onto NMP adsorbent.     

A Fluorescein-based Fluorogenic Probe for Fluoride Ion Based on the Fluoride-induced Cleavage of <Emphasis Type="Italic">tert</Emphasis>-butyldimethylsilyl Ether

A highly sensitive and selective fluorogenic probe for fluoride ion, fluorescein di-tert-butyldimethylsilyl ether (FTBS), was designed and synthesized. FTBS was a colorless, non-fluorescent compound and was synthesized via the one-step reaction of fluorescein with tert-butyldimethylsilyl chloride. Upon incubation with fluoride ion in DMF-water solution (7 : 3, V/V), the Si-O bond of FTBS was cleaved, causing a large increase in fluorescence intensity and thereby allowing a selective detection of fluoride ion. The fluorescence increase is linearly with fluoride concentration in the range 0.1–2.0 μmol L⁻¹ with a detection limit of 0.041 μmol L⁻¹ (3σ). The excellent selective signaling behavior of the proposed probe was found to originate from the high affinity of silicon toward fluoride ion. The method has been successfully applied to the fluoride determination in multi-trace elements injection and toothpaste samples, and the results are agreed well with those obtained by the fluoride-ion selective electrode method.     

Selective Monitoring of Organophosphorus Pesticides by <Superscript>31</Superscript>P-NMR Spectroscopy: Application to Purity Assay of Technical Products and Concentration Determination of Formulated Samples

³¹P nuclear magnetic resonance (NMR) was used as a highly selective, rapid and suitable analytical tool for the simultaneous identification and determination of five important organophosphorus pesticides (OPPs), without any sample preparation, in technical and formulation samples. The quantitative works of ³¹P-NMR spectroscopy were performed in the presence of phosphoric acid as a suitable internal standard. Linear working range for the analysis of trichlorfon, chlorpyrofos, fenithrothion, diazinon and glyphosate was 25–300 mg L⁻¹. Limit of detection (at S/N = 3) for the proposed method, under the optimized experimental conditions, was found to be about 3 mg L⁻¹ for the first four OPPs and 16.3 for the last one. The proposed method was applied to the analysis of a glyphosate formulation and two trichlorfon and chlorpyrofos technical samples. There was excellent agreement between the results by ³¹P-NMR and those by the standard methods. The proposed method is rapid, simple and safe, as toxic samples are analyzed ‘as received’ without sample pre-treatment, permitting the routine analysis of pesticides in real samples.     

Detection of mercury in water by laser-induced breakdown spectroscopy with sample pre-concentration

A method based on pre-concentration, using electrolysis, has been proposed and used for the improvement of detection sensitivity of mercury ions at ultra-trace level of concentration in an aqueous matrix by laser-induced breakdown spectroscopy (LIBS). The experimental evaluation of this method was carried out on mercury chloride (HgCl₂) in triple-distilled water for a concentration range of the element of 0.01–10 mg l⁻¹. A pre-concentration factor of ∼180 was obtained for LIBS detection of mercury emission line at 253.65 nm. The limit of detection (LoD) of ∼0.011 mg l⁻¹ (or ∼11 ppb) for mercury in the water sample was achieved.     

Encapsulation of iron nanoparticles in alginate biopolymer for trichloroethylene remediation

Nanoscale zero-valent iron (NZVI) particles (10–90 nm) were encapsulated in biodegradable calcium-alginate capsules for the first time for application in environmental remediation. Encapsulation is expected to offers distinct advances over entrapment. Trichloroethylene (TCE) degradation was 89–91% in 2 h, and the reaction followed pseudo first order kinetics for encapsulated NZVI systems with an observed reaction rate constant (k _obs) of 1.92–3.23 × 10⁻² min⁻¹ and a surface normalized reaction rate constant (k _sa) of 1.02–1.72 × 10⁻³ L m⁻² min⁻¹. TCE degradation reaction rates for encapsulated and bare NZVI were similar indicating no adverse affects of encapsulation on degradation kinetics. The shelf-life of encapsulated NZVI was found to be four months with little decrease in TCE removal efficiency.     

Study of Enhanced Chemiluminescence of Diperiodatocuprate (III) on 1,10-Phenanthroline/Hydrogen Peroxide/Cetyltrimethylammonium Bromide System

In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H₂O₂) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H₂O₂/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹, and the corresponding detection limit is 1.9 × 10⁻⁹ mol L⁻¹. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10⁻⁹–1.0 × 10⁻⁵ g mL⁻¹, and the corresponding detection limit is 1.8 × 10⁻⁹ g mL⁻¹. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.     

Dependence of the resultant Seebeck coefficient on the thickness of Bi<Subscript>0.88</Subscript>Sb<Subscript>0.12</Subscript> alloy in welded M/Bi–Sb/M (M = Cu and Ni) composites

The local Seebeck coefficient α _L and the resultant Seebeck coefficient α _R of M/Bi_0.88Sb_0.12/M (M = Cu and Ni) composites with different thicknesses t _Bi–Sb of Bi–Sb alloy were measured as functions of z and T, where T is the absolute temperature, z is the distance from a center of Bi–Sb alloy to the middle point of two probes and α _L and α _R were measured using two probes separated by s=1.0 mm and s=t _Bi−Sb+0.1 mm, respectively. As a result, α _L was enhanced extremely at the position of 0.2–0.3 mm away from the interfaces, while the local temperature along a composite varies linearly with changes in z within Bi–Sb alloy. The local maximum of α _R at 344 K appeared at t _Bi−Sb≈0.9 mm, so that it is expected to increase up to −167 μV/K at t _Bi−Sb=0.87 mm from the expression fitted well to the experimental data, which is 2.1 times as large as the intrinsic α at 344 K of Bi–Sb alloy. Such a local enhancement in α _L would probably be caused by a temperature gradient across the depletion layer formed at the interface. The thermoelectric figure of merit ZT of a composite with an optimum t _Bi−Sb of 0.87 mm is expected to reach the large value of 0.98 at 344 K, which corresponds to 4.5 times as high a value as ZT=0.22 at 344 K of Bi–Sb alloy. It is thus considered that the increase in α _L at the interface is available as a useful mean of further increase in ZT of thermoelectric devices.