Characterization of a mini membrane inlet mass spectrometer for on-site detection of contaminants in both aqueous and liquid organic samples

A mini membrane inlet mass spectrometer (mini-MIMS) of a total weight of 12 kg was constructed using a miniature Multipole mass spectrometer, a small vacuum system and a flexible flat sheet membrane inlet, where the exposed membrane area can be changed by a factor of 80. The variable membrane area together with the possibility of operating the Multipole at pressures up to 1 x 10(-3) Torr made it possible to test the system with three microporous membranes (cellulose, polyether sulfone and polypropylene) normally not compatible with standard electron ionization MIMS systems and a standard non-porous polydimethylsiloxane membrane. We found that the hydrophilic cellulose and polyether sulfone membranes had selectivity characteristics opposite to those of the standard silicone membrane. They demonstrated preferential detection of hydrophilic compounds in hydrophobic organic solvents, whereas the silicone membrane preferentially detects hydrophobic organic compounds in aqueous solution. Using the cellulose membrane, organic contaminants and water could be detected in organic solvents at 10-100 ppm levels by weight, the relative high detection limits primarily caused by interference from a high chemical background from the solvent. When being used with the standard silicone membrane the mini-MIMS behaved just like most standard MIMS systems with detection limits of volatile organic compounds in water at concentrations just below 1 ppm. The hydrophobic microporous polypropylene membrane was not found to be useful with the mini-MIMS.     

Utilization of a multimembrane inlet and a cyclic sudden sampling introduction mode in membrane inlet mass spectrometry

Sudden sampling introduction into a membrane inlet mass spectrometer (MIMS) considerably improves the selectivity of the membrane inlet and is therefore applicable even for compounds with low permeabilities through a silicone membrane. In this study the basics of cyclic non-steady-state sudden increase sample injection were studied using a three-membrane inlet and a portable sector double-focusing mass spectrometer. The operational parameters of the inlet system providing the most efficient enrichment of volatile organic compounds (VOCs) in air were defined. Simulation of the diffusion process following sudden sample introduction into the three-membrane inlet was also carried out. Experimental testing of the three-membrane inlet system with the cyclic sudden sample injection mode for benzene, toluene, styrene, and xylene in air was performed. The simulation and the experimental results demonstrated that, when this mode is used, the VOCs/nitrogen relative enrichment factor of samples introduced into the mass spectrometer equipped with a three-membrane inlet is increased by a factor of approximately 10(5) compared with a direct introduction method. This effect may be used to decrease detection limits of compounds obtained with mass spectrometry to decrease matrix flow through the inlet at the same detection limits.     

On-line monitoring of biotechnological processes by gas chromatographic-mass spectrometric analysis of fermentation suspensions

An on-line monitoring system has been developed for the control of a biorreactor for the anaerobic pretreatment of an industrial waste water. The monitoring system is based on a process mass spectrometer with a temperature controlled membrane inlet. The membrane introduction mass spectrometer (MIMS) is coupled with a resistively heated metal gas chromatography capillary column, which serves as a transfer line between the bioreactor and the MIMS. Sampling and injection is performed by means of a pneumatically driven membrane probe, which enables monitoring of soluted and gaseous substances in the fermentation broth. The system can also be coupled to other processes.     

Membrane inlet mass spectrometry of volatile organohalogen compounds in drinking water.

The analysis of organic pollutants in drinking water is a topic of wide interest, reflecting on public health and life quality. Many different methodologies have been developed and are currently employed in this context, but they often require a time-consuming sample pre-treatment. This step affects the recovery of the highly volatile compounds. Trace analysis of volatile organic pollutants in water can be performed 'on-line' by membrane inlet mass spectrometry (MIMS). In MIMS, the sample is separated from the vacuum of the mass spectrometer by a thin polymeric hollow-fibre membrane. Gases and organic volatile compounds diffuse and concentrate from the sample into the hollow-fibre membrane, and from there into the mass spectrometer. The main advantages of the technique are that no pre-treatment of samples before analysis is needed and that it has fast response times and on-line monitoring capabilities. This paper reports the set-up of the analytical conditions for the analysis of volatile organohalogen compounds (chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride). Linearity of response, repeatability, detection limits, and spectra quality are evaluated.     

