Ion mobility spectrometry as flow-injection detector and continuous flow monitor for aniline in hexane and water

Ion mobility spectrometry (IMS) was used as a flow-injection detector to quantitatively examine the ionization chemistry of aniline in hexane. A 5-microl sample was vaporized at 15-90-sec intervals in a flowing air stream and analyzed with an IMS equipped with acetone reactant ion chemistry, ambient temperature drift tube and membrane-based inlet. Precision was 3-11% relative standard deviation for 1-100 ppm aniline in hexane with 90-sec injection intervals and detection limits were ca. 0.5 ppm with 5-microl injections. Matrix effects with amine and organic solvent mixtures were observed and corrected for low and medium proton affinity interferences with standard addition methods. Pronounced fouling of the IMS occurred when a continuous water flow was introduced for aqueous flow injection-IMS. Continuous water monitoring without degraded IMS performance was possible by sampling air flow through a Silastic tube immersed in an aqueous sample.     

Improving GC-MS screening analysis by functional-group-related silica gel fractionation of industrial wastewater extracts

The separation of the components of complex industrial waste water extracts according to their functional groups has been accomplished by use of small silica gel columns eluted with a hexane – dichloromethane – methanol gradient. The six fractions obtained covered a polarity range from aliphatic fatty acids to (aromatic) polyhydroxy and polyether compounds. Recovery of model compounds was between 75 and 105%. Used prior to GC-MS analysis this fractionation substantially enhances chromatographic resolution and facilitates peak identification. The procedure was exemplarily applied to an extract of anaerobically treated tannery waste water. Phenols, aromatic acids, and aromatic and aliphatic (poly)hydroxy acids, in the low ppm range, were determined as main constituents. Since fractionation extends the range of detection, trace substances such as chlorocresol, dichlorobenzoic acid, mercaptobenzothiazole, and mercaptoacetic acid were also detectable at the ppb level.     

树莓状超疏水多孔复合棉纤维的制备及油水分离性能

基于聚多巴胺（PDA）的化学性质和树莓状纳米粒子的粗糙结构,以聚多巴胺包覆的棉纤维为基底,制备了具有多重粗糙度的树莓状超疏水多孔复合棉纤维材料.通过扫描电子显微镜观察树莓状超疏水多孔复合棉纤维表面的微观形貌,PDA-SiO₂纳米粒子稳定地固定在聚多巴胺涂覆的棉纤维表面.经过氟化改性的树莓状超疏水多孔复合棉纤维具有超疏水性,水接触角为158.2°,油接触角为0°.油/水分离实验结果表明,树莓状超疏水多孔复合棉纤维对己烷/水混合物的分离效率可达99.4%以上,使用20次后仍维持较高的分离效率.同时,其具有较高的溶剂吸附能力（13~34 g/g）、重复使用性及机械稳定性,吸油能力可与硅气凝胶相媲美.     

Determination of butyltin, methyltin and tetraalkyltin in marine food products with gas chromatography-atomic absorption spectrometry

Extraction methods were developed for the determination of butyltin, methyltin and tetraalkyltin in marine food products. Alkyltins were complexed with either diphenylthiocarbazone (dithizone) or tropolone from enzymatically hydrolysed samples. Tetraalkyltins were extracted with hexane. Butyl or methyl derivatives of the alkyltins were made by Grignard reaction for analysis by gas chromatography-atomic absorption spectrometry. Many of the examined marine food products contained ppb levels of alkyltins. Tetramethyltin and tetraethyltin levels were less than the method detection limits of 0.8 and 0.7 ng/g (as Sn), respectively.     

Development of an automated method for determining oil in water by direct aqueous supercritical fluid extraction coupled on-line with infrared spectroscopy

