Development and Characterization of a Sol-Gel-Functionalized Glass Carbon Electrode Probe for Sensing Ultra-Trace Amounts of NH3 and NH4+ in Water.

This study centers on the development and characterization of an innovative electrochemical sensing probe composed of a sensing mesoporous functional sol-gel coating integrated onto a glassy carbon electrode (sol-gel/GCE) for the detection of NH3 and/or NH4+ in water. The main interest for integrating a functional sol-gel coating onto a GCE is to increase the selective and sensing properties of the GCE probe towards NH3 and/or NH4+ ions. The structure and surface morphology of the newly developed sol-gel/GCE probe were characterized employing scanning electron microscopy (SEM), atomic force microscopy (AFM), dynamic light scattering (DLS), and Fourier-transform infrared (FTIR), while the electrochemical sensing properties were evaluated by Berthelot's reaction, cyclic voltammetry (CV), and adsorptive square wave-anodic striping voltammetry (Ads SW-ASV). It is shown that the newly developed sol-gel coating is homogeneously deposited on the GCE with a sub-micron and uniform thickness close to 630 nm and a surface roughness of 25 nm. The sensing testing of the sol-gel/GCE probe showed limits of detection and limits of quantitation of 1.7 and 5.56 nM of NH4+, respectively, as well as a probe sensitivity of 5.74 × 10-1 µA/µM cm-2. The developed probe was fruitfully validated for the selective detection of NH3/NH4+ in fresh and sea water samples. Computed Student texp (0.45-1.25) and Fexp (1.69-1.78) (n = 5) tests were less than the theoretical ttab (2.78) and Ftab (6.39) at 95% probability.

Investigations on the Impact of a Series of Alkoxysilane Precursors on the Structure, Morphology and Wettability of an Established Zirconium-Modified Hybrid Anticorrosion Sol-Gel Coating.

The current study reports on the impact of a series of functional alkoxysilanes on the wettability and structure of a well-established silicon/zirconium hybrid anticorrosion sol-gel coating. The selected functional alkoxysilanes comprise tetra ethylorthosilicate (TEOS), 3-glycidyloxypropyltrimethoxysilane (GPTMS), 3-aminopropyltriethoxysilane (APTES) and vinyltriethoxysilane (VTES) and are incorporated at various concentrations (1, 5, 10 and 20%) within the silicon/zirconium sol-gel material. The prepared materials are successfully processed as coatings and cured at different temperatures in the range of 100-150 °C. The characterisation of the structures and surfaces is performed by dynamic light scattering (DLS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), silicon nuclear magnetic resonance spectroscopy (29Si-NMR), atomic force microscopy (AFM) and static water contact angle (WCA). Structural characterisations (DLS, FTIR,29Si-NMR) show that the functional alkoxysilanes effectively bind at the surface of the reference sol-gel material, resulting in the formation of functional core-shell nanoparticles. WCA results show that the hydrophobic properties of all materials decrease with curing temperature, and AFM analysis demonstrated that this behaviour is associated with a decrease in roughness. The physico-chemical processes taking place are critically assigned and discussed.

Innovative Sol-gel functionalized polyurethane foam for sustainable water purification and analytical advances.