Direct detection of large fat-soluble biomolecules in solution using membrane inlet mass spectrometry and desorption chemical ionization

This paper presents the first membrane inlet mass spectrometry system capable of detecting large biomolecules, such as testosterone (M(r) 288), testosterone acetate (M(r) 330) and alpha-tocopherol (M(r) 430, vitamin E). The result was obtained using a home-made chemical ionization ion source with a thermostated tubular silicone membrane mounted right in the centre of a methane CI plasma. The liquid sample was flushed through the inside of the membrane for a period of 20-25 min, where the analyte diffused into the membrane. Following this trapping period the analyte was released from the membrane into the mass spectrometer by the combined action of heat radiation from the filament and charge transfer from the chemical ionization plasma. As a result of this stimulated desorption a good desorption peak was obtained as the analyte vaporized out of the membrane. Retinol (M(r) 286, vitamin A), cholecalciferol (M(r) 384, vitamin D3) and cholesterol (M(r) 386) were also detected. However, these compounds (all containing a long hydrocarbon chain and being aliphatic alcohols) did not give a protonated molecule. They gave a series of cluster ions with the dominant located 20 mass units below the molecular ion. The detection limits of the new desorption chemical ionization MIMS technique were at low or sub-micromolar concentrations (high ppb levels) and the reproducibility was within 20%, when the area of the desorption peak was used for quantitation.     

Fast and direct screening of polyaromatic hydrocarbon (PAH)-contaminated sand using a miniaturized membrane inlet mass spectrometer (mini-MIMS)

A miniaturized membrane inlet mass spectrometer (mini-MIMS; total weight 10 kg everything included) was equipped with a small sample cell using a flat sheet silicone membrane mounted close to the ionizing region of a multipole mass spectrometer. Spiked sand samples were placed in small stainless steel vials and dropped into the heated sample cell (>150 degrees C). A hole in the vial in front of the membrane and above the sand made it possible for the polyaromatic hydrocarbon (PAH) residuals to penetrate the membrane and enter the mass spectrometer as they evaporated from the sample. Using this simple setup we were able to quantitatively (approximately 10% relative standard deviation (RSD)) detect PAHs with up to five aromatic rings and with detection limits in the low parts-per-million (ppm) range. The vial system solves one of the major difficulties in analysis of larger PAHs using a MIMS. Normally, analysis of PAHs with more than two rings is hampered by a long memory effect due to the sticking of the PAHs to the inlet system, the membrane and surfaces in the vacuum system. By removing the vial from the sample cell within 2 min, we were able to analyze samples at 5-10 min intervals. The preliminary laboratory experiments presented here show much promise with respect to the development of a hand held (<10 kg) on-site mass spectrometry system for PAH screening at contaminated sites.     

Improving the selectivity of non-polar alkanes, alkenes, and aromatic hydrocarbon compounds by the application of acetonitrile as a Cl reagent

The selective enhancement of membrane introduction mass spectrometry for non-polar alkanes, alkenes, and aromatic hydrocarbon compounds by the application of acetonitrile as a chemical ionization reagent was investigated. Acetonitrile Cl is able to produce specific fragment ions for many of the compounds test and this can be used to identify and quantify the parent neutrals. This method provided relatively high detection limits of the test compounds. This method could potentially be useful for analytical applications such as the detection of non-polar hydrocarbons for environmental studies if CH₃CN Cl/MIMS is coupled with a preconcentration method.     