A direct aqueous supercritical fluid extraction (SFE) system was developed which can be directly interfaced to an infrared spectrometer for the determination of oil in water. The technique is designed to provide an environmentally clean, automated alternative to established IR methods for oil in water analysis which require the use of restricted organic solvents. The SFE-FTIR method involves minimum sample handling stages, with on-line analysis of a 500 ml water sample being complete within 15 min. Method accuracy for determining water samples spiked with gasoline, white spirit, kerosene, diesel or engine oil was 81-100% with precision (RSD) ranging from 3 to 17%. An independent evaluation determined a 2 ppm limit of quantification for diesel in industrial effluents. The results of a comparative study involving an established IR method and the SFE-FTIR method indicate that oil levels calculated using an accepted equation which includes coefficients derived from reference hydrocarbon standards may result in significant errors. A new approach permitted the derivation of quantification coefficients for the SFE-FTIR analyses which provided improved results. In situations where the identity of the oil to be analysed is known, a rapid off-line SFE-FTIR system calibration procedure was developed and successfully applied to various oils. An optional in-line silica gel clean-up procedure incorporated within the SFE-FTIR system enables the same water sample to be analysed for total oil content including vegetable oils and selectively for petroleum oil content within a total of 20 min. At the end of an analysis the SFE system is cleaned using an in situ 3 min clean cycle.     

A sensitive colorimetric method for the micro determination of iodine in marine water

More than 70% of the earth surface is covered by water bodies. Marine pollution is associated with the discharge of oils, petroleum products, sewage agricultural wastes, pesticides, heavy metals, waste substances and dumping of radioactive waters in sea. This in turn results in hazards to human health, hindrance to aquatic organisms and impairment of quality for use of sea water. Sea water is reported to contain iodine but the concentration varies according to the location and depth. Here a simple and sensitive method is described for the determination of iodine using leucocrystal violet as a reagent in different samples of sea water. The method is based on the oxidation of iodine to iodate with bromine water and the liberation of free iodine from the iodate by addition of potassium iodide in acedic medium. This iodine selectively oxidises leucocrystal violet to form the crystal violet dye. Beer's law is obeyed over the concentration range of 0.04-0.36 ppm of iodine at lambda(max) 592 nm. The dye was further extracted in chloroform. The extracting system obeys Beer's law in the range of 0.008-0.08 ppm at lambda(max) 588 nm.     

Polymer coatings to passivate calcite from acid attack: polyacrylic acid and polyacrylonitrile

The extent of passivation of calcite toward dissolution by aqueous acids arising from polymeric coatings based on polyacrylic acid or polyacrylonitrile is evaluated using a channel flow cell technique with microdisc electrode detection. In situ passivation with polyacrylic acid leads to a reduction in the reactivity of calcite toward acid attack with a reduction in the rate constant by up to an order of magnitude compared with untreated calcite. Ex situ passivation with polyacrylic acid for 24 h results in good coverage of the calcite by the polymer but it is shown to erode from the surface when exposed to an aqueous acid solution. In contrast, polyacrylonitrile is demonstrated to form a regular coating after exposure for just 1 h and offers robust potent protection from aqueous acid attack.     

Equilibrium studies of mercury(II) complexes with penicillamine

A solid-phase microextraction method coupled with a flame photometric detector was developed for the analysis of organophosphorus pesticides in water. Two kinds of fiber (100 mum polydimethyl siloxane (PDMS) and 85 mum polyacrylate (PA) fibers) were used and compared. Parameters that may affect the extraction, such as the duration of absorption and desorption, temperature of absorption, ionic strength, elutropic strength, and concentration of humic acid were investigated. Higher sensitivity and lower detection limits were achieved using a PA fiber than using a PDMS fiber. The detection limit is less than 0.3 mug l(-1) for most of the analytes, except for mevinphos (420 mug l(-1)). The precision is better than 9%.     

Effects of polyacrylic acid on the room-temperature phosphorescence of selected compounds

Polyacrylic acid solutions of 4-phenylphenol, p-aminobenzoic acid, 1,2-benzocarbazole, and 5,6-benzoquinoline were spotted on filter paper and the results obtained by room-temperature phosphorescence were compared with similar samples spotted on filter paper without polyacrylic acid. Improvements in sensitivity ranged from 26 times to 1.1 times and limits of detection from 100 times to 1.1 times for the samples on filter paper with polyacrylic acid. The relative standard deviations for the samples with polyacrylic acid added were also improved.     