Nanomaterial combined polymeric membranes such as polyurethane foams (PUFs) have garnered enormous attention in the field of water purification due to their ease of management and surface modification, cost-effectiveness, and mechanical, chemical, and thermal properties. Thus, this study reports the use of novel Sol-gel impregnated polyurethane foams (Sol-gel/PUFs) as new dispersive solid phase microextractors (d- µ SPME) for the efficient separation and subsequent spectrophotometric detection of Eosin Y (EY) textile dye in an aqueous solution with a pH of 3-3.8. The Sol gel, PUFs, and Sol gel-impregnated PUFs were characterized using scanning electron microscopy (SEM), goniometry measurements, dynamic light scattering (DLS), energy dispersive spectroscopy (EDS), UV-Visible, and FTIR spectra. Batch experiment results displayed a remarkable removal percentage (96% ± 5.4%) of the EY from the aqueous solution, with the total sorption time not exceeding 60 min. These data indicate rate-limited sorption via diffusion and/or surface complex ion associate formations after the rapid initial sorption steps. A pseudo-second order kinetic model thoroughly explained the sorption kinetics, providing a sorption capacity (qe) of 37.64 mg g-1, a half-life time (t1/2) of 0.8 ± 0.01 min, and intrinsic penetration control dye retention. The thermodynamic results revealed a negative value for ΔG° (-78.07 kJ mol-1 at 293 K), clearly signifying that the dye uptake was spontaneous, as well as a negative value for ΔH° (-69.58 kJ mol-1) and a positive value for ΔS° (147.65 J mol-1 K-1), making clear the exothermic nature of EY adsorption onto the sorbent, with a growth in randomness at the molecular level. A ternary retention mechanism is proposed, involving the "weak base anion exchanger" of {(-CH2-OH+ -CH2-) (Dye anion)-}Sol-gel/PUF and/or {(-NH2 + -COO-) (Dye anion)-}Sol-gel/PUF via solvent extraction and "surface adsorption" of the dye anion on/in the Sol-gel/PUFs membranes in addition to H-bonding, including surface complexation and electrostatic π-π interaction, between the dye and the silicon/zirconium oxide (Si-O-Zr) and siloxane (Si-O-Si) groups on the sorbent. Complete extraction and recovery (93.65 ± 0.2, -102.28 ± 2.01) of EY dye with NaOH (0.5 M) as a proper eluting agent was achieved using a sorbent-packed mini column. In addition, the established extractor displayed excellent reusability and does not require organic solvents for EY enrichment in water samples, making it a talented nominee as a novel sorbent for EY sorption from wastewater. This study is of great consequence for expanding the applicatio1n of Sol-gel/PUFs in developing innovative spectrophotometric sensing strategies for dye determination. In view of this, it would also be remarkable to perform future studies to explore the analytical implications of this extractor regarding safety and environmental and public health issues associated to the pollutant.

A quercetin based fluorescent chemical sensor for ultra-sensitive determination and speciation of tungsten species in water.

The current study explores the use of quercetin for developing a highly selective spectrofluorimetric methodology for trace determination, speciation and thermodynamic characterization of tungstate (WO42-) species in water. The study relies on the principle of chelate formation between WO42- and quercetin with subsequent increase in the emission intensity. The developed method could be applied successfully in a wide linear range (1.0-400.0 µg L-1) with a detection limit of 0.28 µg L-1 and quantification limit of 0.92 µg L-1 at λex/em = 400/492 nm. The developed method was successfully applied in real tap and waste water samples. The suitability of the proposed method was further validated by inductively coupled plasma-optical emission spectrometry (ICP-OES) in terms of student's t and F tests at 95% confidence. Characterization (NMR, FTIR and electronic spectra), stoichiometry, stability constant, fluorescence mechanism and thermodynamic parameters (ΔH, ΔS, and ΔG) of the produced complex species were evaluated and properly assigned. The fluorescence quenching mechanism of tungstate quercetin complex by Triton X-100 was also evaluated for computing Stern-Volmer quenching constant and approximating quenching sphere. The method showed a clear significance over most of the reported methods for tungsten in literature in terms of good accuracy, robustness, ruggedness, short analytical time and cost-effectiveness.

Biogenic Amines Formation Mechanism and Determination Strategies: Future Challenges and Limitations.

The evolution in foodstuff-monitoring processes has increased the number of studies on biogenic amines (BAs), in recent years. This trend with future perspective needs to be assembled to address the associated health risks. Thus, this study aims to cover three main aspects of BAs: (i) occurrence, physiology, and toxicological effects, most probable formation mechanisms and factors controlling their growth; (ii) recent advances, strategies for determination, preconcentration steps, model technique, and nature of the matrix; and (iii) milestone, limitations with existing methodologies, future trends, and detailed expected developments for clinical use and on-site ultra-trace determination. The core of the ongoing review will discuss recent trends in pre-concentration toward miniaturization, automation, and possible coupling with electrochemical techniques, surface-enhanced Raman scattering, spectrofluorimetry, and lateral flow protocols to be exploited for the development of rapid, facile, and sensitive on-site determination strategies for BAs.