Biodegradation studies of 4-fluorobenzoic acid and 4-fluorocinnamic acid: an evaluation of membrane inlet mass spectrometry as an alternative to high performance liquid chromatography and ion chromatography

The biodegradation of 4-fluorobenzoic acid (4-FBA) and 4-fluorocinnamic acid (4-FCA) has been monitored by membrane inlet mass spectrometry (MIMS) using a hollow-fibre silicone membrane. A novel in-membrane pre-concentration/thermal desorption (IMP-MIMS) technique was employed for MIMS analysis using an oven temperature profile that allowed semi-volatile organic compounds to be accumulated in the membrane and then released by rapid heating. Air drying of the membrane between the analyte pre-concentration and thermal desorption stages improved mass spectrometric performance by removing residual water from the membrane. The concentrations of 4-FBA and 4-FCA determined by MIMS compare well with data obtained by high performance liquid chromatography (HPLC). Stoichiometric amounts of fluoride were monitored using ion chromatography (IC). Intermediates in the biodegradation pathway were identified by liquid chromatography/mass spectrometry (LC/MS). These data establish the potential of MIMS as an alternative to chromatographic methods for monitoring the biodegradation of semi-volatile organic compounds.     

Determination of mono- and sesquiterpenes in water samples by membrane inlet mass spectrometry and static headspace gas chromatography

A membrane inlet mass spectrometric (MIMS) method is presented and compared with a static headspace gas chromatographic method (HSGC) for the determination of terpenes in water. The MIMS method provides a very simple and fast analysis of terpenes in water, detection limits being relatively low, from 0.2 mug l(-1) for monoterpenes to 2 mug l(-1) for geraniol. The analysis of terpenes by the HSGC (equipped with flame ionization detector, FID) method is more time-consuming and the detection limits (2 mug l(-1) for monoterpenes to 100 mug l(-1) for geraniol) are higher than with MIMS. However, the HSGC method has the advantage of determining individual mono- and sesquiterpene compounds, whereas MIMS provides only separation of different classes of terpenes. Both methods were applied to the analysis of mono- and sesquiterpenes in several condensation water samples of pulp and paper mills.     

Membrane Introduction Mass Spectrometry (MIMS): A Versatile Tool for Direct,Real‐Time Chemical Measurements

Membrane introduction mass spectrometry (MIMS) is a direct, continuous, on‐line measurement technique. It utilizes a membrane to semi‐selectively transfer analyte mixtures from a sample to a mass spectrometer, rejecting the bulk of the sample matrix, which can be a gas, liquid or solid/slurry. Analyte selectivity and sensitivity are affected by optimizations at the membrane, ionization and the mass spectrometer levels. MIMS can be roughly classified by the acceptor phase that entrains analyte(s) to the mass spectrometer after membrane transport, either a gaseous acceptor phase (GP‐MIMS) or condensed acceptor phase (CP‐MIMS). The aim of this article is to provide an introduction to MIMS as a technique and to explore current variants, recent developments and modern applications, emphasizing examples from our group, the Applied Environmental Research Laboratories as well as selected work from others in this emerging area. Also provided is a synopsis of current and future directions for this versatile analytical technique. Copyright © 2014 John Wiley & Sons, Ltd.     

Solid phase micro-extraction in a miniature ion trap mass spectrometer

Fiber introduction mass spectrometry (FIMS), a variation of solid-phase microextraction (SPME) and membrane introduction mass spectrometry (MIMS), is employed with a miniature mass spectrometer. The inlet system, constructed of commercially available vacuum parts, allows the direct introduction of the SPME needle vacuum chamber into the mass spectrometer. Thermal desorption of the analyte from the poly(dimethylsiloxane) (PDMS) coated fiber was achieved with a built in nichrome heater, followed by electron ionization of the analytes internal to the cylindrical ion trap (CIT). The system has been tested with several volatile organic compounds (VOC) in air and to analyze the headspace over aqueous solutions, with limits of detection in the low ppb range. The signal rise (10-90%) and fall (90-10%) times for the system ranged from 0.1 to 1 s (rise) and 1.2 to 6 s (fall) using heated desorption. In addition, this method has been applied to quantitation of toluene in benzene, toluene, xylene (BTX) mixtures in water and gasoline. This simple and rapid analysis method, coupled to a portable mass spectrometer, has been shown to provide a robust, simple, rapid, reproducible, accurate and sensitive (low ppb range) fieldable approach to the effective in situ analysis of VOC in various matrices.     