Rapid characterization of fatty alcohol ethoxylates by non-aqueous capillary electrophoresis

Fatty alcohol ethoxylates (FAE) (a mixture of nonionic surfactants) have been characterized using NACE with UV detection. Phenyl polyurethane derivatives of these compounds were previously obtained by reaction with phenyl isocyanate. The derivatization reaction only requires microwave irradiation for 30 s (600 W). Phenyl polyurethanes were separated and characterized using a BGE containing a mixture of ammonium nitrate (15 mM), acetic acid (1.5%) and 9:1 v/v methanol/ACN. After optimization of the instrumental conditions for the separation, phenyl polyurethane compounds (formed from the corresponding FAE) with ethylene oxide numbers (EON) of 6 (certified standard and industrial samples), 7 and 10 (both as industrial samples), and 5.5 (microemulsion phase) were successfully separated and characterized. The properties of these FAE nonionic surfactants are very important in the petroleum industry, which requires characterization of the quality of the purchased materials as well as the final products in the microemulsion-oil-water stream process. This analytical objective has been achieved by the proposed NACE methods, allowing FAE to be distinguished from 5.5 to 10 EON with errors below 4%, and shows advantages against to HPLC methods.     

Preparation of a polyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction

We report on the fabrication and performances of a solid-phase microextraction (SPME) fiber based on a stainless steel wire coated with a covalently attached polyacrylonitrile (PAN)/multi-walled carbon nanotubes (MWCNTs) composite. This new coating is obtained by atom transfer radical polymerization (ATRP) of acrylonitrile mixed with MWCNTs. ATRP is initiated from 11-(2-bromo-2-methylpropionyloxy)-undecyl-phosphonic acid molecules grafted on the wire surface via the phosphonic acid group. The extraction performances of the fibers are assessed on different classes of compounds (polar, non-polar, aromatic, etc.) from water solutions by headspace extraction. The optimization of the parameters affecting the extraction efficiency of the target compounds was studied as well as the reproducibility and the repeatability of the fiber. The fibers sustain more than 200 extractions during which they remain chemically stable and maintain good performances (detection limits lower than 2 μg/l, repeatability, etc.). Considering their robustness together with their easy and inexpensive fabrication, these fibers could constitute promising alternatives to existing products.     

Chromatographic determination of copper speciation in jet fuel

A method is described that allows one to distinguish and quantitate two different classes of copper compounds in the same hydrocarbon sample. This will enable the study of the effects of different copper compounds on the performance and stability of petroleum samples. Copper N,N'-disalicylidene-1,2-propylenediamine (CuDMD) and several copper carboxylates were preconcentrated from a hydrocarbon matrix using a column packed with polyvinylpyrrolidone, (C(6)H(9)NO)(x), a novel polymeric stationary phase. The copper complexes were then sequentially eluted using a step gradient program beginning with hexane/isopropyl alcohol as the eluent and ending with an acetic acid/isopropyl alcohol eluent. The copper complexes were detected by serial UV absorbance and flame atomic absorbance (FAA) detection. With on-column preconcentration and FAA detection, the limits of detection were 7 and 40 ppb copper for CuDMD and the copper carboxylates respectively. With this method, it was possible to distinguish between the two different classes of copper compounds in the same hydrocarbon sample, which will help to provide an understanding of the catalytic activity of different copper compounds, leading to a better understanding of the factors causing fuel instability. The method promises to be a valuable tool in the analysis and characterization of copper compounds in petroleum samples.     

Studies in atomic-fluorescence spectroscopy--VIII. Atomic fluorescence and atomic absorption of thallium and mercury with electrodeless discharge tubes as sources

Atomic-fluorescence measurements, with microwave-excited electrodeless discharge tubes as sources of excitation, are described for thallium and mercury. The limits of detection by atomic fluorescence are 0.12 ppm for thallium and 0.08 ppm for mercury; the corresponding limits by atomic absorption (using the same instrument and source) are 6 and 10 times as great. The preparation, operation and spectral characteristics of thallium and mercury discharge tubes are described and comparisons are made with a thallium hollow cathode lamp and thallium and mercury spectral discharge lamps.     

