Photochemical degradation of typical halogenated herbicide 2,4-D in drinking water with UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript>/micro-aeration

UV/H₂O₂/micro-aeration is a newly developed process based on UV/H₂O₂. Halogenated pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) photochemical degradation in aqueous solution was studied under various solution conditions. The UV intensity, initial 2,4-D concentrations and solution temperature varied from 183.6 to 1048.7 μW·cm⁻², from 59.2 to 300.0 μg·L⁻¹ and from 15 to 30°C, respectively. The concentration of hydrogen peroxide (H₂O₂) and pH ranged from 0 to 50 mg·L⁻¹ and 5 to 9, and different water quality solutions (tap water, distilled water and deionized water) were examined in this study. With initial concentration of about 100 μg·L⁻¹, more than 95.6% of 2,4-D can be removed in 90 min at intensity of UV radiation of 843.9 μW·cm⁻², H₂O₂ dosage of 20 mg·L⁻¹, pH 7 and room temperature. The removal efficiency of 2,4-D by UV/H₂O₂/micro-aeration process is better than UV/H₂O₂ process. The photodecomposition of 2,4-D in aqueous solution follows pseudo-first-order kinetics. 2,4-D is greatly affected by UV irradation intensity, H₂O₂ dosage, initial 2,4-D concentration and water quality solutions, but it appears to be slightly influenced by pH and temperature. There is a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicates that higher removal capacity can be achieved by the improvement of these factors. Finally, a preliminary cost analysis reveals that UV/H₂O₂/micro-aeration process is more cost-effective than the UV/H₂O₂ process in the removal of 2,4-D from drinking water.     

Detection of peroxyacetyl nitrate in air using chemiluminescence aerosol detector

A method for the rapid and sensitive determination of peroxyacetyl nitrate (PAN) in air based on a chemiluminescence reaction with an alkaline solution of luminol in the chemiluminescence aerosol detector is described. The PAN is chromatographically separated from nitrogen dioxide and ozone in a packed column filled with 5 % OV-1 on Chromosorb 30/60 and the eluted PAN is detected via the direct reaction with the luminol solution consisting of 0.002 mol L^?1 luminol, 1 vol. % Brij-35 and 0.1 mol L^?1 KOH. The limit of detection is 14.9 ng m^?3 (3 ppt) of PAN. Alternatively, the PAN after separation is thermally converted to NO₂ which is detected by the chemiluminescence reaction with a solution consisting of 0.002 mol L^?1 luminol, 0.5 mol L^?1 KOH, 0.2 mol L^?1 Na₂SO₃, 0.1 mol L^?1 KI, 0.05 mol L^?1 EDTA and 0.5 vol. % triton X-100. The alternative approach affords the simultaneous determination of PAN and NO₂. The limit of detection is 50 ppt of PAN and 50 ppt of NO₂. The time resolution is 3 min. The method was applied to the measurement of ambient peroxyacetyl nitrate in air.     

Improvement in the determination of traces of uranium in aqueous medium having high dissolved organic carbon and chloride ion by alpha-spectrometry

During this work the determination of uranium in the range of μg·L⁻¹ to tens of μg·L⁻¹ was done by alpha-spectrometry after electroplating the aliquots of water sample using (NH₄)₂SO₄ as an electrolyte. In general, the determination of uranium by alpha-spectrometry needs its separation from other transuranics specially thorium. The process described here does not involve any sample digestion and radiochemical separation of uranium from other transuranics. In this method an aliquot (1 to 3 mL) of the sample was dried and dissolve in (NH₄)₂SO₄ and thereafter the sample was electroplated on a stainless steel (SS) planchet by using an electrochemical cell of special design. The proposed techniques have a distinct advantage over the determination of uranium by adsorptive stripping voltammetry (AdSV) in which uranium-chloranilic (2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) acid complex was used for concentrating the uranium from the solution. Since in the case of AdSv, the determination of uranium was not possible for samples having dissolved organic carbon (DOC) more than 15 mg·L⁻¹ and Cl⁻ concentration is in the range of 40,000 μ·g⁻¹. In the case of spike experiments with ²³²U the recovery was observed in the range of 90–95% in aqueous medium having higher concentration of Cl⁻ and DOC as indicated above.     