A Comparison of Membrane Inlet Mass Spectrometry and Nitric Oxide (NO) Electrode Techniques to Detect NO in Aqueous Solution

The NO electrode and membrane inlet mass spectrometry (MIMS) have the advantage of being sensitive, direct, and real time detectors of NO in aqueous solution. They do not require reacting NO with labels or purging of NO with an inert gas. We show that the NO electrode and MIMS are comparable in sensitivity detecting NO concentrations to 0.5 nM in aqueous solution, and both give identical results in a biological measurement, the reactions of deoxyhemoglobin with nitrite.     

Detection of volatile organic sulfur compounds in water by headspace gas chromatography and membrane inlet mass spectrometry

Two gas chromatographic methods, GC-FID (flame ionization detection) and GC-ELCD (electrolytic conductivity detector) are compared in tlie analysis of volatile organic sulfur compounds (VOSCs) in water samples with a membrane inlet mass spectrometry (MIMS) technique. Carbon disulfide, ethanethiol, dimethyl sulfide, ethyl-methyl sulfide, thiophene, and dimethyl disulfide were used as test compounds. Linear dynamic ranges were found to be two decades with the GC-ELCD method and four decades with the GC-FID and MIMS methods. Detection limits were at low (μg/1 levels with the two gas chromatographic methods and clearly below μg/1 level with the MIMS method. Analysis of one sample takes 40 min with the gas chromatographic methods and five minutes with the MIMS method. The selectivity was good, especially with the GC-ELCD and the MIMS method. In addition, quantitative results obtained with spiked water samples by the three methods are compared.     

快速测量挥发性有机物的膜进样-飞行时间质谱仪的设计和应用

研制了一种膜进样-微型飞行时间质谱仪, 该仪器使用双层50 μm硅橡胶膜作为大气压下直接进样的接口. 实验结果表明, 随着样品流速的提高, 膜富集效率信号强度呈线性提高. 双膜中间具有真空差分系统, 富集得到的样品被迅速抽走, 进样系统中样品无记忆效应. 样品在膜中的响应时间为100 s, 而打开差分系统后仅需10 s信号即下降为平稳状态. 与毛细管直接进样相比, 双层膜的富集作用显著, 在相同的实验条件下使用膜进样技术测定10×10-6 (体积分数)苯、甲苯和对二甲苯的信号强度分别提高了280, 370和600倍. 膜进样系统与真空紫外光软电离方式联用, 对于苯的检出限已经达到了25×10-9 (体积分数), 线性范围为3个数量级. 由于采用了软电离方法, 无碎片离子产生, 所以能够根据分子量进行快速定性分析. 将该仪器应用于香烟主烟气中可挥发性有机物的在线分析, 得到50多种可挥发性的有机物. 实验结果表明, 膜进样-飞行时间质谱将在在线分析(特别是环境监测)方面具有广泛的应用空间.     

Determination of phenolic compounds in water using membrane inlet mass spectrometry

Two membrane inlet mass spectrometric (MIMS) methods for determining phenolic compounds in water are described and compared, namely direct analysis and analysis after acetylation of the phenolic compounds. Direct analysis of phenolic compounds in water is a very simple and rapid method and detection limits are relatively low (from 30 mug 1(-1) for phenol to 1000 mug 1(-1) for 4-nitrophenol). Analysis of phenolic compounds after aqueous acetylation is also a very simple and rapid method, and the detection limits are even two orders of magnitude lower than in the direct analysis. For example the detection limit of phenol acetate is 0.5 mug 1(-1) and that of 4-nitrophenol is 10 mug 1(-1). The acetylation method was also tested in the analysis of phenolic compounds from contaminated surface water samples.     