A highly conductive thin film composite based on silver nanoparticles and malic acid for selective electrochemical sensing of trichloroacetic acid.

A highly conductive thin film composite based on silver nanoparticles (AgNPs) and malic acid (MA) was deposited on glassy carbon electrode (GCE) for the selective and sensitive electrochemical sensing of trichloroacetic acid (TCA). The casting solution containing MA functionalized AgNPs was employed as a precursor for the thermal deposition of the AgNPs integrated MA thin film composite onto the GCE surface. The uniform coverage of AgNPs within the thin film composite at GCE was obtained by field emission scanning electron microscopy (FESEM). A significantly high charge transfer resistance of the modified electrode (85.7â€¯Ω for AgNPs-MA/GCE in 2 mM [Fe(CN)6]3-/4- at a bias of +0.235 V as compared to bare GCE (38.01 Ω) verified the optimum coating of AgNPs-MA composite at the surface of the electrode. The AgNPs-MA composite deposited GCE revealed substantial electrocatalytic activity toward TCA reduction with significantly enhanced reduction current. The novel electrode manifested a linear square wave voltammetric (SWV) response over the concentration ranges of 0.1-2 (R2 = 0.9953) and 4-100 µM (R2 = 0.9969) with a limit of detection (LOD) and limit of quantification (LOQ) of 30 nM and 92.5 nM, respectively. The modified electrode exhibited an excellent long-term stability (30 days) with the retention of >95% of initial current. The selectivity of the proposed electrode for the determination of TCA was examined in the presence of dichloroacetic acid (DCA) and monochloroacetic acid (MCA) with the retention of high recovery percentages.

Synthesis, spectroscopic, thermal, antimicrobial and electrochemical characterization of some novel Ru(iii), Pt(iv) and Ir(iii) complexes of pipemidic acid.

Three new solid complexes of pipemidic acid (Pip-H) with Ru3+, Pt4+ and Ir3+ were synthesized and characterized. Pipemidic acid acts as a uni-dentate chelator through the nitrogen atom of the -NH piperazyl ring. The spectroscopic data revealed that the general formulas of Pip-H complexes are [M(L) n (Cl) x ]·yH2O ((1) M = Ru3+, L: Pip-H, n = 3, x = 3, y = 6; (2) M = Pt4+, L: Pip-NH4, n = 2, x = 4, y = 0 and (3) M = Ir3+, L: Pip-H, n = 3, x = 3, y = 6). The number of water molecules with their locations inside or outside the coordination sphere were assigned via thermal analyses (TG, DTG). The DTG curves refer to 2-3 thermal decomposition steps where the first decomposition step at a lower temperature corresponds to the loss of uncoordinated water molecules followed by the decomposition of Pip-H molecules at higher temperatures. Thermodynamic parameters (E*, ΔS*, ΔH* and ΔG*) were calculated from the TG curves using Coats-Redfern and Horowitz-Metzeger non-isothermal models. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were carefully used to assign properly the particle sizes of the prepared Pip-H complexes. The biological enhancement of Pip-H complexes rather than free chelate were assessed in vitro against four kinds of bacteria G(+) (Staphylococcus epidermidis and Staphylococcus aureus) and G(-) (Klebsiella and Escherichia coli) as well as against the human breast cancer (MCF-7) tumor cell line.

A simple and low cost dual-wavelength ß-correction spectrophotometric determination and speciation of mercury(II) in water using chromogenic reagent 4-(2-thiazolylazo) resorcinol.

