Analysis of gaseous arsenic species and stability studies of arsine and trimethylarsine by gas chromatography-mass spectrometry

A rapid method based on gas chromatography-mass spectrometry was developed for analysis of four volatile arsenic species: arsine, monomethylarsine (MMA), dimethylarsine (DMA) and trimethylarsine (TMA). With the proposed method gaseous arsenic species could be determined in less than 2 min and no pre-treatment for gas phase samples was needed, which minimized the risks of species conversion before analysis. The detection limits for different species were 24–174 pg. The standards for arsine, MMA and DMA were prepared by reaction between arsenic acid, monomethylarsonic acid or dimethylarsinic acid with tetrahydroborate(III) and nitric acid. The effect of pH on recovery of different arsine species was examined and is discussed. The TMA was obtained commercially as liquid. Also stability of inorganic (arsine) and organic (TMA) gaseous arsenic species in air was studied as a function of time.     

Study of crystallinity and thermomechanical analysis of annealed poly(ethylene terephthalate) films

The objective of this article was the determination of the degree of crystallinity of a series of heat-set poly(ethylene terephthalate) (PET) films and their study by thermomechanical analysis (TMA) in order to elucidate a peculiar behaviour that takes place around the glass transition region. For this purpose, amorphous cast Mylar films from DuPont were annealed at 115 °C for various periods of time. Four methods were used to study the crystallinity of the samples prepared: differential scanning calorimetry (DSC), density measurements (DM), wide-angle X-ray diffraction (WAXD), and Fourier transform infrared spectroscopy (FT-IR). From the results obtained, the following conclusions are drawn: amorphous PET Mylar films can be crystallized in a degree of about up to 30% after thermal treatment for 30 min (cold crystallization) above glass transition temperature. When these semicrystalline samples are subjected to TMA, they show a two step penetration of the probe into them, which decreases with the increase of the degree of crystallinity. The first step of penetration was attributed to the shrinkage of the amorphous or semicrystalline sample, which takes place on the glass transition temperature, while the second step was attributed to the continuous softening of the sample, and the reorganization of the matter which takes place on heating run due to cold crystallization.     

水热法制备MoO3-GQDs的三甲胺气敏性能

采用水热法制备了一系列具有不同碳量子点(GQDs)含量的MoO3?GQDs纳米复合材料,利用X射线衍射、扫描电子显微镜、透射电子显微镜、FTIR等对MoO3?GQDs复合材料进行了表征,研究了其气敏性能。结果表明,复合材料中GQDs的含量对MoO3?GQDs复合材料的气敏响应和选择性有显著影响。MoO3?GQDs纳米复合材料(S?6,GQDs悬浮液的含量为6 mL)传感器在230℃时对三甲胺(TMA)表现出高的气敏响应和好的气敏选择性;该传感器对1000μL·L^-1 TMA的响应为74.08;对1000μL·L^-1 TMA的响应时间和恢复时间分别为73和34 s;S?6复合材料气敏传感器在230℃时可以检测到1μL·L^-1的TMA。     

Determination of epoxy groups in epoxy resins by reaction-based headspace gas chromatography

This work reports on a new method for the determination of epoxy groups in epoxy resins by reaction-based headspace gas chromatography (HS-GC). After epoxy resins reacted with hydrochloric acid (HCl) solution, the remaining HCl reacted with bicarbonate solution in a closed headspace vial to form carbon dioxide that was measured by HS-GC. It was found that the first reaction can be finished in 30 min at room temperature and the second reaction, together with headspace equilibration, can be achieved within 15 min at 60 °C. The results showed that the method has a good precision and accuracy, in which the relative standard deviation in the repeatability measurement was 4.20%, and the relative differences between the data obtained by the HS-GC method and the reference method were within 8.04%. The present method is simple, efficient, and suitable for the used in the epoxy resin related research and applications.     

