GC/MS on an LC/MS instrument using atmospheric pressure photoionization

Atmospheric pressure (AP) GC/MS was first introduced by Horning et al. [E.C. Horning, M.G. Horning, D.I. Carroll, I. Dzidic, R.N. Stillwell, Anal. Chem. 45 (1973) 936] using ⁶³Ni as a beta-emitter for ionization. Because, at the time special instrumentation was required, the technique was only applied with consistency to negative ion environmental studies where high sensitivity was required [T. Kinouchi, A.T.L. Miranda, L.G. Rushing, F.A. Beland, W.A. Korfmacher, J. High Resolut. Chromatogr., Chromatogr. Commun. 13 (1990) 281]. Currently, AP ion sources are commonly available on LC/MS instruments and recently a method was reported for converting an AP-LC/MS ion source to a combination AP-LC/MS:GC/MS source [C.N. McEwen, R.G. McKay, J. Am. Soc. Mass Spectrom. 16 (2005) 1730]. Here, we report the use of atmospheric pressure photoionization (APPI) with GC/MS and compare this to AP chemical ionization (APCI) GC/MS and electron ionization (EI) GC/MS. Using a nitrogen purge gas, we observe excellent chromatographic resolution and abundant molecular M⁺ and MH⁺ ions as well as structurally significant fragment ions. Comparison of a 9.8 eV UV lamp with a 10.6 eV lamp, as expected, shows that the higher energy lamp gives more universal ionization and more fragment ions than the lower energy lamp. While there are clear differences in the fragment ions observed by APPI-MS versus EI-MS, there are also similarities. As might be expected from the ionization mechanism, APPI ionization is similar to low energy EI. These odd electron fragment ions are useful in identifying unknown compounds by comparison to mass spectra in computer libraries.     

High‐resolution GC/MS studies of a light crude oil fraction

The continuous development in analytical instrumentation has brought the newly developed Orbitrap‐based gas chromatography / mass spectrometry (GC/MS) instrument into the forefront for the analysis of complex mixtures such as crude oil. Traditional instrumentation usually requires a choice to be made between mass resolving power or an efficient chromatographic separation, which ideally enables the distinction of structural isomers that is not possible by mass spectrometry alone. Now, these features can be combined, thus enabling a deeper understanding of the constituents of volatile samples on a molecular level. Although electron ionization is the most popular ionization method employed in GC/MS analysis, the need for softer ionization methods has led to the utilization of atmospheric pressure ionization sources. The last arrival to this family is the atmospheric pressure photoionization (APPI), which was originally developed for liquid chromatography / mass spectrometry (LC/MS). With a newly developed commercial GC‐APPI interface, it is possible to extend the characterization of unknown compounds. Here, first results about the capabilities of the GC/MS instrument under high or low energy EI or APPI are reported on a volatile gas condensate. The use of different ionization energies helps matching the low abundant molecular ions to the structurally important fragment ions. A broad range of compounds from polar to medium polar were successfully detected and complementary information regarding the analyte was obtained.     

Determination of estrogens and progestogens by mass spectrometric techniques (GC/MS, LC/MS and LC/MS/MS)

Steroid sex hormones and related synthetic compounds have been shown to provoke alarming estrogenic effects in aquatic organisms, such as feminization, at very low concentrations (ng/L or pg/L). In this work, different chromatographic techniques, namely, gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS), are discussed for the analysis of estrogens, both free and conjugated, and progestogens, and the sensitivities achieved with the various techniques are inter-compared. GC/MS analyses are usually carried out after derivatization of the analytes with bis(trimethylsilyl)trifluoroacetamide (BSTFA). For LC/MS and LC/MS/MS analyses, different instruments, ionization techniques (electrospray (ESI) and atmospheric pressure chemical ionization (APCI)), ionization modes (negative ion (NI) and positive ion (PI)) and monitoring modes (selected ion monitoring (SIM) and selected reaction monitoring (SRM)) are generally employed. Based on sensitivity and selectivity, LC/ESI-MS/MS is generally the method of choice for determination of estrogens in the NI mode and of progestogens in the PI mode (instrumental detection limits (IDLs) 0.1-10 ng/mL). IDLs achieved by LC/ESI-MS in the SIM mode and by LC/ESI-MS/MS in the SRM mode were, in general, comparable, although the selectivity of the latter is significantly higher and essential to avoid false positive determinations in the analysis of real samples. Conclusions and future perspectives are outlined.     