Separation of Nile Blue-labelled fatty acids by CE with absorbance detection using a red light-emitting diode

The separation of fatty acids derivatised with Nile Blue (NB) by CE with detection using a red light-emitting diode (LED) was examined. NB was selected as the derivatisation agent due to its high molar absorption coefficient of 76,000 M(-1) cm(-1) at 633 nm, making it well suited for sensitive absorbance detection using a red 635 nm LED. NB-labelled fatty acids were separated by both MEKC using SDS micelles, i-PrOH and n-BuOH and by NACE in a number of solvents including MeOH, EtOH and ACN. The sensitivity of NACE was superior to MEKC, with detection limits of 5x10(-7)-7x10(-7) M obtained for each acid, approximately 20 times lower than the MEKC method. The NACE detection limits are approximately 100 times lower than previous reports on the separation of fatty acids by CE using indirect absorbance detection, ten times lower than using indirect fluorescence detection and are inferior only to those obtained using precapillary derivatisation and direct fluorescence detection. The efficiency of the NACE method was also superior to MEKC and allowed the separation of unsaturated fatty acids to be examined, although it was not possible to baseline-resolve linoleic (C18:2) and linolenic (C18:3) acids in a reasonable time. The method was used to analyse the fatty acid profile of two edible oils, namely sunflower and sesame oils, after alkali hydrolysis, where it was possible to identify both the saturated and unsaturated fatty acids in each sample.     

Determination of mercury in SRM crude oils and refined products by isotope dilution cold vapor ICP-MS using closed-system combustion

Mercury was determined by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS) in four different liquid petroleum SRMs. Samples of approximately 0.3 g were spiked with stable (201)Hg and wet ashed in a closed system (Carius tube) using 6 g of high-purity nitric acid. Three different types of commercial oils were measured: two Texas crude oils, SRM 2721 (41.7+/-5.7 pg g(-1)) and SRM 2722 (129+/-13 pg g(-1)), a low-sulfur diesel fuel, SRM 2724b (34+/-26 pg g(-1)), and a low-sulfur residual fuel oil, SRM 1619b (3.5+/-0.74 ng g(-1)) (mean value and 95% CI). The Hg values for the crude oils and the diesel fuel are the lowest values ever reported for these matrices. The method detection limit, which is ultimately limited by method blank uncertainty, is approximately 10 pg g(-1) for a 0.3 g sample. Accurate Hg measurements in petroleum products are needed to assess the contribution to the global Hg cycle and may be needed in the near future to comply with reporting regulations for toxic elements.     

Analysis of drying oils used as binding media for objects of art by capillary electrophoresis with indirect UV and conductivity detection

Capillary electrophoresis (CE) was applied to analyse the long-chain fatty acid composition of vegetable oils, and their degradation products formed upon ageing when drying oils are used as binding media. The analytes were detected with contactless conductivity detection (CCD) and indirect UV absorption, both detectors positioned on-line at the separation capillary. The long-chain fatty acids were resolved in a background electrolyte (BGE) consisting of phosphate buffer (pH = 6.86, 15 mM) containing 4 mM sodium dodecylbenzensulfonate, 10 mM Brij 35, 2% (v/v) 1-octanol and 45% (v/v) acetonitrile. As in this system dicarboxylic analytes, the products of oxidative degradation of unsaturated fatty acids, cannot be determined, a suitable background electrolyte was developed by the aid of computer simulation program PeakMaster. It makes use of a 10 mM salicylic acid, 20 mM histidine buffer, pH 5.85, which combines buffering ability with the optical properties obligatory for indirect UV detection. This buffer avoids system eigenpeaks, which are often impairing the separation efficiency of the system. Separation of the dicarboxylic analytes was further improved by a counter-directed electroosmotic flow (EOF), obtained by dynamically coating the capillary wall with 0.2 mM cetyltrimethylammonium bromide. Long-chain fatty acids and their decomposition products could be determined in recent and aged samples of drying oils, respectively, and in samples taken from two paintings of the 19th century.     

Separation and determination of perfluorinated carboxylic acids using capillary zone electrophoresis with indirect photometric detection

Perfluorinated carboxylic acids (PFCAs) belong to anthropogenic fluoroorganic compounds that have been detected in the natural environment and living organisms including humans. A capillary zone electrophoretic method with indirect UV detection using 2,4-dinitrobenzoic acid (2,4-DNBA) as a chromophore probe has been developed for analysis of PFCAs (C6-C12) in water. Optimal analyte resolution and detection sensitivity was obtained with 50 mM Tris solution of pH 9.0 and 50% methanol as a background electrolyte (BGE). The baseline separation of C6-C12 PFCAs was obtained within 20 min with detection limits in the range from 0.6 to 2.4 ppm.     