The most common problems in spectrophotometric determination of various complex species originate from the background spectral interference. Thus, the present study aimed to overcome the spectral matrix interference for the precise analysis and speciation of mercury(II) in water by dual-wavelength ß-correction spectrophotometry using 4-(2-thiazolylazo) resorcinol (TAR) as chromogenic reagent. The principle was based on measuring the correct absorbance for the formed complex of mercury(II) ions with TAR reagent at 547nm (lambda max). Under optimized conditions, a linear dynamic range of 0.1-2.0µgmL-1 with correlation coefficient (R2) of 0.997 were obtained with lower limits of detection (LOD) of 0.024µgmL-1 and limit of quantification (LOQ) of 0.081µgmL-1. The values of RSD and relative error (RE) obtained for ß-correction method and single wavelength spectrophotometry were 1.3, 1.32% and 4.7, 5.9%, respectively. The method was validated in tap and sea water in terms of the data obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) using student's t and F tests. The developed methodology satisfactorily overcomes the spectral interference in trace determination and speciation of mercury(II) ions in water.

Adsorption characteristics of polycyclic aromatic hydrocarbons from non-aqueous media using activated carbon derived from phenol formaldehyde resin: kinetics and thermodynamic study.

Porous carbons were prepared by carbonization and activation of phenol formaldehyde resin by gasification with CO2 at 900 °C. Prepared activated carbon from phenol formaldehyde was characterized by measuring thermogravimetry (TG), differential thermal analysis (DTA), pH, surface area, porosity, and pore size distribution. The specific surface area (SSA) of these carbons ranges from 562 to 1904 m2/g, while their point of zero charge (pHPZC) varies from 2.6 to 8.8. The ability of the prepared activated carbon by gasification with CO2 at 900 °C from phenol formaldehyde resin (PFAC) to remove a series of polycyclic aromatic hydrocarbons (PAHs), e.g., naphthalene, fluorene, phenanthrene, pyrene, and fluoranthene, from mixtures of organic solvents with different polarities and chemical structures was tested. The adsorption capacity increases with the increasing the SSA and pHPZC of the carbons, confirming the roles of dispersive interactions. The kinetics and thermodynamics of the adsorption of phenanthrene as a model compound of PAH on PFAC in the organic solvent were studied. The adsorption capacity became notably greater with an increase in contact time and initial phenanthrene concentration.

Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples.

A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries.

Synthesis and Characterization of Silver Nanoparticles-Filled Polyethersulfone Membranes for Antibacterial and Anti-Biofouling Application.

BACKGROUND: The membrane processes are interesting and economical techniques for reuse of municipal and industrial wastewater as well as seawater desalination. However their drawbacks can be resumed in the fouling and biofouling due to the deposition and adsorption phenomenon of the components and the development of biofilm on membrane surface. Several studies have focused on the effect of the incorporation of nanoparticles in polymeric membrane matrix on the biofouling properties. Few relevant patents to the topic have been reviewed and cited. METHODS: Polyethersulfone (PES) membranes filled with silver nanoparticles (AgNPs) were prepared by non-solvent induced phase separation (NIPS) process using polyvinylpyrrolidone (PVP) as additive and N-Methyl-2-pyrrolidone (NMP) as solvent. Dope solution compositions, coagulation bath (CB) compositions, time before immersion in CB and casting speed were systematically studied. Membrane structure was characterized by scanning electron microscopy, contact angle, streaming potential measurement and X-ray diffraction (XRD). RESULTS: Membrane performance was assessed by pure water permeability, antifouling property, porosity and mechanical property. Silver nanoparticles (AgNPs) were prepared by the chemical reduction of silver nitrate solution with freshly prepared fructose solution, using PVP as capping agent and NaOH as accelerant and settled using acetone. The synthesized AgNPs were firstly characterized by Dynamic light scattering (DLS) technique, UV-visible spectrophotometer and X-ray diffraction spectroscopy (XRD). Then, we have selected a 15% PES mixed with 15% of PVP dope solution to prepare PESAgNPs blended membranes. CONCLUSION: All the nanocomposite membranes showed superb antibacterial and anti-biofouling performances, indicating that AgNPs in the PES membranes could be an effective approach to minimize membrane biofouling.

Interactions between Carbon Nanomaterials and Biomolecules.