红景天挥发油的GC／MS／DS和GC／IR／DS研究

红景天挥发油的ＧＣ／ＭＳ／ＤＳ和ＧＣ／ＩＲ／ＤＳ研究阎吉昌，张宏徐少敏卫永弟，阎雪（东北师范大学测试中心，长春，１３００２４）（吉林省石油化工研究院，白求恩医科大学）关键词红景天，色谱／质谱，色谱／红外，复杂有机混合物应用色谱／质谱／计算机（ＧＣ／Ｍ...     

GC/MS-positive ion chemical ionization and MS/MS study of volatile benzene compounds in five different woods used in barrel making

Extracts from acacia, chestnut, cherry, mulberry, and oak wood, used in making barrels for aging wine and spirits were studied by GC/MS positive ion chemical ionization (PICI). Wood chips were extracted by a 50% water/ethanol solution and a tartrate buffer pH 3.2-12% ethanol (model wine) solution. The principal compounds identified in extracts were guaiacol-containing aldehydes and alcohols, such as benzaldehyde and derivatives, vanillin and syringaldehyde, cinnamaldehyde and coniferaldehyde, eugenol and methoxyeugenol, guaiacol and methoxyguaiacol derivatives. PICI using methane as reagent gas produced a high yield of the protonated molecular ion of volatile phenols, compound identification was confirmed by collision-induced-dissociation (CID) experiments on [M + H](+) species. MS/MS fragmentation patterns were studied with standard compounds: guaiacol-containing molecules were characterized by neutral methyl and methanol losses, benzaldehyde derivatives by CO loss. Acacia wood extracts contained significant syringaldehyde and anisaldehyde, but no eugenol and methoxyeugenol. Significant syringaldehyde, eugenol and methoxyeugenol, and high vanillin were found in chestnut and oak wood extracts; low presence of volatile benzene compounds was found in mulberry wood extracts. Cherry wood extracts were characterized by the presence of several benzaldehyde derivatives and high trimethoxyphenol.     

Analysis of turkish lignite tar by coupled LC/GC,GC/MS,and capillary SFC

This work describes the analysis of a pyrolysis product of a lignite sample obtained from the Turkish Goynuk reserve. The aliphatic, aromatic and polar compounds present in the tar are separated and identified by various chromatographic techniques: Capillary gas chromatography/mass spectrometry (GC/MS), on-line high performance microbore liquid chromatography/capillary gas chromatography (LC/GC) and capillary supercritical fluid chromatography (SFC). The suitability of each technique for this particular application is discussed, and semi-quantitative results are presented for the major components detected.     

Liquid chromatography/negative ion atmospheric pressure photoionization mass spectrometry: a highly sensitive method for the analysis of organic explosives

Gas chromatography/mass spectrometry (GC/MS) is applied to the analysis of volatile and thermally stable compounds, while liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI‐MS) and liquid chromatography/electrospray ionization mass spectrometry (LC/ESI‐MS) are preferred for the analysis of compounds with solution acid‐base chemistry. Because organic explosives are compounds with low polarity and some of them are thermally labile, they have not been very well analyzed by GC/MS, LC/APCI‐MS and LC/ESI‐MS. Herein, we demonstrate liquid chromatography/negative ion atmospheric pressure photoionization mass spectrometry (LC/NI‐APPI‐MS) as a novel and highly sensitive method for their analysis. Using LC/NI‐APPI‐MS, limits of quantification (LOQs) of nitroaromatics and nitramines down to the middle pg range have been achieved in full MS scan mode, which are approximately one order to two orders magnitude lower than those previously reported using GC/MS or LC/APCI‐MS. The calibration dynamic ranges achieved by LC/NI‐APPI‐MS are also wider than those using GC/MS and LC/APCI‐MS. The reproducibility of LC/NI‐APPI‐MS is also very reliable, with the intraday and interday variabilities by coefficient of variation (CV) of 0.2–3.4% and 0.6–1.9% for 2,4,6‐trinitrotoluene (2,4,6‐TNT). Copyright © 2008 John Wiley & Sons, Ltd.     

Development of a headspace GC/MS analysis for carbonyl compounds (aldehydes and ketones) in household products after derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine.

Carbonyl compounds (aldehydes and ketones) are suspected to be among the chemical compounds responsible for Sick Building Syndrome and Multiple Chemical Sensitivities. A headspace gas chromatography/mass spectrometry (GC/MS) analysis for these compounds was developed using derivatization of the compounds into volatile derivatives with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). For GC/MS detection, two ionization modes including electron impact ionization (EI) and negative chemical ionization (NCI) were compared. The NCI mode seemed to be better because of its higher selectivity and sensitivity. This headspace GC/MS (NCI mode) was employed as analysis for aldehydes and ketones in materials (fiber products, adhesives, and printed materials). Formaldehyde was detected in the range of N.D. (not detected) to 39 microg/g; acetaldehyde, N.D. to 4.1 microg/g; propionaldehyde, N.D. to 1.0 microg/g; n-butyraldehyde, N.D. to 0.10 microg/g; and acetone, N.D. to 3.1 microg/g in the samples analyzed.     