Determination of human serum albumin using aurothiomalate as electroactive label

A new electroactive label has been used to monitor immunoassays in the determination of human serum albumin (HSA) using glassy-carbon electrodes as supports for the immunological reactions. The label was a gold(I) complex, sodium aurothiomalate, which was bound to rabbit IgG anti-human serum albumin (anti-HSA-Au). The HSA was adsorbed on the electrode surface and the immunological reaction with gold-labelled anti-HSA was then performed for one hour by non-competitive or competitive procedures. The gold(I) bound to the anti-HSA was electrodeposited in 0.1 mol L⁻¹ HCl at −1.00 V for 5 min then oxidised in 0.1 mol L⁻¹ H₂SO₄ solution at +1.40 V for 1 min. Silver electrodeposition at −0.14 V for 1 min followed by anodic stripping voltammetry were then performed in aqueous 1.0 mol L⁻¹ NH₃–2.0×10⁻⁴ mol L⁻¹ AgNO₃. For both non-competitive and competitive formats, calibration plots in the ranges 5.0×10⁻¹⁰ to 1.0×10⁻⁸ mol L⁻¹ and 1.0×10⁻¹⁰ to 1.0×10⁻⁹ mol L⁻¹ HSA, respectively, with estimated detection limits of 1.5×10⁻¹⁰ mol L⁻¹ (10 ng mL⁻¹) and 1.0×10⁻¹⁰ mol L⁻¹ (7 ng mL⁻¹), respectively, were obtained. Levels of HSA in two healthy volunteer urine samples were also evaluated, using both immunoassay formats.     

Flow injection spectrofluorimetric determination of iron(III) in water using salicylic acid

A simple and fast flow injection fluorescence quenching method for the determination of iron in water has been developed. Fluorimetric determination is based on the measurement of the quenching effect of iron on salicylic acid fluorescence. An emission peak of salicylic acid in aqueous solution occurs at 409 nm with excitation at 299 nm. The carrier solution used was 2 × 10⁻⁶ mol L⁻¹ salicylic acid in 0.1 mol L⁻¹ NH₄⁺/NH₃ buffer solution at pH 8.5. Linear calibration was obtained for 5–100 μg L⁻¹ iron(III) and the relative standard deviation was 1.25 % (n = 5) for a 20 μL injection volume iron(III). The limit of detection was 0.3 μg L⁻¹ and the sampling rate was 60 h⁻¹. The effect of interferences from various metals and anions commonly present in water was also studied. The method was successfully applied to the determination of low levels of iron in real samples (river, sea, and spring waters).     

Poly(3,4-ethylenedioxythiophene)-modified nafion membrane for direct methanol fuel cells

Membranes Nafion 117 are modified with poly(3,4-ethylenedioxythiophene) (PEDT) by chemical polymerization of EDT with H₂O₂ or FeCl₃ as the oxidants in a two-compartment cell. Depending on the oxidant and polymerization conditions, PEDT is deposited either as a thin film on the membrane surface or inside the Nafion membrane depending on whether FeCl₃ or H₂O₂ is used as the oxidant. The decrease in the ionic conductivity and methanol permeability is studied as a function of the polymerization time. A linear dependence is found with H₂O₂ and a t ^−1/2 dependence, with FeCl₃. The contributions of PEDT and Nafion to the overall conductivity of the composite membranes are separated by impedance measurements. The modified membranes (FeCl₃) are also tested in direct methanol fuel cells (DMFC). The methanol permeation through the membranes is measured by operating the fuel cell in an electrolysis mode. The influence of the modified membranes on the DMFC current-voltage characteristics is studied with 2 M CH₃OH and O₂ at 1.2 bar_abs and 80°C. Membrane electrode assemblies (MEAs) are prepared by hot pressing the modified membrane between two commercial gas diffusion electrodes with 1 mg cm⁻² of Pt loading. A decrease of the methanol permeation of 25% is observed at MEA with the modified membrane (1 h polymerization time), compared with that of MEA with a Nafion membrane. However, the overall DMFC performance decreases in the same relation: a maximal power density of 36 W cm⁻² is measured at MEA with a PEDT-modified membrane compared with 45 W cm⁻² for MEA with a Nafion membrane. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1330–1339. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Characteristics and formation of [AlO4Al12(OH)24(H2O)12]7+ in electrolysis process

[AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺ (Al₁₃) formation in electrolysis process is studied. The results detected by²⁷Al NMR spectroscopy show that high content of Al₁₃ polymer is formed in the partially hydrolyzed aluminum solution prepared by controlled electrolysis process. In the produced electrolyte of total Al concentration ([Al_T]) 2.0 mol · L⁻¹ with a basicity (B = OH/Al molar ratios) of 2.0, the content of Al₁₃ polymer is over 60% of total Al. Dynamic light scattering shows that the size distribution of the final electrolyte solutions ([Al_T] = 2.0 mol · L⁻¹) is trimodal with B = 2.0 and bimodal with B = 2.5. The aggregates of Al₁₃ complexes increase the particle size of partially hydrolyzed aluminum solution.     

