Solid-phase extraction versus solid-phase microextraction for the determination of chlorinated paraffins in water using gas chromatography-negative chemical ionisation mass spectrometry

Solid-phase extraction (SPE) and solid-phase microextraction (SPME) were evaluated for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples using gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS). For SPE optimisation, four commercially available SPE cartridges were tested and several SPE parameters, such as the elution solvent, elution volume and breakthrough volume were studied. The best results were obtained with Varian Bond Elut-C18. In order to achieve a high selectivity in the determination of SCCPs, GC-NCI-MS was used. Quality parameters of the optimised SPE and SPME procedures were determined, and the best results were obtained for the SPE/GC-NCI-MS method with LODs of 5 and 20 ng l(-1) for tap and river water, respectively. This method was successfully applied to the analysis of SCCPs in river water samples at concentrations below the microg l(-1) level.     

A multicommuted flow system with solenoid micro-pumps for paraquat determination in natural waters

A flow system designed with solenoid micro-pumps is proposed for the determination of paraquat in natural waters. The procedure involves the reaction of paraquat with dehydroascorbic acid followed by spectrophotometric measurements. The proposed procedure minimizes the main drawbacks related to the standard chromatographic procedure and to flow analysis and manual methods with spectrophotometric detection based on the reaction with sodium dithionite, i.e. high solvent consumption and waste generation and low sampling rate for chromatography and high instability of the reagent in the spectrophotometric procedures. A home-made 10-cm optical-path flow cell was employed for improving sensitivity and detection limit. Linear response was observed for paraquat concentrations in the range 0.10–5.0 mg L⁻¹. The detection limit (99.7% confidence level), sampling rate and coefficient of variation (n = 10) were estimated as 22 μg L⁻¹, 63 measurements per hour and 1.0%, respectively. Results of determination of paraquat in natural water samples were in agreement with those achieved by the chromatographic reference procedure at the 95% confidence level.     

Variations in trace element concentrations in human blood serum in the normal state investigated by instrumental neutron activation analysis

Using instrumental neutron activation analysis, the variations in the serum levels of Br, Cs, Na, Rb, Se, and Zn were investigated in 18 persons in the normal state. By determining the element levels in relation to changes is the serum water content, information about the binding to the serum protein was obtained. The influence of physiological factors on the serum element levels was investigated. Changes in the concentrations due to variations in the protein/water ratio and in the zinc level as a result of different posture were observed. When standardized sampling procedures were used, the variations in the serum element concentrations during one hour and from day were found to be less than 10%.     

One-step controllable fabrication of superhydrophobic surfaces with special composite structure on zinc substrates

Stable superhydrophobic platinum surfaces have been effectively fabricated on the zinc substrates through one-step replacement deposition process without further modification or any other post-treatment procedures. The fabrication process was controllable, which could be testified by various morphologies and hydrophobic properties of different prepared samples. By conducting SEM and water CA analysis, the effects of reaction conditions on the surface morphology and hydrophobicity of the resulting surfaces were carefully studied. The results show that the optimum condition of superhydrophobic surface fabrication depends largely on the positioning of zinc plate and the concentrations of reactants. When the zinc plate was placed vertically and the concentration of PtCl(4) solution was 5 mmol/L, the zinc substrate would be covered by a novel and interesting composite structure. The structure was composed by microscale hexagonal cavities, densely packed nanoparticles layer and top micro- and nanoscale flower-like structures, which exhibit great surface roughness and porosity contributing to the superhydrophobicity. The maximal CA value of about 171° was obtained under the same reaction condition. The XRD, XPS and EDX results indicate that crystallite pure platinum nanoparticles were aggregated on the zinc substrates in accordance with a free deposition way.     