Challenges in the identification process of phenidate analogues in LC‐ESI‐MS/MS analysis: Information enhancement by derivatization with isobutyl chloroformate

A new analytical technique for the structural elucidation of four representative phenidate analogues possessing a secondary amine residue, which leads to a major/single amine‐representative fragment/product ion at m/z 84 both in their GC‐EI‐MS and LC‐ESI‐MS/MS spectra, making their identification ambiguous, was developed. The method is based on “in vial” chemical derivatization with isobutyl chloroformate in both aqueous and organic solutions, followed by liquid chromatography‐electrospray ionization mass spectrometry (LC‐ESI‐MS/MS). The resulting carbamate derivatives promote rich fragmentation patterns with full coverage of all substructures of the molecule, enabling detailed structural elucidation and unambiguous identification of the original compounds at low ng/mL levels.     

Preparation of doubly 13C-labelled benzylpenicillin as internal standard for residue analytical use with GC/MS and LC/MS

A simple and rapid method is described for the preparation of doubly ¹³C-labelled benzylpenicillin for use in isotope dilution analyses of benzylpenicillin residues. The product is characterized by IR, NMR, GC/MS and LC/MS. Tissue analyses demonstrate its advantage with residue analytical methods using mass spectrometric techniques for measurement. Different fragmentation patterns are observed when using GC/EI-MS or LC/electrospray-MS. The consequences for residue analysis are discussed. Received: 28 May 1997 / Revised: 23 July 1997 / Accepted: 25 July 1997     

Confirmation of moxidectin residues in cattle fat by liquid chromatography/mass spectrometry

Moxidectin, a potent new endo- and ectoparasitic agent, is determined in cattle tissues by liquid chromatography (LC) with fluorescence detection. The original confirmatory method for moxidectin in cattle fat, the target tissue for regulatory purposes, was LC with mass spectrometry (MS) using thermospray (TSP) ionization and selected ion monitoring. As newer ionization techniques for LC/MS made TSP obsolete and with the availability of a new generation of benchtop LC/MS instrumentation, the confirmation of moxidectin in cattle fat was re-evaluated. The ionization techniques of atmospheric pressure chemical ionization versus electrospray ionization, the detection techniques of single-stage MS versus tandem MS, and the instrumentation of ion trap versus quadrupole were investigated. The final confirmatory method was based on full-scan single-stage MS. Even with full-scan detection, the analysis required at least 10-fold less extract than the original TSP method. The applicability of this new confirmatory method was demonstrated on both ion trap and quadrupole instruments.     

Study on the photostability of guaiazulene by high-performance liquid chromatography/mass spectrometry and gas chromatography/mass spectrometry

The photostability of guaiazulene (1,4-dimethyl-7-isopropylazulene; GA), a natural azulenic compound used in cosmetic and health-care products, as well as in pharmaceutical preparations, was investigated in solution (methanol, ethanol, acetonitrile), by different techniques: gas chromatography/mass spectrometry (GC/MS) and high-performance liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry and UV detection (LC/APCI-MS and HPLC/UV). A solar simulator (xenon-arc lamp) was used as UV-A radiation source. The study involved: monitoring compound decomposition, identifying products of photodegradation (PPs), assessing the role of oxygen and evaluating the kinetics of the process. Minor PPs are volatile compounds and were characterized by GC/MS, while oligomeric polyoxygenated compounds, tentatively characterized on the basis of MS and MS/MS spectra, were found to be the main photoproducts. The photodegradation was found to be enhanced by the presence of oxygen; nevertheless, determination of the singlet oxygen quantum yield for GA gave a lower value than that for the reference standard Rose Bengal. The obtained results and the developed stability-indicating methods (GC/MS and LC/MS) are of interest for stability studies and/or quality control purposes of GA as raw material or cosmetic products.     

High-temperature (GC)2/MS investigations

The analysis of low volatile compounds by (GC)²/MS using high-temperature stable glass-capillary columns and a commercially available GC/quadrupole MS instrument is described. It will be shown that no special modifications or procedures are required in analyzing organic compounds exceeding carbon numbers of 50. The application to industrially and naturally occuring high boiling mixtures will be discussed.     

