Effects of injection volume change on gas chromatographic sensitivity determined with two contrasting calibration approaches for volatile organic compounds

In this study, the effects of injection volume change on gas chromatographic detection properties have been evaluated using gas-phase standards containing three aromatic volatile organic compounds (VOC): benzene, toluene, and xylene (commonly called BTX). To examine such effects on GC sensitivity, a series of calibration data sets were obtained using standards of three concentration values (3, 6, and 10 ppm) at each of five selected injection volumes (20 to 1000 microL). The results were initially examined in terms of the fixed standard volume (FSV) approach to allow the direct comparison of calibration patterns between different injection volumes. Identical data sets were then re-organized so that the calibration data could also be compared across variable injection volumes for a given standard concentration (at all three concentrations), i.e. by the fixed standard concentration (FSC) approach. The results of our comparative analysis between the FSV and the FSC approaches indicate that the calibration patterns of VOC are highly sensitive to changes in injection volume or injection-related conditions. It is thus suggested that the former approach is more reasonable for reducing uncertainties associated with the GC-based quantification of atmospheric pollutants.     

Headspace-mass spectrometry determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics

A simple and fast method has been developed for the determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers (BTEX) in soils. Samples were introduced in 10 mL standard glass vials of a headspace (HS) autosampler together with 150 μL of 2,6,10,14-tetramethylpentadecane, heated at 90 °C for 10 min and introduced in the mass spectrometer by using a transfer line heated at 250 °C as interface. The volatile fraction of samples was directly introduced into the source of the mass spectrometer which was scanned from m/z 75 to 110. A partial least squares (PLS) multivariate calibration approach based on a classical 3³ calibration model was build with mixtures of benzene, toluene and o-xylene in 2,6,10,14-tetramethylpentadecane for BTEX determination. Results obtained for BTEX analysis by HS-MS in different types of soil samples were comparables to those obtained by the reference HS-GC-MS procedure. So, the developed procedure allowed a fast identification and prediction of BTEX present in the samples without a prior chromatographic separation.     

Determination of benzene, toluene, ethylbenzene and xylenes in soils by multiple headspace solid-phase microextraction

Multiple headspace-solid phase microextraction (MHS-SPME) is a recently developed technique for the quantification of analytes in solid samples that avoids the matrix effect. This method implies several consecutive extractions from the same sample. In this way, the total area corresponding to complete extraction can be directly calculated as the sum of the areas of each individual extraction when the extraction is exhaustive, or through a mathematical equation when it is not exhaustive. In this paper, the quantitative determination of benzene, toluene, ethylbenzene and xylene isomers (BTEX) in a certified soil (RTC-CRM304, LGC Promochem) and in a contaminated soil by multiple HS-SPME coupled to a gas chromatography-flame ionisation detector (GC-FID) is presented. BTEX extraction was carried out using soil suspensions in water at 30 degrees C with a 75 microm carboxen-polydimethylsiloxane (CAR-PDMS) fibre and calibration was carried out using aqueous BTEX solutions at 30 degrees C for 30 min with the same fibre. BTEX concentration was calculated by interpolating the total peak area found for the soils in the calibration graphs obtained from aqueous solutions. The toluene, ethylbenzene, o-xylene and m,p-xylene concentrations obtained were statistically equal to the certified values.     

Moment theory for the analytical determination of rate constants for solute permeation at the interface of spherical molecular aggregates

Moment equations were developed on the basis of the Einstein equation for diffusion and the random walk model to analytically determine the rate constant for the interfacial solute permeation from a bulk solvent into molecular aggregates (k_in) and the inverse rate constant from the molecular aggregates to the bulk solvent (k_out). The moment equations were in good agreement with those derived in a different manner. To demonstrate their effectiveness in one concrete example, the moment equations were used to analytically determine the values of k_in and k_out of three electrically neutral solutes, i.e. resorcinol, phenol, and nitrobenzene, from the first absolute (μ_1A) and second central (μ_2C) moments of their elution peaks, as measured by electrokinetic chromatography (EKC), in which the sodium dodecyl sulfate (SDS) micelles were used as a pseudostationary phase. The values of k_in and k_out should be determined with no chemical modifications and no physical action with the molecular aggregates because they are dynamic systems formed through weak interactions between the components. The moment analysis of the elution peak profiles measured by EKC is effective to unambiguously determine k_in, k_out, and the partition equilibrium constant (k_in/k_out) under appropriate experimental conditions.     