Reduction of silver(II) oxide by the solvent in acid media

The reaction of silver(II) oxide with water to yield silver(I) ions and oxygen is an important side-reaction in procedures which use silver(II) oxide as the oxidant. This reaction has been examined in solutions which were 0.01-1M in respect to sulphuric or perchloric acid. The rate of reduction varied directly with the amount of solid added and was a complex function of the concentrations of hydrogen ions, silver(I) ions and anions present. The kinetic results have been used to postulate a mechanism for the reaction.     

Development of novel reagent for Hantzsch reaction for the determination of formaldehyde by spectrophotometry and fluorometry.

A novel reagent, acetoacetanilide (AAA), was introduced to the determination of formaldehyde based on Hantzsch reaction. A simple and highly sensitive fluorometric method was achieved by using AAA. The main advantages in the use of this reagent are: the reaction is carried out at room temperature without any heating system, the cyclization product based on Hantzsch reaction is soluble in water, and the product can be detected by spectrophotometry and fluorometry. The maximum absorption wavelength of the product occurs at 368 nm, and the maximum excitation and emission wavelengths are found at 370 and 470 nm, respectively. Several important experimental variables of the procedures were examined; particularly, the reaction temperature, reaction time, concentrations of reagents, and pH of the reagent solution were optimized for improving the detecting sensitivity. The calibration graph was linear in the range of 1 x 10(-7) - 1 x 10(-6) M or much higher concentrations. The limit of detection (LOD), based on three times of the standard deviation of the reagent blank, was 2.0 x 10(-8) M. The proposed method was applied to the determination of formaldehyde in environmental water samples. Many foreign species commonly existing in water samples did not interfere with the determination of formaldehyde in the proposed method.     

Novel Spectrophotometric Method for Determination of Macro-paracetamol via Reaction with Bromine

The reaction between Br2 and paracetamol(p-AAP) leads to the formation of a coloured product, which can be used for spectrophotometric determination of the p-AAP content in its pure form and in different pharmaceutical preparations with p-AAP. The stoichiometric composition of the reaction was found to be n(p-AAP)∶n(bromine)=1∶3. The effects of pH and time on the spectra of p-AAP-bromine redox reaction product were studied. The interference of different additives on the measured spectra of the obtained product was also studied. The results obtained by the present method were compared with those obtained by the standard method. The F- and t- test values were calculated for both of the applied procedures and they met a confidence level of 99%. The proposed procedure actually needs no separation of these drugs from their sources before analysis and was unaffected by interference of other phenolic compounds. The proposed method is simpler and faster than the repoeted ones.     

A continuous two-phase reaction system coupled on-line with capillary chromatography for the determination of polar solutes in water

Gas chromatographic procedures are described for the determination of carboxylic acids and chlorinated anilines in water samples. Propionic acid and 2,6-difluorobenzoic acid in aqueous solution have been simultaneously alkylated and extracted by means of a continuous two-phase reaction system, and then quantitated by on-line coupled capillary gas chromatography; tetrahexyl-ammonium hydrogen sulfate was used as phase transfer catalyst and pentafluorobenzyl bromide as reagent. A factorial design approach was used to optimize on-line derivatization of aqueous propionic acid with regard to pH and concentration of phase transfer catalyst. Alkylation and extraction, under optimized conditions, followed by quantitation of the pentafluorobenzyl ester by flame ionization detection furnished a linear calibration for concentrations between 0.1 and 10 μg/ml. The relative standard deviation was 9–15 %. The continuous two-phase reaction system was also used to determine (chlorinated) anilines present in water at concentrations of 0.1–1 μg/ml; pentafluorobenzoyl chloride was used as reagent and analysis was performed by capillary gas chromatography with flame ionization or electron capture detection. The on-line acylation of p-chloroaniline was optimized with regard to pH, reagent concentration, and reaction time. The on-line reaction system worked satisfactorily for both applications, although excess reagent caused some problems with the chromatography.     