Flash pyrolysis of Silopi asphaltite in a free-fall reactor under vacuum

Flash pyrolysis experiments on asphaltite samples were performed in a free-fall reactor under vacuum to determine the effects of pyrolysis temperature, feed rate and particle size. Maximum liquid yield of 13 wt.% was obtained in free-fall reactor under vacuum when the pyrolysis temperature was 700 °C, feed rate was 0.4 g min⁻¹ and particle sizes were between 0.075 and 0.250 mm. The liquid products obtained at various pyrolysis conditions were analyzed by gas chromatography/mass spectrometer (GC/MS) and liquid products were classified as following: C5–C10, C11–C15, C16–C20 and C20+. The amount of saturated hydrocarbons decreased while the amount of unsaturated hydrocarbons increased with increase of temperature. While percent of C5–C10 unsaturated hydrocarbons continuously increased with increase of temperature, the percent of C11–C15 unsaturated hydrocarbons increased up to 750 °C and then started to diminish. Functional group analysis of solid residue was carried out using Fourier transform infrared spectrometry (FT-IR). The proximate analysis of solid residue indicated that percent of fixed carbon and ash increased with temperature.     

顶空气相色谱法测定化妆品中15种挥发性有机溶剂残留

建立了化妆品中15种挥发性有机溶剂残留的顶空气相色谱测定方法。样品经60 ℃、30 min静态顶空后,采用气相色谱-氢火焰离子化检测器进行检测,外标法定量。加标回收试验结果表明: 15种挥发性有机溶剂残留平均回收率为62.8%～116%,相对标准偏差均小于5%。方法的检出限为0.09～0.68 mg/kg。该方法可有效克服基体干扰,一次进样可同时分离和测定化妆品中15种挥发性有机溶剂,准确灵敏,简单快速,适用于化妆品中挥发性有机溶剂残留的检测。     

An accurate and reliable analysis of trimethylamine using thermal desorption and gas chromatography–time of flight mass spectrometry

Trimethylamine (TMA) is well-known for manifesting the odor of rotting fish and urine. The analysis of TMA in environmental samples generally suffers from low reproducibility and poor sensitivity. In this study, a technique for the quantitative analysis of gas phase TMA was developed using thermal desorption (TD)-gas chromatography (GC)-time of flight mass spectrometry (TOF-MS). This new approach yielded good linearity (R² = 0.9930), precision (RSE = 1.59%), and high sensitivity with the method detection limit (MDL) of 51 pg, i.e., detection of 0.021 ppb of TMA at 1 L sample (limit of detection (LOD): 5.32 pg (0.002 ppb). This method was tested against gas samples collected from two representative sources of TMA: (1) rotten thornback fish and (2) cat urine-soaked clay. The concentration of TMA in these samples, when analyzed after treatment at varying dilution ratios, averaged 293 ± 29.7 ppm (RSE = 3.82%) and 74.1 ± 5.78 ppb (RSE = 3.19%), respectively. The feasibility of this approach, when tested with TD–GC–Quadruple (Q) MS, showed a good compatibility with moderately reduced sensitivity. The results of this study demonstrated that one can achieve highly reliable and reproducible analysis of TMA from environmental samples when using thermal desorption (for pretreatment) and detection (by the TOF or Q-MS system).     

顶空气相色谱法测定盐酸司他斯汀中6种残留溶剂

建立了顶空气相色谱法(HS-GC)测定盐酸司他斯汀中乙醚、丙酮、异丙醇、四氢呋喃、甲苯与二甲苯6种有机溶剂残留量的方法.样品用二甲基亚砜溶解,在110 ℃加热20 min,使气液平衡,采用氢火焰离子化检测器(FID),以DB-1701(60 m x 0.320 mm,1.00 μm)为分析柱,程序升温测定.在优化的气相...     