Cutoff performance of Escherichia coli by charged and noncharged polyacrylonitrile ultrafiltration membranes

Cutoff performance of Escherichia coli (E. coli) was studied by three types of polyacrylonitrile (PAN) ultrafiltration (UF) membranes without and with charge groups of sulfonate sodium salt (SSS) and trimethylammonium chloride (TMA). These UF membranes were prepared by phase inversion method in water coagulation bath with various concentrations of dimethylsulfoxide (DMSO) and used for the E. coli cutoff experiments under 2.5 kPa applied pressure. With the increase of the polymer concentration in the DMSO cast solution, the pore size of the molecular size exclusion effect of the resultant UF membrane decreased. For UF experiments of E. coli suspension solution with 10⁷ colony forming unit/unit volume (cfu/ml), the permeability of the bacteria through the membrane was in the range of about 10⁻³% in PAN homopolymer membranes. It was found that E. coli permeation through copolymer UF membranes with SSS and TMA groups was completely restricted. Difference of the E. coli cutoff performance in these UF membranes was discussed in comparison with membrane filtration properties such as molecular sieve effect, permeation rate of solute and membrane morphology.     

Selective lanthanum ions optical sensor based on covalent immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane

An optical sensor membrane is described for the determination of lanthanum(III) ions based on the immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane. 4-Hydroxysalophen is covalently bonded to a transparent hydrolyzed triacetylcellulose film. The sensing membrane in contact with lanthanum ions at pH 4.0 changes color from white-yellow to orange (323 to 433 nm). Under the optimum conditions, the proposed membrane displayed a linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻² M La(III) with a limit of detection of 1 × 10⁻⁷ M. The response time of the membrane was within 5–6 min depending on the concentration of La(III) ions. The selectivity of the probe towards lanthanum ions was found to be excellent. The sensor was successfully applied to the determination of La(III) in water, industrial waste water, and in NIST-615 (glass matrix) and NIST-3127a (lanthanum solution) samples with satisfactory results.     

Platinum electrode coated with a bentonite–carbon composite as an environmental sensor for detection of lead

A Pt wire coated with a bentonite–carbon composite in a poly(vinyl chloride) membrane was used for detection of lead. The sensor has a Nernstian slope of 29.42±0.50 mV per decade over a wide range of concentration, 1.0×10⁻⁷ to 1.0×10⁻³ mol L⁻¹ Pb(NO₃)₂. The detection limit is 5.0×10⁻⁸ mol L⁻¹ Pb(NO₃)₂ and the electrode is applicable in the pH range 3.0–6.7. It has a response time of approximately 10 s and can be used at least for three months. The electrode has good selectivity relative to nineteen other metal ions. The practical analytical utility of the electrode is demonstrated by measurement of Pb(II) in industrial waste and river water samples.     

Separation of Tc(VII) from Tc(IV) by solvent extraction

The solvent extraction of Tc(IV) and Tc(VII) by isoamyl alcohol has been studied. The TcCl ₆ ²⁻ and TcO ₄ ⁻ ions are both extracted from 3M H₂SO₄ solution but hydrolyzed Tc(IV) species are not. This permits the separation of the two valence states of technetium. The air oxidation of carrier-free hydrolyzed^99mTc(IV) may be limited by the presence of⁹⁹Tc carrier in the same chemical form. Paper chromatography and electrophoresis were used to identify TcCl ₆ ²⁻ , TcO ₄ ⁻ and hydrolyzed species. It was also found that the hydrolyzed ReCl ₆ ²⁻ can reduce TcO ₄ ⁻ to Tc(IV).     

Determination of bisphenol-a and related compounds in human saliva by gas chromatography—mass spectrometry