Copolymerisation alternee du methacrylate de methyle et du styrene complexes par du Chlorure de Zinc en milieu aqueux

In this paper we present some of our copolymerization results of methyl methacrylate with styrene in the presence of a complexing agent, zinc chloride. The reaction rates were studied as function of the level of complexing agent, water and time. It was found that the complexing agent level and the water level have opposite effect on the reaction yield, the reaction yield increasing as the level of the complexing agent is increased. The reaction time has also a positive effect on the yield. Using the interrelations between the various factors affecting the reaction an equation was derived; it relates the reaction yield with the following variables: monomers, complexing agent and water concentration as well as the reaction time. The experimental results were compared with theoretical values obtained from this equation and it showed a good fit.     

Uptake and UV-photooxidation of gas-phase polyaromatic hydrocarbons on the surface of atmospheric water films. 2. Effects of dissolved surfactants on naphthalene photooxidation

The adsorption and photochemical transformations of gas-phase naphthalene were studied in a flow-tube reactor with a view to understanding the photochemical reactions occurring in thin water films such as those of aerosols and fogs. Suwannee River fulvic acid (SRFA) was chosen as a surrogate for the surface active humic-like substances present in atmospheric water films. Experiments were performed on both 450 and 22 mum water films over a wide concentration range of SRFA (0-1000 mg.L-1). The effect of singlet oxygen on the reaction rate in the presence and absence of SRFA was ascertained. Naphthalene molecules can be bound to SRFA through hydrophobic interactions and be distributed in both the water and the SRFA regions. The rate constants for the photochemical reactions of naphthalene were fitted to a model that described the effect of SRFA in these two regions. The kinetic study on the 22 mum film revealed a greater surface reaction enhancement than for the 450 mum film at low SRFA concentrations. However, there was no surface reaction enhancement at high SRFA concentrations. To compare with SRFA, the effect of a conventional surfactant, sodium dodecyl sulfate, on the uptake and photochemical transformations of naphthalene was also studied.     

Formation kinetics of the pink azo dye in the determination of nitrite in natural waters

The kinetics of the reaction for the formation of the pink azo dye in the determination of nitrite in both fresh water and sea water was studied at different acidities, temperatures, and concentrations of N-1 naphthylethylenediamine (NED). It was found that the reaction is considerably faster in sea water than in fresh water, and that increase in the acidity slightly increases the molar absorptivity. A concentration of NED (4.29 × 10^?6 M) between the extremes described in the literature and 4.2 × 10^?3 M sulphanilamide are recommended for both manual determination and flow-injection analysis with respect to rapid reaction and a low reagent blank.     

Application of sequential injection analysis to the determination of cationic surfactants based on the sensitized molybdenum-bromopyrogallol red reaction.

The aim of this work was to develop a simple, automatic system for the evaluation of cationic surfactants by combining sequential injection analysis and the sensitized effect of cationic surfactants on the reaction between metal ions and chelating dyes. This reaction is based on the increase in absorbance of the complex formed among molybdenum, bromopyrogallol red and increasing concentrations of cationic surfactants. Under optimum conditions, two calibration plots were obtained for a concentration range between 2.50 x 10(-7) mol dm(-3) (detection limit) and 5.00 x 10(-4) mol dm(-3) of cetylpyridinium chloride, used as standard. Solubilization of water insoluble complexes formed for concentrations of cationic surfactants greater than 1.00 x 10(-4) mol dm(-3) were successfully achieved with Triton X-405. RSD values lower than 5.0% were obtained in all cases. The quality of the results obtained for 18 water samples were evaluated by comparison with conventional methods, with no statistically significant differences for a 95% confidence level.     

Density Functional Study on the Mechanism of Collision Reaction among Protons, N2 and Water Vapor

The mechanism of collision reaction among protons, N2 and water vapor was theoretically studied using Density Functional Theory. The geometries of reactants, transition states, intermediates and products were optimized at the B3LYP/6-311 G^** level by the BERNY gradient analysis method. Transition states and intermediates have been identified by vibrational frequency analysis. The relationship among reactants, intermediates, transition states and products was affirmed by IRC calculation. The variations of energy and geometry along the IRC-determined reaction paths were described. The possible reaction pathways were represented and the optimal one was decided from the viewpoint of energy.     