Method for simultaneous analysis of eight vitamin E isomers in various foods by high performance liquid chromatography and fluorescence detection

The objective of this study was to optimize a method to investigate the occurrence and to quantify the full isomeric composition of vitamin E (α-, β-, γ- and δ-tocopherols and tocotrienols) in 6 vegetables (raw and cooked), 3 herbs/spices, raw and cooked eggs, vegetable oils (canola, olive and soybean), flaxseed and sorghum (flour and seeds) and soy (flour) by HPLC with fluorescence detection. Different conditions of extraction and analysis were tested. The optimized method consisted of direct extraction with solvent (hexane:ethyl acetate, 85:15, v/v). For analysis normal phase column was used with mobile phase consisting of hexane:isopropanol:acetic acid (98.9:0.6:0.5) with isocratic elution and fluorescence detection. Excellent separation of all isomers was obtained along with adequate quantification in the foods analyzed. Recovery rates of standards ranged from 91.3 to 99.4%. The linearity range for each isomer varied from 2.5 to 137.5 ng/mL (R2 greater than 0.995 in all cases). Detection limits ranged from 21.0 to 48.0 ng/mL for tocopherols and from 56.0 to 67.0 ng/mL for tocotrienols, while quantification limits ranged from 105.0 to 240.0 ng/mL for tocopherols and from 280.0 to 335.0 ng/mL for tocotrienols. The optimized method was considered simple, fast and reliable, and also preserved vitamin E isomers when compared to validated methods involving saponification.     

Plasmas for lab-on-the-chip applications

Two small-size plasmas used as detectors of halogenated hydrocarbons and suitable for miniaturized instrumentation are discussed. A reduced pressure dielectric barrier discharge was integrated in a diode laser atomic absorption spectrometer and the already reported chlorine detection limits of 5 ppm (v/v) can be improved with one order of magnitude by spatially resolved measurements. A microstructured electrode discharge at atmospheric pressure was coupled with a miniaturized Échelle spectrometer and detection limits were found to be 20 ppb for chlorine as well as for fluorine.     

Comparison of highly-fluorinated chloroformates as direct aqueous sample derivatizing agents for hydrophilic analytes and drinking-water disinfection by-products

Four highly-fluorinated alkyl and aryl chloroformates, including 2,2,3,3,4,4,5,5-octafluoro-1-pentyl chloroformate (OFPCF), 2,3,4,5,6-pentafluorobenzyl chloroformate (PFBCF), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octyl chloroformate (TDFOCF), and 2-(2,3,4,5,6-pentafluorophenoxy)-ethyl chloroformate (PFPECF), were synthesized and tested as reagents for the direct water derivatization of polar and hydrophilic analytes. The goal of this research was to develop an optimal derivatizing agent to aid in the identification of highly polar ozonation drinking water disinfection by-products (DBPs) that are believed to be missed with current analytical procedures. The chemical properties (reactivity, selectivity, derivatization products, and their chromatographic and spectral features) for the four chloroformates were investigated using a set of highly polar standard analytes, including malic and tartaric acids, hydroxylamine, valine, 2-aminoethanol, resorcinol, 1,3,5-trihydroxybenzene, and 2,4-dihydroxybenzoic acid. Upon derivatization, the analytes were extracted from the aqueous solvent and analyzed by gas chromatography (GC)-mass spectrometry (MS) in the electron capture negative ionization (ECNI) mode. Positive chemical ionization (PCI)-MS was used for confirmation of molecular ions that were weak or absent in ECNI mass spectra. Of the four derivatizing reagents tested, OFPCF showed the best performance, with good reaction efficiency, good chromatographic and spectroscopic properties, low detection limits (10-100 fmol), and a linear response more than two orders of magnitude. Further, the entire procedure from raw aqueous sample to ready-to-inject hexane solutions of the derivatives requires less than 10 min. PFBCF showed ideal applicability for derivatizing aminoalcohols and aminoacids. The two chloroformates with the highest intrinsic stability (TDFOCF and PFPECF) failed to derivatize some of the analytes. Finally, the OFPCF derivatizing agent was tested with simulated ozonated drinking water (aqueous fulvic acid treated with ozone), and three highly polar reaction by-products were determined.