Summary A simple and sensitive method for the determination of trace amounts of bisphenol-A (BPA), bisphenol-A diglycidyl dimethacrylate (bis-GMA), bisphenol-A dimethacrylate (bis-DMA) and triethyleneglycol dimethacrylate (TEGDMA) in human saliva is proposed. These materials are used in dental restorations, as composites and sealants, and are sometimes detected in human saliva after dental treatment. The proposed method involves protein precipitation using acetonitrile followed by acidification, evaporation of the solvent and dissolution with dichloromethane prior to injection into a GC-MS. Thermal derivatization in the injection system was used for the identification and quantification of bis-GMA. Clean-up is not necessary using SIM mode. Bisphenol-F (BPF) was used as internal standard. The linear range was 15 to 1000 μg·L⁻¹ for BPA, 50 to 10 000 μg·L⁻¹ for bis-GMA, 50 to 1000 μg·L⁻¹ for bis-DMA and 1 to 100 μg·L⁻¹ for TEGDMA. The detection limits were 3,15,10 and 0.3 μg·L⁻¹ for BPA, bis-GMA, bis-DMA and TEGD-MA, respectively. Validation of the proposed method was carried out by using the standard addition methodology. Samples of 10 mL of human saliva collected 1 h after dental treatment were analysed in order to assess the applicability of the method to detect and quantify such compounds originated from methacrylic resins used in odontological treatment.     

Determination of Carboxylic Acids from Plant Root Exudates by Ion Exclusion Chromatography with ESI-MS

Ion-exclusion chromatography (IEC) coupled with electrospray ionization quadrupole mass spectrometry (ESI-MS) has been used for the analysis of carboxylic acids. The use of ESI-MS provides increased specificity and sensitivity compared to existing detection methods. This paper applies IEC-ESI-MS to the analysis of carboxylic acids in commonly found root exudates and shows that the separation of nine carboxylic acids (pyruvic, oxalic, lactic, malonic, maleic, succinic, tartaric, aconitic and citric acids) can be achieved by IEC within 8 min. The ESI provided reasonable signals from negative ions, [M−H]⁻ in the negative ionization mode. Linear plots of peak area versus concentration were obtained in the range 50–25,000 μg L⁻¹ for MS detection under optimized MS conditions. The detection limits of target organic acids, based upon signal to noise ratio (S/N = 3), ranged from 10 to 30 μg L⁻¹. The reproducibility of peak areas was <2.5% (n = 5). The proposed method was used for the confirmation and quantification of carboxylic acids in nutrient solutions containing root exudates.     

Competition Between O2 and H2O2 in the Oxidation of Fe(II) in Natural Waters

The oxidation rates of nanomolar levels of Fe(II) in seawater (salinity S = 36.2) by mixtures of O₂ and H₂O₂ has been measured as a function of pH (5.8–8.4) and temperature (3–35∘C). A competition exists for the oxidation of Fe(II) in the presence of both O₂ (μ mol⋅L⁻¹ levels) and H₂O₂ (nmol⋅L⁻¹ levels). A kinetic model has been applied to explain the experimental results that considers the interactions of Fe(II) with the major ions in seawater. In the presence of both oxidants, the hydrolyzed Fe(II) species dominate the Fe(II) oxidation process between pH 6 and 8.5. Over pH range 6.2–7.9, the FeOH⁺ species are the most active, whereas above pH 7.9, the Fe(OH)⁰₂ species are the most active at the levels of CO²⁻₃ concentration present in seawater. The predicted Fe(II) oxidation rate at [Fe(II)]₀ = 30nmol⋅L⁻¹ and pH = 8.17 in the oxygen-saturated seawater with [H₂O₂]₀ = 50nmol⋅L⁻¹ (log ₁₀ k = −2.24s⁻¹) is in excellent agreement with the experimental value of log ₁₀ k = −2.29s⁻¹ ([H₂O₂]₀ = 55nmol⋅L⁻¹, pH = 8).     

Fabrication and development of interfacial polymerized thin-film composite nanofiltration membrane using different surfactants in organic phase; study of morphology and performance

The effects of addition of cationic cetyltrimethylammonium bromide (CTAB), non-ionic (Triton X-100) and anionic sodium dodecyl sulfate (SDS) surfactants in organic phase for preparing the composite nanofiltration membranes were investigated. The interfacial polymerization technique was employed by applying trimesoyl chloride (TMC) and piperazine (PIP) as the reagents for the preparation of poly(piperazineamide) on a UF support. The obtained thin layer membranes were placed in oven for 2 min at 70 °C. Water permeation performance, salt rejection, membrane surface charge, chemical structure and membrane morphology including top surface and cross-section were investigated for characterization of the prepared membranes using IR-ATR, SEM, filtration and zeta potential measurement. The prepared membranes using SDS showed higher flux compared to the other membranes. SEM surface images demonstrate some defects and cracks on the thin layer surface of the membrane prepared with SDS. For membrane containing CTAB, the salt rejection increased in the order of Na₂SO₄ > NaCl > MgCl₂ with variation around 50–90%.     