Trace analysis of parabens,triclosan and related chlorophenols in water by headspace solid-phase microextraction with in situ derivatization and gas chromatography–tandem mass spectrometry

An in situ derivatization solid-phase microextraction method has been developed for the determination of parabens, triclosan and related chlorophenols in water. Acetylated derivatives are selectively determined using gas chromatography with tandem mass spectrometry. Parameters affecting both derivatization and SPME procedures, such as fiber coating, extraction mode, temperature, volume of derivatizating reagent and ionic strength, are studied and optimized through a multifactorial experimental design. The performance of the method is studied in terms of accuracy, linearity, precision and limits of detection. Quantitative recoveries (≥82%) and satisfactory precision (RSD ≤ 12%) are obtained. Limits of detection at the low picogram per millilitre level are achieved for all target compounds. Linearity is studied in a wide range of concentrations and an analysis of variance with a lack-of-fit test is run to validate the calibration data. Extraction time profiles are also obtained. Finally, the applicability of the proposed method is demonstrated for several real samples including river water, wastewaters and swimming pool water. Since no matrix effects are observed, quantification can readily be carried out by external calibration with ultrapure water standards.     

Trace determination of α-keto acid in natural waters

Numerous chromatographic methods have been developed to detect α-keto acids in physiological or sea-water samples. These methods generally involve derivatization in a strongly acidic medium with elevated temperatures, desalting, preconcentration, and liquid-liquid extraction procedures prior to chromatographic analysis. These procedures may introduce significant errors because of adsorption losses, contamination, or decomposition of the α-keto acids. To avoid these potential problems, a chemically mild method to detect α-keto acids in sea water was developed. The method is based on the reaction of α-keto acids with 2,4-dinitrophenylhydrazine in sea water to form stable hydrazone derivatives. Desalting of the reaction mixture and preconcentration of the hydrazone derivatives is accomplished by a column-switching technique. The derivatives are separated by reversed-phase, high-performance liquid chromatography and detected by absorption spectrometry. Quantification of α-keto acids in the nM to μM concentration range shows complete recovery in sea water, excellent precision at 10–20 pmol (<5% relative standard deviation), and absorbances that are linearly related to α-keto acid concentrations. The detection limit of this method is 1–5 pmol for a 2-ml injection. Applications of this method to the detection of α-keto acids in marine sediment and sea-water samples are illustrated, and the first shipboard results are presented.     

Simultaneous spectrophotometric determination of nitrite and nitrate by flow injection analysis.

A new catalytic spectrophotometric method is reported for the simultaneous determination of nitrite and nitrate by flow injection analysis, based on the catalytic effect of nitrite on the redox reaction between pyrogallolsulfonephthalein and potassium bromate in acidic media. Nitrate can also be on-line reduced to nitrite with a modified copper-coated cadmium reduction column. The reaction was monitored spectrophotometrically by measuring the decrease in the absorbance of pyrogallolsulfonephthalein at 465 nm. Various analytical parameters such as effects of acidity, reagent concentrations, flow rates, sample sizes, lengths of the reaction coil and temperatures were studied and were optimized. Under the optimized conditions, the calibration graph was linear for 2.4 to 160 ng ml(-1) of nitrite and 4.0 to 100 ng ml(-1) of nitrate. The influences of potential interfering cations and anions for nitrite and nitrate determination were studied. The method is successfully applied for food and water samples. Up to ten samples can be analyzed per hour.     

