Gold-activated luminol chemiluminescence for the selective determination of cysteine over homocysteine and glutathione.

This work reports a chemiluminescence assay for the highly selective determination of cysteine in biological fluids without separation techniques. The method is based on the ability of cysteine to selectively enhance the metal-catalyzed chemiluminescence generated by the oxidation of luminol from gold tetrachloride anions under alkaline conditions. The selectivity of the method stems from the fact that, under strongly alkaline conditions, the formation of the four-membered ring transition state of cysteine is less favorable as compared to the formation of the respective 5- and 9- membered ring transition states of homocysteine and glutathione, respectively. These transition states exert stronger hindrance and hydrophobic interactions repelling the negatively charged luminol dianion and possibly exhibit lower reducing ability for dissolved oxygen, towards the formation of superoxide radicals, thus reducing the oxidation of luminol. Under the optimum experimental conditions, the linear range of the method extended from 0.5 to 20 µΜ while cysteine could be determined at concentrations as low as 0.5 µM, with good reproducibility (<3.5%) and recoveries between 80 and 93% in artificial and real biological fluids.

Aqueous photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid. Formation of disinfection byproducts in chlorinated swimming pool water.

The photochemical behavior of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid (ODPABA) was studied in different aqueous solutions and under different conditions. ODPABA photolysis was performed under laboratory conditions using a xenon light source and under natural sunlight conditions in sea, swimming pool as well as in distilled water. The influence of dissolved organic matter (DOM) on the degradation kinetics was also studied in the presence of various concentrations of humic acids (HA). The phototransformation was shown to proceed via pseudo-first-order reaction in all cases and the reaction rates followed the order: distilled water > swimming pool water > seawater, depending mainly on the presence of dissolved organic matter that retarded the photolysis reaction. Kinetic experiments were monitored with HPLC/UV-DAD and the half-lives (t 1/2) varied between 1.6 and 39 h in simulated solar irradiation and between 27 and 39 h in natural sunlight conditions. The product distribution during illumination was strongly dependent on the constitution of the irradiated media. Irradiation of the aqueous ODPABA solutions gave rise to several transformation products that were isolated by means of solid-phase extraction (SPE) and identified using GC-MS techniques. These were formed mainly through dealkylation and hydroxylation reactions and were detected in all aqueous solutions investigated. In the case of swimming pool water some additional byproducts were isolated and were tentatively identified as chlorinated intermediates, formed by the subsequent chlorination of the parent molecule as well as other intermediates.

Design of water hyacinth ponds for removing algal particles from waste stabilization ponds.

In this study it was demonstrated that when water hyacinth ponds (WHPs) are used for polishing the effluent from waste stabilization ponds (WSPs), suspended solids (mostly algal particles) are efficiently separated, which also resulted in the reduction of insoluble forms of COD and nutrients. The high pH of the WSPs effluent was easily adjusted to 6-7 as it passed through the WHPs. However, the use of water hyacinth rapidly reduced dissolved oxygen at the first cell to less than three mg/L or very frequently to a level of anaerobic state. Reduction of suspended solids at the WHPs mainly depends on the detention time and pH. An empirical separation model incorporating the detention time and pH dependence was developed.

A simple empirical model for activated sludge thickening in secondary clarifiers.

A simple empirical model for the thickening function of the activated sludge secondary clarifiers is presented. The proposed approach relies on the integration of previous models and it is based on the phenomenon of dilution of the incoming activated sludge in the feeding well of the settling tanks. The method provides a satisfactory description of sludge stratification within the clarifier. The only requirements are limited to parameters which are readily incorporated into the routine analysis performed in an activated sludge plant, thereby eliminating the need for additional experimental or computational effort. The method was tested in a full-scale activated sludge plant and it was found that it describes fairly well the return sludge concentration, the diluted sludge blanket concentration, the sludge blanket solids concentration and the sludge blanket height of full-scale secondary clarifiers.

Spectrofluorometric determination of vanadium based on the formation of a ternary complex between vanadium, peroxides, and 2-alpha-pyridylthioquinaldinamide. Application to the determination of hydrogen peroxide and peroxy acids.

A selective and sensitive method for the determination of the total amount of vanadium in nutritional and biological substrates is proposed. The method is based on the reaction of vanadium with 2-alpha-pyridylthioquinaldinamide (PTQA) in the presence of H2O2. The product of this reaction emits constant fluorescence, in a sulfuric acid environment, at 490 nm, with the exciting radiation set at 340 nm. Various parameters such as acidity, flow rate, solvents, and temperature were studied. The presence of a surface-active agent was also considered in order to increase sensitivity. At the optimal conditions, a calibration curve was constructed, revealing a linear range of 2-100 microg L(-1) and a detection limit as low as 0.5 microg L(-1) while the RSD ranged in the area of 0.1-1.8%, depending on vanadium concentration. The method was successfully applied to the analysis of a wide variety of food samples, which are known to contribute to the dietary required amount of vanadium and to relevant biological matrixes. Reversing the conditions of the above reaction, the effect of the peroxy group on the vanadium-PTQA system was examined. The formation of a vanadyl complex was revealed which was suitable for the determination of hydrogen peroxide and peroxy acids. Linear calibration curves in the range of 0.2-50 microM for H2O2 and 0.1-2 microM for a respective peroxy acid were obtained, yielding detection limits of 0.05 and 0.03 microM, respectively.

Gas chromatographic determination of 2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid sunscreen agents in swimming pool and bathing waters by solid-phase microextraction.

A method has been developed for the trace determination of two sunscreen constituents (2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid) in water samples, which are commonly used in commercial formulations. The method employs solid-phase microextraction (SPME) and gas chromatography with flame ionization and mass spectrometric detection. The technique was developed with headspace and direct sampling in order to demonstrate the applicability of these SPME extraction modes for the identification of these two UV absorbing compounds in waters. The main parameters affecting the SPME process, such as desorption time, extraction time profile, salt additives, pH, and temperature, were investigated. The poly(dimethylsiloxane) 100-microm and polyacrylate 85-microm fiber coatings were found to be the most efficient for the extraction of these compounds from aqueous matrices. Linear calibration curves in the wide range of 10-500 microg/l were obtained for both compounds yielding typical RSD values of 5-9% for both extraction modes. The recoveries were relatively high, 82-98%, with quantitation limits below 1 microg/l. A comparison between the proposed methods and the conventional multiresidue solid-phase extraction revealed that the proposed technique(s) can be reliably used for sunscreen residue measurement in water samples with satisfactory results.