Flow injection potentiometric detection of trimethylamine in seafood using tungsten oxide electrode

A simple flow injection gas/diffusion method for the determination of trimethylamine (TMA) in seafood with potentiometric detection using tungsten oxide electrode has been developed. The method is based on the diffusion of TMA through a PTFE membrane from a sodium hydroxide donor stream to a phosphate buffer acceptor stream. The TMA in the acceptor stream passes through an electrochemical flow cell containing a tungsten oxide wire and a silver/silver chloride electrode, where TMA was sensitively detected. The parameters affecting the sensitivity of the electrode such as sodium hydroxide concentration, buffer concentration, pH, flow rate and injected volume were studied in details. The electrode response was linear in the concentration range from 1 to 10 μg ml⁻¹ TMA with a correlation coefficient (R²) of 0.991 and a detection limit of 0.05 μg ml⁻¹ TMA. The intra- and inter-days precision (R.S.D.) was found to be, respectively, 1.20 and 1.6% (n=6). The method was applied to the determination of TMA in fish tissue and recoveries of 99-100% were obtained for fish extracts. Results were in close agreement with those obtained by the existing classical official method. Common interference from those species that can diffuse through the membrane were removed by the addition of formaldehyde to the seafood extract. The method is simple, feasible with satisfactory accuracy and precision and thus, could be used for monitoring seafood quality with a sampling rate of 20±2 sample h⁻¹.     

静态顶空-气相色谱/质谱法同时检测环境水体中59种挥发性有机物

静态顶空法是一种简单、环保的样品前处理方法.通过对比试验,优化了影响静态顶空进样方法灵敏度的主要因素,确定了较佳的样品盐度(40%)、平衡温度(80℃)、平衡时间(10 min)、平衡压力(0.103 4 MPa)、定量环平衡时间(20 s)、进样时间(3 min)等前处理方法参数.采用优化后水样前处理条件及1.00 k V的检测器电压,59种挥发性有机物在特定的线性范围内,标准曲线线性相关系数均大于0.998,方法检出限为丙烯腈4.4μg/L、硝基苯7.6μg/L,其余挥发性有机物(VOCs)介于0.06~1.4μg/L,饮用水源水及污水处理厂进水实际样品加标回收率为60%~110%,精密度(RSD)为0.33%~22%(n=6).建立的静态顶空-气相色谱/质谱法(HS-GC/MS)水样前处理过程自动化,可同时对水中59种挥发性有机物进行检测.     

Rapid determination of furfural in biomass hydrolysate by full evaporation headspace gas chromatography

This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for rapid determination of furfural in the biomass hydrolysate. The data show that a near-complete mass transfer of furfural in the sample from biomass hydrolysate to the vapor phase (headspace) was achieved within 3 min at 105°C when a very small (<40 μL) sample was added to a 20 mL headspace sample vial. The acid-catalyzed furfural decomposition under these conditions was negligible. The furfural in the vapor phase was then determined by HS-GC using a flame ionization detector. The results showed that the method has an excellent measurement precision (RSD<0.5%) and accuracy (recovery=100.2±1.7%) for furfural quantification in carbohydrate hydrolysate samples. The method requires no sample pretreatment, so it is simple, rapid and accurate, and suitable for applications in lignocellulosic biomass conversion to fuel ethanol or other high value-added products.     

Gas transport property of polyallylamine–poly(vinyl alcohol)/polysulfone composite membranes

Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO₂, N₂, CH₄ gases and CO₂/N₂ gas mixture (20 vol% CO₂ and 80 vol% N₂) and CO₂/CH₄ gas mixture (10 vol% CO₂ and 90 vol% CH₄). The plots of gas permeance or flux versus feed gas pressure imply that CO₂ permeation through the membranes follows facilitated transport mechanism whereas N₂ and CH₄ permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO₂/N₂ gas mixture, the membranes with 10 wt% PAAm content show the highest CO₂ permeance of about 1.80 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/N₂ selectivity of 80 at 0.1 MPa feed gas pressure. For CO₂/CH₄ gas mixture, the membranes with 20 wt% PAAm content display the highest CO₂ permeance of about 1.95 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/CH₄ selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO₂ permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO₂ permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.     