On-site determination of polynuclear aromatic hydrocarbons in seawater by stir bar sorptive extraction (SBSE) and thermal desorption GC-MS

The identification and quantification of semi-volatile contaminants dissolved in water is currently done in laboratory after a sampling step. This procedure is not satisfactory first because risks of samples contamination and analytes losses remain, in particular when these are present in ultra-trace concentrations, and secondly because procedures are time-consuming. The coupling of the stir bar sorptive extraction (SBSE), a new device of extraction technique, and a new generation of gas chromatography mass spectrometry (GC-MS), the field apparatus EM 640 S from Bruker, could be an answer to the challenge of on-site analysis. This analytical system was used to analyze 24 PAHs, among them 15 EPA priority pollutants. It was shown that this coupling led to encouraging results with LODs around the sub-ppt level for most of the compounds and R.S.D. included between 1 and 48%. The existence of competition phenomena between the various analytes inside the absorbent phase was demonstrated with the release (up to 80%) of light compounds. This result shows the necessity to work on the kinetic domain rather than on the thermodynamic equilibrium that is influenced by nature and concentration of other compounds. The matrix effects were also studied through the comparative analysis of ultrapure water, artificial and natural seawaters spiked with PAHs and the influence of ionic strength and particulate organic matter was investigated.     

The oxidation of organic substances by compounds of trivalent manganese: XIV. Oxidation of malonic acid by manganese(III) sulfate in sulfuric acid medium and with hexaquomanganese(III) ions in noncomplexing perchloric acid medium

The oxidation of malonic acid by manganese(III) sulfate in a medium of sulfuric acid and by hexaquomanganese(III) ions in a noncomplexing perchloric acid medium was studied.The reaction stoichiometry was found and the effect of the concentrations of H⁺, Mn²⁺, and HSO₄^? ions and of the initial reactant concentrations on the course and rate of the reaction was studied.The optimum conditions have been found for analytical use of the reaction, procedures have been proposed for the determination of malonic acid using the two reagents, and the accuracy and reproducibility of the determinations have been found.     

天然水中可溶性硅酸与铝盐作用机理探讨

通过考察单核铝和溶解铝浓度的变化, 对天然水体中溶解性硅酸与铝盐的反应机理进行研究. 试验过程中, 采用8-羟基喹啉荧光分光光度法测定铝浓度并结合热力学计算进行机理验证. 结果表明: 单体硅酸和聚硅酸主要与溶液中的单核铝反应生成溶解性硅铝酸盐. 单体硅酸与单核铝的结合能力较弱; 聚硅酸与单核铝的结合能力则较强, 反应产物主要为二啮或三啮配合物. 溶液pH对反应过程有着重要影响, 偏碱性环境对硅酸与单核铝间的反应具有促进作用.     

Reactivity Tracers of the Hydrolysis of Fe(II)‐Bis(salicylidene) Complexes: Initial–Transition States Analysis and Enhanced Impact of Tensides on the Kinetic Trends

The kinetics of the acid hydrolysis reaction of Fe(II)‐bis(salicylidene) complexes were followed under pseudo–first‐order conditions ([H⁺] >> [complex]) at 298 K. The ligands of the studied azomethine complexes were derived from the condensation of salicylaldehyde with different five α‐amino acids. The hydrolysis reactions were studied in acidic medium at different ratios (v/v) of aqua–organic mixtures. The decrease in the dielectric constant values of the reaction mixture enhances the reactivity of the reaction. The transfer chemical potentials of the initial and transition states (IS–TS) from water into mixed solvents were determined from the solubility measurements combined with the kinetic data. Nonlinear plots of logk_obs versus 1/D (the reciprocal of the dielectric constant) suggest the influence of the solvation of IS–TS on the reaction reactivity. Furthermore, the acid hydrolysis reactions were screened in the presence of different concentrations of cationic and anionic tensides. The addition of surfactants to the reaction mixture accelerates the reaction reactivity. The obtained kinetic data were used to determine the values of δ_mΔG^# (the change in the activation barrier) for the studied complexes when transferred from “water to various ratios (v/v) of water–co‐organic binary mixtures” and from “water to water containing different [surfactant].” It was found that the reactivity of the acid hydrolysis reaction was controlled by the hydrophobicity of the studied chelates.