A clever strategy for permeability studies of methyl bromide and some organic compounds through high-barrier plastic films

An analytical strategy has been proposed and optimized to study the permeability of several flexible plastic materials, some of them with high-barrier properties, versus naphthalene, methyl bromide, toluene, ethylbenzene, and ortho- and para-xylenes. The strategy involves using a system of concentric plastic bags made from the materials to be tested polyethylene (PE) and used as permeable plastics to facilitate the homogeneous distribution of a solid compound, such as naphthalene, in vapour phase. After the permeation test, the vapour phase containing the pollutants that cross the plastic barrier is trapped in a 12% ethanol–water solution and further analysed by SPME in headspace mode. Several experimental conditions as well as different samples were tested. The results obtained are shown and discussed.     

Field analysis of benzene, toluene, ethylbenzene and xylene in water by portable gas chromatography-microflame ionization detector combined with headspace solid-phase microextraction

In this work, portable gas chromatography-microflame ionization detection (portable GC-μFID) coupled to headspace solid-phase microextraction (HS-SPME) was developed for the field analysis of benzene, toluene, ethylbenzene and xylene (BTEX) in water samples. The HS-SPME parameters such as fiber coating, extraction times, stirring rate, the ratio of headspace volume to sample volume, and sodium chloride concentration were studied. A 65 μm poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) SPME fiber, 900 rpm, 3.0 ml of headspace (1.0 ml water sample in 4.0 ml vial), and 35% sodium chloride concentration (w/v) were respectively chosen for the best extraction response. An extraction time of 1.0 min was enough to extract BTEX in water samples. The relative standard deviation (R.S.D.) for the procedure varied from 5.4% to 8.3%. The method detection limits (MDLs) found were lower than 1.5 μg/l, which was enough sensitive to detect the BTEX in water samples. The optimized method was applied to the field analysis of BTEX in wastewater samples. These experiment results show that portable GC-μFID combined with HS-SPME is a rapid, simple and effective tool for field analysis of BTEX in water samples.     

Vapor-phase testing of the memory-effects in benzene- and toluene-imprinted polymers conditioned at elevated temperature

The preparation of polymers imprinted with common aromatic solvents such as benzene and toluene is an under-exploited subject of research. The present study was aimed at the understanding of whether true solvent memory effects can be achieved by molecular imprinting, as well as if they are stable at elevated temperature. A set of copolymers, comprising low and high cross-linking levels, was prepared from four different combinations of functional monomer and cross-linker, namely methacrylic acid (MAA)/ethylene glycol dimethacrylate (EGDMA), methyl methacrylate (MMA)/EGDMA, MAA/divinyl benzene (DVB) and MMA/DVB. Each possible combination was prepared separately in benzene, toluene and acetonitrile. The obtained materials were applied as coatings onto nickel–titanium (Ni–Ti) alloy wires which were incorporated into solid-phase microextraction devices and finally tested for their ability to competitively adsorb vapors from the headspace of an aqueous solution containing a few volatile organic compounds.     

分散体系形成中表面活性剂使用量的判据

通过对甲苯等有机溶剂/水/表面活性剂体系的水基化分散,利用MalvernMicroplus型激光粒度仪对乳化后的分散相粒子大小及其分布进行研究.结果表明,表面活性剂的使用量对分散结果的影响具有局限性,对于具体体系,表面活性剂的临界胶束浓度[CMC(CMC_O+CMC_W)是这种局限性的量化标志,超出CMC的表面活性剂是多余的,对最终的分散结果无作用,同时也会影响分散体系的稳定性.     