Antimony biomethylation by mixed cultures of micro-organisms under anaerobic conditions

The volatile antimony compound trimethylantimony (TMA) was detected in headspace gases over anaerobic soil enrichment cultures spiked with potassium antimony tartrate. The presence of TMA was variable (12 positives from 104 cultures) and dependent upon both the inoculum source (environmental sample) and enrichment culture conditions. Positives for TMA formation were obtained with variable frequency for four of the six soils tested and for three types of enrichment culture, designed to encourage growth of nitrate-reducing, methane-producing or fermentative bacteria. The identity of the volatile antimony compound produced in each of the three types of enrichment culture was confirmed by gas chromatography–mass spectrometry and gas chromatography–atomic absorption spectroscopy. There was no evidence of any other volatile antimony compound in the headspace gases. These data suggest that the capability to generate TMA is widely distributed in the terrestrial environment and is attributable to different metabolic types of micro-organisms. © 1998 John Wiley & Sons, Ltd.     

Hg(II)-imprinted thiol-functionalized mesoporous sorbent micro-column preconcentration of trace mercury and determination by inductively coupled plasma optical emission spectrometry

Hg(II)-imprinting thiol-functionalized mesoporous sorbent was prepared by a sol–gel method and characterized by X-ray diffraction (XRD), FT-IR spectroscopy and nitrogen gas adsorption–desorption. The static adsorption capacity of the Hg(II)-imprinted and non-imprinted sorbent was 78.5 and 26.6 mg g⁻¹, respectively. The breakthrough capacity was 4.46 mg g⁻¹, and the relative selectivity coefficient for Hg(II) in the presence of Cd and Pb was 3.3 and 3.9, respectively. A new method using a micro-column packed with Hg(II)-imprinting thiol-functionalized mesoporous sorbent has been developed for preconcentration of trace mercury prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analyte have been investigated. The limit of detection was 0.39 ng ml⁻¹ with a concentration factor of 150 times. The developed method has been applied to the determination of trace mercury in some biological and environmental samples with satisfactory results. The accuracy was assessed through recovery experiments and analysis of certified reference material.     

Dynamic Vapour Generation and Head Space Determination of m-XYLENE for Pharmacokinetic Studies

Abstract

A custom designed vapour generation-exposure chamber assembly and head space analysis method were evaluated for use in pharmacokinetic investigations. The predicted m-xylene concentration was within 1% of the average value measured by gas chromatography-flame ionization detection (GC-FID) in the glass exposure chamber during controlled vapourization of m-xylene. The concentration variability was ± 13% and 4% respectively, with and without rats in the chamber. Blood and tissue samples from male, Sprague Dawley rats exposed to 1100 ppm of xylene, were analyzed by means of a static head space (HS)-GC analysis method. The average m-xylene level in the blood of exposed animals was ca. 5000 ng/mL. m-Xylene was detected in brain, kidney, skin, fat and liver. The analytical precision for duplicate samples was < ± 5% for all tissues, except liver and skin. The feasibility of detection of m-xylene in unhomogenized tissue by HS-GC analysis was demonstrated.     

Determination of polybrominated diphenyl ethers in soil by ultrasonic assisted extraction and gas chromatography mass spectrometry

An analytical method for the determination of polybrominated diphenyl ethers (PBDEs) in soil was developed. Soil samples were placed in small glass columns and PBDEs extracted from soil, with a low volume of ethyl acetate (5 mL, 2× 15 min), assisted by sonication. PBDEs were determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC–MS–SIM) and residues were confirmed by their retention times, selected ions and qualifier–target abundance ratios. Recovery studies were performed at 10, 1, 0.1 and 0.05 μg/kg fortification levels, and the recoveries obtained ranged from 81 to 104% with a relative standard deviation between 1 and 9%. The detection limit of the method varied from 2 to 30 pg/g and the quantification limit ranged from 7 to 100 pg/g for the different PBDEs studied. The developed method was linear over the range assayed, 0.01–10 μg/kg with determination coefficients equal or higher than 0.997. The proposed method was used to determine PBDEs levels in soil samples from different areas of Spain and PBDEs were detected in some samples with values ranging from 1.3 to 5.6 μg/kg.     