Interactions between carbon nanomaterials, including carbon dots, fullerene, carbon nanotube, graphene, and graphene oxide, and biomolecules play an important role in the field of nanobiotechnology. Due to the unique properties of carbon nanomaterials and the magnificent features of their colloids, it shows high potential in fibrillation inhibition, high sensitivity sensor fabrication, bioimaging, drug delivery, and other areas. Hereby, we will go over different families of carbon nanomaterials regarding to the interaction between carbon nanomaterials and biomolecules at the interface, and their applications will be reviewed as well.

Extractive liquid-liquid spectrofluorometric determination of trace and ultra concentrations of bromate in water samples by the fluorescence quenching of tetraphenylphosphonium iodide.

A low cost and selective spectrofluorimetric method has been developed for trace determination of bromate ions in water. The method has been based upon complete extraction of the produced yellow colored ion associate of the reagent tetraphenylphosphonium iodide (TPP(+) I(-)) and bromate ions from aqueous media into chloroform and measuring the fluorescence quenching at λex/em=242/305nm. The composition, stability and the most probable mechanism of the produced associate have been determined. The plot of fluorescence intensity of TPP(+) I(-)vs. bromate concentration was linear in the range 0.86-150.0µgL(-1). The limits of detection (LOD) and quantification (LOQ) of BrO3(-) were 0.24 and 0.76µgL(-1), respectively. The method was found free from most of the interferences present in chromatographic, spectrofluorometric and spectrophotometric methods. Intra and inter-day laboratory accuracy and precision for analysis of bromate in water were determined. The method provides better performance compared to the international standard method recently issued (ISO 11206:2011). The method was applied satisfactorily for analysis of 1.0µgL(-1) bromate in the presence of high excess of chloride (50mg/L) without pretreatment with a relative standard deviation (RSD) of ±2.9%. The method was applied for analysis of bromate in various water samples. Statistical comparison of the results of the proposed method with those obtained by the standard method revealed no significant differences in the accuracy and precision.

Spectroscopic and electrochemical characterization of some Schiff base metal complexes containing benzoin moiety.

The ligation behavior of bis-benzoin ethylenediamine (B2ED) and benzoin thiosemicarbazone (BTS) Schiff bases towards Ru(3+), Rh(3+), Pd(2+), Ni(2+) and Cu(2+) were determined. The bond length of M-N and spectrochemical parameters (10Dq, ß, B and LFSE) of the complexes were evaluated. The redox characteristics of selected complexes were explored by cyclic voltammetry (CV) at Pt working electrode in non aqueous solvents. Au mesh (100 w/in.) optically transparent thin layer electrode (OTTLE) was also used for recording thin layer CV for selected Ru complex. Oxidation of some complexes occurs in a consecutive chemical reaction of an EC type mechanism. The characteristics of electron transfer process of the couples M(2+)/M(3+) and M(3+)/M(4+) (M=Ru(3+), Rh(3+)) and the stability of the complexes towards oxidation and/or reduction were assigned. The nature of the electroactive species and reduction mechanism of selected electrode couples were assigned.

Analysis of spironolactone residues in industrial wastewater and in drug formulations by cathodic stripping voltammetry.

The redox behavior of spironolactone (SP) drug in Britton-Robinson (BR) buffer of pH 2-11 was investigated by differential pulse cathodic stripping voltammetry (DPCSV) and cyclic voltammetry (CV) at hanging mercury dropping electrode (HMDE). At pH 9-10.5, the DPCSV of SP drug showed two cathodic peaks at -1.15 and -1.38 V at the HMDE vs. Ag/AgCl reference electrode. In the CV, at pH 9-10, the dependence of the cathodic peak current, Ip , c and peak potential, Ep,c of the second peak (Ep,c2) on the scan rate (ν) and on the depolizer (SP) concentrations was typical of an electrode coupled (EC) chemical reaction type mechanism. The plot of Ip , c at -1.380 V of the DPCSV vs. SP concentration at pH 9 was linear over the concentration range of 1.2×10-10-9.6×10-7 M. The lower limit of detection (LLOD) and limit of quantification (LOQ) of the drug were 1.1×10-11 and 4.14×10-11 M, respectively. The method was successfully applied for the analysis of SP residues in industrial wastewater, in pure form (98.2±3.1%) and in drug formulations e.g. Aldactone® tablet (98.35±2.9%).The method was validated by comparison with HPLC and the official data methods.