Acetic acid permeation through photovoltaic backsheets: Influence of the composition on the permeation rate

Acetic acid, which is formed during degradation of the most frequently used photovoltaic (PV) encapsulant ethylene vinyl acetate (EVA), is linked to several PV module failure mechanisms like corrosion of interconnectors, cells or potential induced degradation (PID). An evaluation of a new measurement technique and data analysis for acetic acid permeation through photovoltaic backsheet films is described. The influence of the layer composition of the multilayer backsheets on the acetic acid permeation rates (AATR) was determined by investigating the permeation properties of the individual layers as well as the whole polymeric multilayer composites. Various polymeric backsheet types based on PET-core layers showing a very high barrier for acetic acid permeation were compared to fully polyamide material stacks which allow for a much higher transmission of acetic acid through the backsheet out of the module. Incorporated Al-layers were found to not affect the AATRs of PET based backsheets.     

Direct synthesis of nitrogen-doped graphene on platinum wire as a new fiber coating method for the solid-phase microextraction of BXes in water samples: Comparison of headspace and cold-fiber headspace modes

In this work, a new solid-phase microextraction fiber was prepared based on nitrogen-doped graphene (N-doped G). Moreover, a new strategy was proposed to solve problems dealt in direct coating of N-doped G. For this purpose, first, Graphene oxide (GO) was coated on Pt wire by electrophoretic deposition method. Then, chemical reduction of coated GO to N-doped G was accomplished by hydrazine and NH₃. The prepared fiber showed good mechanical and thermal stabilities. The obtained fiber was used in two different modes (conventional headspace solid-phase microextraction and cold-fiber headspace solid-phase microextraction (CF-HS-SPME)). Both modes were optimized and applied for the extraction of benzene and xylenes from different aqueous samples. All effective parameters including extraction time, salt content, stirring rate, and desorption time were optimized. The optimized CF-HS-SPME combined with GC-FID showed good limit of detections (LODs) (0.3–2.3 μg/L), limit of quantifications (LOQs) (1.0–7.0 μg/L) and linear ranges (1.0–5000 μg/L). The developed method was applied for the analysis of benzene and xylenes in rainwater and some wastewater samples.     

Isothermal vapor-liquid equilibrium at T = 333.15 K and excess volumes and molar refractivity deviation at T = 298.15 K for the ternary mixtures {di-methyl carbonate (DMC) + ethanol + benzene} and {DMC + ethanol + toluene}

Isothermal vapor-liquid equilibrium data at 333.15 K are reported for the ternary systems {di-methyl carbonate (DMC) + ethanol + benzene} and {DMC + ethanol + toluene} as determined with headspace gas chromatography. The experimental ternary vapor-liquid equilibrium (VLE) data were correlated with different activity coefficient models. The excess volume (V^E) and deviations in molar refractivity (ΔR) data are reported for the binary systems {DMC + benzene} and {DMC + toluene} and also for the ternary systems {DMC + ethanol + benzene} and {DMC + ethanol + toluene} at 298.15 K. These V^E and ΔR data were correlated with the Redlich-Kister equation for binary systems and the Cibulka equation for ternary systems.     

Kinetic study on solute permeation at the interface of molecular aggregates by partial filling capillary electrophoresis

Moment analysis method using partial filling CE was developed for the kinetic study on solute permeation at the interface of spherical molecular aggregates. Moment equations for partial filling CE were developed by classifying CE systems into five categories according to the migration velocities of solute and molecular aggregate. The method was applied to the study on the dissolution of electrically neutral solutes into SDS micelles. Elution peaks were measured by partial filling CE while changing the concentration of SDS and the filling ratio of SDS micellar zone to the capillary (ϕ_M). Partition equilibrium constants (K_p) and rate constants of interfacial solute permeation of SDS micelles (k_in and k_out) were determined from the first absolute and second central moments of the elution peaks by using the moment equations. Their values were comparable irrespective of ϕ_M and were almost the same as those previously measured by complete filling CE. The positive correlation of K_p with the hydrophobicity of the solutes was explained in terms of the change in k_in and k_out. It was demonstrated that the moment analysis method using partial filling CE is effective for studying solute permeation kinetics at the interface of spherical molecular aggregates.     