Preparation and characterization of pyrolytic chars from different biomass samples

In the present work four different biomass samples (pine cone, soybean cake, corn stalk and peanut shell) were pyrolyzed to 550 °C in an inert gas atmosphere and a comparison between the properties of chars produced has been performed. Characterization of biomass samples was carried out with FT-IR, ¹³C NMR, SEM and EDX. The influence of the parent material on char quality was investigated. The chars were characterized by their proximate and ultimate analysis and surface areas by N₂ adsorption at 77 K using BET equation. The morphological changes in carbonaceous solids were observed by scanning electron microscopy (SEM), and FT-IR spectra were obtained to evaluate the functional groups. The results obtained from the different techniques were combined to give an overview of the chemical and physical properties of the biomass char samples.     

Production of liquid fuels and chemicals from pyrolysis of Bangladeshi bicycle/rickshaw tire wastes

Tire wastes in the form of used bicycle/rickshaw tires available in Bangladesh were pyrolyzed in a fixed-bed fire-tube heating reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and feed size on the product yields and liquid product composition. Final temperature range studied was between 375 and 575 °C and the highest liquid product yield was obtained at 475 °C. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR, ¹H NMR and GC–MS techniques. The results show that it is possible to obtain liquid products that are comparable to petroleum fuels and valuable chemical feedstock from bicycle/rickshaw tire wastes if the pyrolysis conditions are chosen accordingly.     

Pure and doped lanthanum cobaltites obtained by combustion method

We report the synthesis of La_1−xSr_xCoO₃ nanopowders by solution combustion method using metal nitrates and -alanine (alanine method) or urea (urea method) as fuel. The influence of metal nitrates/organic substance molar ratio and the type of fuel was investigated. The isolated complex precursors were characterized by atomic absorption spectroscopy (AAS), FT-IR spectra and DTA–TG analysis. The La_1−xSr_xCoO₃ (x = 0–0.3) powders were characterized by X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray analysis (SEM–EDX), as well as by specific surface area measurements. XRD patterns indicate the formation of single-phase LaCoO₃ (rhombohedral) when as-synthesized powders were calcined at 873 K, 3 h in the case of the alanine method and at 1073 K, 3 h for urea-based system. Also, strontium doped lanthanum cobaltites obtained by both methods at 1273 K are single phase with rhombohedral perovskite-like structure as XRD data have proved. SEM investigation of pure and doped lanthanum cobaltites reveal that the samples prepared by both methods have fine particles with tendency of agglomerates formation with different shapes, spongy aspect and high porosity. La_1−xSr_xCoO₃ nanopowders obtained by alanine method have larger specific surface area values than those prepared by urea method.     

Determination of total sugar content in lignocellulosic hydrolysates by using a reaction headspace gas chromatographic technique

This paper investigates a new analytical technique for the quantitative detection of total sugar content in lignocellulosic hydrolysates by reaction headspace gas chromatography (HS-GC). By detecting the carbon dioxide (CO₂) generated from the reaction between sugars in lignocellulosic hydrolysates and potassium dichromate, the total sugar content in lignocellulosic hydrolysates can be quantified. The data illustrate that the conversion of sugars in lignocellulose hydrolysates can be achieved under the given conditions (at 90 °C for 30 min), the relative standard deviation of this HS-GC technique in the total sugar content determination was within 3.35%, and the measured total sugar content in 15 lignocellulose hydrolysate samples closely matched those measured by the reference spectrophotometric technique (relative differences <7.69%). The present technique is efficient, reliable and suitable to be used in the total sugar content quantification in lignocellulose hydrolysate related research and process control.