Spectrofluorometric determination and chemical speciation of trace concentrations of tungsten species in water using the ion pairing reagent procaine hydrochloride.

A highly selective and low cost extractive spectrofluorimetric method was developed for determination of trace concentrations of tungsten (VI) in water. The method was based upon solvent extraction of the developed ion associate [(PQH(+))(2)·WO(4)(2-)] of the fluorescent ion-pairing reagent [2-(diethylamino)ethyl 4 aminobenzoate] hydrochloride namely procaine hydrochloride, PQH(+)·Cl(-) and tungstate (WO(4)(2-)) in aqueous solution of pH 6-7 followed by measuring the resulting fluorescence enhancement in n-hexane at λ(ex/em)=270/320nm. The fluorescence intensity of PQH(+)·Cl(-) increased linearly on increasing tungstate concentration in the range 25-250µgL(-1). The limits of detection (LOD) and quantification (LOQ) of tungsten (VI) were found 7.51 and 24.75µgL(-1), respectively. Chemical composition of the developed ion associate and the molar absorptivity at 270nm were found to be [(PQH(+))(2)·WO(4)(2-)] and 2.7×10(4)Lmol(-1)cm(-1), respectively. Other oxidation states (III, IV, V) of tungsten species could also be determined after oxidation with H(2)O(2) in aqueous solution to tungsten (VI). The method was applied for analysis of tungsten in certified reference material (IAEA Soil-7) and wastewater samples. The results were compared successfully (>95%) with the data of inductively coupled plasma-mass spectrometry (ICP-MS).

Analysis of some selected catechins and caffeine in green tea by high performance liquid chromatography.

Green tea seems to have a positive impact on health due to the catechins-found as flavanols. Thus, the present study was aimed to develop a low cost reversed phase high performance liquid chromatographic (HPLC) method for simultaneous determination of flavanol contents, namely catechin (C), epicatechin (EC), epigallocatechin (EGC), epicatechin 3-gallate (ECG) and epigallocatechin 3-gallate (EGCG) and caffeine in 29 commercial green tea samples available in a Saudi Arabian local market. A C-18 reversed-phase column, acetonitrile-trifluoroacetic acid as a mobile phase, coupled with UV detector at 205 nm, was successfully used for precise analysis of the tested analytes in boiled water of digested tea leaves. The average values of N (No. of theoretical plates), HETP (height equivalent of theoretical plates) and R(s) (separation factor) (at 10 µg ml(-1) of the catechins EC, EGC, EGCG and ECG) were 2.6×10(3)±1.2×10(3), 1.7×10(-3)±4.7×10(-4) cm and 1.7±5.53×10(-2), respectively. The developed HPLC method demonstrated excellent performance, with low limits of detection (LOD) and quantification (LOQ) of the tested catechins of 0.004-0.05 µg ml(-1) and 0.01-0.17 µg ml(-1), respectively, and recovery percentages of 96-101%. The influence of infusion time (5-30 min) and temperature on the content of the flavanols was investigated by HPLC. After a 5 min infusion of the tea leaves, the average concentrations of caffeine, catechin, EC, EGC, ECG and EGCG were found to be in the ranges 0.086-2.23, 0.113-2.94, 0.58-10.22, 0.19-24.9, 0.22-13.9 and 1.01-43.3 mg g(-1), respectively. The contents of caffeine and catechins followed the sequence: EGCG>EGC>ECG>EC>C>caffeine. The method was applied satisfactorily for the analysis of (+)-catechin, even at trace and ultra trace concentrations of catechins. The method was rapid, accurate, reproducible and ideal for routine analysis.

Chemical speciation of chromium(III) and (VI) using phosphonium cation impregnated polyurethane foams prior to their spectrometric determination.