Flow rate influence on direct contact membrane distillation experiments: Different empirical correlations for Nusselt number

Direct contact membrane distillation (DCMD) experiments using distilled water are reported. Influence on the process of feed and permeate flow rates through the cell has been investigated in a wide flow range, from 2 to 8 l/min. Two main effects have been studied, its effect on the heat transfer coefficient and on the effective membrane thickness. An empiric dependence of the membrane thickness with linear velocity through the cell has been included in the equation for mass flux through the membrane obtained from the “Dusty-Gas” model with satisfactory results.     

Polydimethylsiloxane-based permeation passive air sampler. Part I: Calibration constants and their relation to retention indices of the analytes

A simple and cost effective permeation passive sampler equipped with a polydimethylsiloxane (PDMS) membrane was designed for the determination of time-weighted average (TWA) concentrations of volatile organic compounds (VOCs) in air. Permeation passive samplers have significant advantages over diffusive passive samplers, including insensitivity to moisture and high face velocities of air across the surface of the sampler. Calibration constants of the sampler towards 41 analytes belonging to alkane, aromatic hydrocarbon, chlorinated hydrocarbon, ester and alcohol groups were determined. The calibration constants allowed for the determination of the permeability of PDMS towards the selected analytes. They ranged from 0.026 cm² min⁻¹ for 1,1-dichloroethylene to 0.605 cm² min⁻¹ for n-octanol. Further, the mechanism of analyte transport across PDMS membranes allowed for the calibration constants of the sampler to be estimated from the linear temperature programmed retention indices (LTPRI) of the analytes, determined using GC columns coated with pure PDMS stationary phases. Statistical analysis using Student's t test indicated that there was no significant difference at the 95% probability level between the experimentally obtained calibration constants and those estimated using LTPRI for most analyte groups studied. This correlation allows the estimation of the calibration constants of compounds not known to be present at the time of sampler deployment, which makes it possible to determine parameters like total petroleum hydrocarbons in the vapor phase.     

Correlations between the Rayleigh ratio and the wavelength for toluene and benzene

The values of the Rayleigh ratio of two pure liquid, toluene and benzene, at various wavelengths have been collected from the literature, and a correlation between the Rayleigh ratio and the wavelength in the form of power law has been developed for each liquid and can be used to compute accurately the Rayleigh ratio at any wavelength between 420 and 700 nm. The Rayleigh ratio scales with the wavelength with a power of −4.17 and −4.38, respectively, for toluene and benzene, which deviate significantly from the Rayleigh law (−4.0). However, if the effect of the wavelength on their refractive indexes is accounted for, the power is reduced to −4.0 and −4.2 for toluene and benzene, respectively.     

Design of a microfluidic device for comprehensive spatial two‐dimensional liquid chromatography

This study discusses the design aspects for the construction of a microfluidic device for comprehensive spatial two‐dimensional liquid chromatography. In spatial two‐dimensional liquid chromatography each peak is characterized by its coordinates in the plane. After completing the first‐dimension separation all fractions are analyzed in parallel second‐dimension separations. Hence, spatial two‐dimensional liquid chromatography potentially provides much higher peak‐production rates than a coupled column multi‐dimensional liquid chromatography approach in which the second‐dimension analyses are performed sequentially. A chip for spatial two‐dimensional liquid chromatography has been manufactured from cyclic olefin copolymer and features a first‐dimension separation channel and 21 parallel second‐dimension separation channels oriented perpendicularly to the former. Compartmentalization of first‐ and second‐dimension developments by physical barriers allowed for a preferential flow path with a minimal dispersion into the second‐dimension separation channels. To generate a homogenous flow across all the parallel second‐dimension channels, a radially interconnected flow distributor containing two zones of diamond‐shaped pillars was integrated on‐chip. A methacrylate ester based monolithic stationary phase with optimized macroporous structure was created in situ in the confines of the microfluidic chip. In addition, the use of a photomask was explored to localize monolith formation in the parallel second‐dimension channels. Finally, to connect the spatial chip to the liquid chromatography instrument, connector ports were integrated allowing the use of Viper fittings. As an alternative, a chip holder with adjustable clasp locks was designed that allows the clamping force to be adjusted.     