A study of the aerobic reaction between dopamine and Fe(III) in the presence of S<Subscript>2</Subscript>O<Subscript>3</Subscript><Superscript>2−</Superscript>

The reaction between Fe(III) and dopamine in aqueous solution in the presence of Na₂S₂O₃ was followed through UV–Vis spectroscopy, pH and oxy-reduction potential (Eh) measurements. The formation and quick disappearing of the complex [Fe(III)HL¹⁻]²⁺, HL¹⁻ = monoprotonated dopamine was observed with or without S₂O₃ ²⁻ at pH 3. An unexpected reaction occurs in presence of thiosulfate forming the stable anion complex [Fe(III)(L²⁻)₂]¹⁻, L²⁻ = dopacatecholate (λ = 580 nm) and the auto-increasing of the pH, from 3 to 7. It was proposed that H⁺ and molecular oxygen are consumed by free radical thiosulfate formed during the reaction.     

Properties of naproxen ion-selective electrodes

Naproxen membrane electrodes based on different plasticizers and the quaternary ammonium salts (QASs) dimethyldidecylammonium bromide, methyltrioctylammonium chloride, or tetraoctylammonium chloride, were prepared. The following basic parameters were investigated for the optimal electrode: measurement range (10⁻⁴ − 10⁻¹ mol L⁻¹), slope of the linear range of the calibration curve (−58.3 mV decade⁻¹), limit of detection (6.0 × 10⁻⁵ mol L⁻¹), lifetime (2.5 months), dependence of the electrode potential on pH (5.5 − 9.0), reproducibility of potential (1.2 mV) and selectivity coefficients in relation to selected organic and inorganic anions. The electrode was utilized for determination of naproxen in tablets by the calibration curve method and the standard addition method.      

Oxygen permeation and stability of Zr0.8Y0.2O0.9‒La0.8Sr0.2CrO3-δ dual-phase composite

A tubular membrane made of Zr_0.8Y_0.2O_1.9 (60 vol%) and was prepared by a standard ceramic process. Oxygen permeation through the membrane tube was examined by exposing its outer shell to air and sweeping its inner wall with pure helium or CO balanced with helium. An oxygen flux of 9.2×10⁻⁹ mol cm⁻² s⁻¹ was measured at 950°C under air/He gradient, and a larger flux of 3.2×10⁻⁸ mol cm⁻² s⁻¹ at 930°C under air/CO gradient. The membrane tube was found to exhibit excellent stability under highly reducing atmosphere and elevated temperatures. The oxygen permeation rate is likely to be increased through the modification of the surface and reduction of the membrane thickness.     

FAD-modified SiO2/ZrO2/C ceramic electrode for electrocatalytic reduction of bromate and iodate

SiO₂/ZrO₂/C carbon ceramic material with composition (in wt%) SiO₂ = 50, ZrO₂ = 20, and C = 30 was prepared by the sol–gel-processing method. A high-resolution transmission electron microscopy image showed that ZrO₂ and the graphite particles are well dispersed inside the matrix. The electrical conductivity obtained for the pressed disks of the material was 18 S cm⁻¹, indicating that C particles are also well interconnected inside the solid. An electrode modified with flavin adenine dinucleotide (FAD) prepared by immersing the solid SiO₂/ZrO₂/C, molded as a pressed disk, inside a FAD solution (1.0 × 10⁻³ mol L⁻¹) was used to investigate the electrocatalytic reduction of bromate and iodate. The reduction of both ions occurred at a peak potential of −0.41 V vs. the saturated calomel reference electrode. The linear response range (lrr) and detection limit (dl) were: BrO₃ ⁻, lrr = 4.98 × 10⁻⁵–1.23 × 10⁻³ mol L⁻¹ and dl = 2.33 μmol L⁻¹; IO₃ ⁻, lrr = 4.98 × 10⁻⁵ up to 2.42 × 10⁻³ and dl = 1.46 μmol L⁻¹ for iodate.     

Determination of p-nitroaniline by the tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system using non-equilibrium stationary state

This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn²⁺-KBrO₃-H₂SO₄. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L⁻¹ tartrate, 4.0 mL 0.7 mol L⁻¹ H₂SO₄, 1.5 mL 1.5×10⁻⁴ mol L⁻¹ MnSO₄, 4.0 mL 0.4 mol L⁻¹ acetone and 7.0 mL 0.05 mol L⁻¹ KBrO₃ was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10⁻⁷∼3.75×10⁻⁵ mol L⁻¹ with a lower detection limit of 2.50×10⁻⁸ mol L⁻¹.