Fast and selective sorptions of Cr(VI) species from aqueous media onto tetraphenylphosphonium bromide (TPP(+) · Br(-)) physically immobilized polyurethane foams (PUFs) sorbent were achieved. Based on the Scatchard model of binding sites of the PUFs and Langmuir and Dubinin-Radushkevich (D-R) adsorption models of Cr(VI) retention onto TPP(+) · Br(-) immobilized PUFs, a dual retention mechanism involving absorption related to "weak-base anion ion exchange" and an added component for "surface adsorption" was proposed. Thus, the TPP(+) · Br(-) loaded PUFs were successfully packed in column mode for preconcentration of trace and ultra trace concentrations of Cr(VI) as halochromates [CrO(3)C](-)(aq) from aqueous HCl media. The retained [CrOCl(3)](-)(aq) species were recovered with NaOH (1.0 mol L(-1)) and analyzed by flame atomic absorption spectrometry. Cr(III) species after oxidation to Cr(VI) with H(2)O(2) in aqueous KOH (1.0 mol L(-1)) were also retained and could be recovered by the proposed method. The limits of detection (LOD) and quantification (LOQ) of Cr(VI) were 0.04 and 0.13 µg L(-1), respectively. The chemical speciation of Cr(III, VI) species in various water samples at trace and ultra trace levels were carried out by TPP(+) · Br(-) loaded PUFs packed column. The enhancement factor and sensitivity factor of [CrO(3)C](-)(aq) sorption were 80.0 and 30.0, respectively.

Spectrofluorometric determination and chemical speciation of trace concentrations of chromium (III & VI) species in water using the ion pairing reagent tetraphenyl-phosphonium bromide.

A highly selective, and low cost extractive spectrofluorometric method has been developed for determination of trace concentrations of chromium (III & VI) in water samples using the fluorescent reagent tetraphenylphosphonium bromide (TPP(+) · Br(-)). The method was based upon solvent extraction of the produced ion associate [TPP(+) · CrO(3)Cl(-)] of TPP(+) · Br(-) and halochromate in aqueous HCl and measuring the fluorescence quenching of TPP(+) · Br(-) in chloroform at λ(ex/em)=242/305 nm. The fluorescence intensity of TPP(+)Br(-) decreased linearly on increasing the chromium (VI) concentration in the range of 1-114 µg L(-1). The limits of detection (LOD) and quantification (LOQ) of chromium (VI) were 0.43 and 1.42 µg L(-1), respectively. Chromium (III) species after oxidation to chromium (VI) with H(2)O(2) in alkaline solution were also determined. Chemical speciation of chromium (III & VI) species at trace levels was achieved. The method was applied for analysis of chromium in certified reference material (IAEA Soil-7) and in tap- and wastewater samples and compared successfully (>95%) with the inductively coupled plasma-mass spectrometry (ICP-MS) results.

Part 1. Spectrophotometric determination of trace mercury (II) in dental-unit wastewater and fertilizer samples using the novel reagent 6-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-4(3H)-one and the dual-wavelength beta-correction spectrophotometry.

A simple and low cost method was developed and validated for the determination of trace mercury (II) ions in dental-unit wastewater and fertilizer samples. The method was based upon the reaction of mercury (II) ions with the novel reagent 6-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-4(3H)-one, the formed complex shows an absorption maximum at 505 nm (lambda(max)) in Britton-Robinson (B-R) buffer (pH 4-6).The corrected absorbance of the formed complex at lambda(max) was obtained employing beta-correction spectrophotometric method. Beer's-Lambert law and Ringbom's plots of the colored Hg-reagent complex were obeyed in the concentration range of 0.2-2.0 and 0.32-0.96 microg mL(-1) mercury (II) ions, respectively with a relative standard deviation in the range of 2.1+/-1.3%. The limits of detection (LOD) and quantification (LOQ) of the procedure were 0.026 and 0.086 microg mL(-1) Hg(2+), respectively. The proposed method was applied for the analysis of mercury (II) in dental-unit wastewater and fertilizer samples. The validation of the method was tested by comparison with the data obtained by the inductively coupled plasma-mass spectrometry (ICP-MS). The statistical treatment of data in terms of Student's t-tests and variance ratio f-tests has revealed no significance differences.