Diffusion-based calibration for solid-phase microextraction of benzene, toluene, ethylbenzene, p-xylene and chlorobenzenes from aqueous samples

Short-term solid-phase microextraction (SPME) was performed to test a recently proposed semi-empirical model for the prediction of concentrations of analyte in water samples from the fibre-extracted mass without further calibration. The mass uptake rates obtained for benzene, toluene, ethylbenzene and p-xylene (BTEX) differ considerably from the before published, showing that interfibre comparability is a serious issue. The relative prediction errors are between -55% for benzene and +82% for p-dichlorobenzene under optimal conditions, i.e. they are by an order of magnitude higher than originally published. A sensitivity analysis shows the dominant influence of the estimated thickness of the diffusional boundary layer around the fibre on the concentration predicted. Empirical modification of the model equation for this parameter yields satisfactory results under the conditions tested for both BTEX and the selected chlorobenzenes.     

水溶性凝胶渗透色谱测定芸芝多糖各组分的分子量及相对含量

用水溶性凝胶渗透色谱法研究了芸芝多糖在水溶性凝胶柱上的吸附影响因素，建立了最佳分离、测试条件，成功地将芸芝多糖的混合物分离为三个组分，并测试各组分的分子量分别为1190000；796000；552000。各组分相对百分含量分别为83．6％，8．9％，7．5％。     

Comparison of particle size and flow rate optimization for chromatography using one-monomer molecularly imprinted polymers versus traditional non-covalent molecularly imprinted polymers

The dependence of enantio-selective chromatographic performance on particle size, as measured by separation factor, was investigated for one-monomer molecularly imprinted polymers (OMNiMIPs) compared to traditionally formed EGDMA/MAA molecularly imprinted polymers (MIPs). Five particle size ranges were compared (<20 μm, 20-25 μm, 25-38 μm, 38-45 μm, and 45-63 μm), revealing that the particle sizes above 25 μm provided the highest separation factor, and thus the best enantiomer separation, for both imprinted polymers. Other chromatographic parameters such as the number of theoretical plates and resolution exhibited only minor changes for the OMNiMIPs as the particle size changed, except for particles 20 μm and below. However, the number of theoretical plates and resolution for EGDMA/MAA are higher for particles in the 20-25 μm range. Thus, chromatographic factors for the EGDMA/MAA polymers are better in this range, despite better enantioselectivity for particle sizes above 25 μm. In contrast, OMNiMIPs generally show the most favorable performance for particle sizes in the 38-45 μm range. It was also found that decreasing flow rate resulted in improved enantioselectivity for both MIPs for all particle sizes.     

Correlations of the rate constants of phosphorylation reactions with the empirical parameters of the solvent polarity

Regression analysis of the solvent effects on the rate constants of nucleophilic substitution at the phosphoryl group was performed with the use of the empirical parameters of solvent polarity which characterize the ability of the solvents to electrophilic and nucleophilic solvation. The nucleophilic solvation of reagents by solvents, as a rule, favors the phosphorylation reactions. In the phosphorylation reactions of anionic nucleophiles, the electrophilic solvation of anions influences negatively the reactions rates. The phosphorylation of amines by chlorides of phosphorus acids is facilitated by the electrophilic solvation of a separated anion. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 271–274, February, 1998.