Determination of pentachlorophenol by negative ion chemical ionization with membrane introduction mass spectrometry

Pentachlorophenol (PCP) was used as a model compound to explore the potential of desorption chemical ionization (DCI) in the determination of polychlorinated pesticides using membrane introduction mass spectrometry (MIMS). A direct insertion membrane probe was modified so that a chemical ionization plasma could be established at the membrane surface. Using selected ion monitoring (SIM) in a tandem triple quadrupole mass spectrometer with isobutane chemical ionization (CI), the PCP detection limit under positive chemical ionization is 20 ppb whereas negative CI gives detection limits in the low ppb range. This performance is achieved without any pre-treatment or derivatization of the sample. Negative ion CI gives a signal that is linear over a concentration range of 2-1000 ppb. Comparison of data obtained with low ppb samples of 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol suggests that the sensitivity of this analytical procedure increases with increase in the number of electronegative substituents in the molecule.     

Comparison of different methods for the determination of volatile organic compounds in water samples

The aim of this work was to compare the characteristics of three methods, membrane inlet mass spectrometry (MIMS), purge-and-trap gas chromatography-mass spectrometry (P&T) and static headspace gas chromatography (HSGC), for the determination of volatile organic compounds in water samples as used in routine analysis. The characteristics examined included linear dynamic ranges, detection limits of selected environmentally hazardous volatile organic compounds (e.g. toluene, benzene and trichloroethene) in water, required analysis time and reproducibility of the analytical methods. The MIMS and P&T methods had the lowest detection limits for all the tested compounds, ranging from 0.1 to 5 mug 1(-1). Linear dynamic ranges using the MIMS method were about four orders of magnitude and using the P&T method about two orders of magnitude. Detection limits of the HSGC method were 10-100 times higher than those of the other two methods, but the linear dynamic ranges were larger, even up to six orders of magnitude. The analysis time per sample was shortest for the MIMS method, from 5 to 10 min, and ranged around from 35 to 45 min for the HSGC and P&T methods. The reproducibilities of the methods were of the same order of magnitude, in the range of 1-13%. Agreement between the analytical results obtained for spiked samples and for environmental water samples by the three different methods was very good.     

Membrane-introduction mass spectrometry (MIMS)

Membrane-introduction mass spectrometry (MIMS) for chemical analysis involves directly sampling analytes in gaseous, liquid and solid samples through a semi-permeable membrane coupled to a mass spectrometer, yielding selective and sensitive quantitation. Because MIMS is an on-line technique, in which samples can be continuously flowed over a membrane interface, it can yield analytical results in real time without the need for sample clean-up and chromatographic separation. This review highlights trends and developments in MIMS over the past decade and describes recent studies that pertain to its use for on-site, in-situ and in-vivo chemical analysis. We report on advancements in instrumentation, including membrane materials, interface configurations and ionization techniques that have extended the range of analytes amenable to MIMS.We summarize the progress made in the miniaturization of mass spectrometers that have resulted in field-portable systems and review recent applications of continuous mobile monitoring and on-site environmental monitoring to yield both temporally and spatially resolved quantitative and semi-quantitative data. Finally, we describe recent work involving the use of MIMS for in-vivo chemical analysis.     

Bestimmung von Methylchlorsilanen in Chlorsilanen mit Hilfe eines Systems Gas-Chromatograph und Massenspektrometer

Zusammenfassung Die Verbindungen (CH₃)₂SiHCl, CH₃SiHCl₂ und (CH₃)₃SiCl wurden in SiHCl₃/SiCl₄-Gemischen gas-chromatographisch analysiert, wobei ein Massenspektrometer mit fester Masseneinstellung als Detektor eingesetzt wurde. Die Nachweisgrenze liegt bei ca. 1 Gew.-ppm für diese Verbindungen.

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Determination of methylchlorosilanes in chlorsilanes with a gas-chromatograph/ mass spectrometer system

Summary The compounds (CH₃)₂SiHCl, CH₃SiHCl₂ and (CH₃)₃SiCl were analyzed in SiHCl₃/SiCl₄ mixtures by gas chromatography using a mass spectrometer being focused on definite peaks as detector. The detection limit was found to be about 1 ppm (wt) of these compounds.