GC/MS analysis of chlorinated paraffins with negative ion chemical ionization

Although chlorinated paraffins (CP) are produced in large amounts (300 000 tonnes per year), little is known about their occurrence in the environment due to the lack of specific and sensitive analytical methods. The present paper describes the GC/MS analysis of different CP's using capillary gas chromatography with on-column injection and negative ion chemical ionization (NCI) mass spectrometry. Chromatographic resolution of groups of isomers and homologues was obtained. The chromatograms and mass spectra are discussed. The suitability of this method for trace analysis of a CP sample using multiple ion detection (MID) is described.     

气相色谱/质谱法分析曼陀罗果实挥发油的化学成分

用水蒸汽蒸馏法从曼陀罗果实中提取挥发油,并用气相色谱/质谱(GC/MS)联用技术对其化学成分进行分离和结构鉴定,用峰面积归一化法确定各成分的相对含量。结果确定了68种化合物,占挥发油总量的82.83%,其主要成分为6-戊基-5,6-二氢化吡喃-2-酮(9.13%)、3,7,11,15-四甲基-2-十六碳烯-1-醇(6.71%)、二苯酮(6.16%)和1-己醇(6.10%)等。     

GC／MS检测信息的综合利用

从充分利用气相色谱／质谱（ＧＣ／ＭＳ）提供的信息来鉴定ＧＣ流出组分的目的出发，并以脂肪醇分析为例讨论了ＧＣ保留指数在ＭＳ谱图解析及ＭＳ鉴定结果的合理性检验方面的作用。总结了ＧＣ保留的同系物规律、极性规律、加和规律及异构物规律来指导ＭＳ谱图解析。提出了含氧化合物官能团相对于－ＣＨ２－质量数的保留指数附加贡献值辅助ＭＳ确定化合物的类别。同时采用了ＧＣ／ＭＳ中选择离子检测方法（ＳＩＭ）在分子离子峰受噪音干扰或太弱以至完全未观测到时来进一步佐证其相对分子质量。     

乙酰乙酸乙酯烯醇式与酮式GC/MS和GC/IR分析

采用ＧＣ／ＭＳ对乙酸乙酯烯醇式在不同离子源温度,接口温度,进样器温度,柱温等条件下的气相色谱行为进行了研究,用重氢交换法和高分辨质谱法对烯醇式和酮式的质谱进行了解析,并通过ＧＣ／ＩＲ研究了烯醇式和酮式的红外光谱。     

Relative response ratios for dual-isotope measurements via coelution and GC/MS

Dual-isotope internal standard measurements by GC/MS which mimic isotope dilution may suffer from non-linear response relations, irreproducibilities or unduly large uncertainties because of variations in ionization efficiences for the respective isotopic forms in the MS source. Such variations may sometimes be avoided via extensive pretreatments, high resolution GC separations and careful control of instrumental parameters. However, an alternative approach is feasible which instead exploits advantages of decreasing GC resolution. By forcing both forms of each analyte to coelute, their relative ionization efficiencies in the MS source should be nearly constant, thereby effectively allowing for constant relative sensitivities over several orders of magnitude in concentration. Thus, constant relative response ratios, required for internal standard calculations, may be attained as a consequence of dramatically lowered GC resolution. Coelution results described herein show linear relative sensitivity relations over much broader ranges than observed for corresponding conventional calibrations with separated components. Coelution methods for dual-isotope GC/MS determinations are compatible with internal standard calculations and thereby offer a powerful alternative to the conventional approach of requiring expensive and labor-intensive additional pretreatments and separations to assure resolution of measured eluates.     

Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods

Polycyclic aromatic hydrocarbons (PAHs) are frequently measured in the atmosphere for air quality assessment, in biological tissues for health-effects monitoring, in sediments and mollusks for environmental monitoring, and in foodstuffs for safety reasons. In contemporary analysis of these complex matrices, gas chromatography (GC), rather than liquid chromatography (LC), is often the preferred approach for separation, identification, and quantification of PAHs, largely because GC generally affords greater selectivity, resolution, and sensitivity than LC. This article reviews modern-day GC and state-of-the-art GC techniques used for the determination of PAHs in environmental samples. Standard test methods are discussed. GC separations of PAHs on a variety of capillary columns are examined, and the properties and uses of selected mass spectrometric (MS) techniques are presented. PAH literature on GC with MS techniques, including chemical ionization, ion-trap MS, time-of-flight MS (TOF-MS), and isotope-ratio mass spectrometry (IRMS), is reviewed. Enhancements to GC, for example large-volume injection, thermal desorption, fast GC, and coupling of GC to LC, are also discussed with regard to the determination of PAHs in an effort to demonstrate the vigor and robustness GC continues to achieve in the analytical sciences.     

Identification and characterization of fenton oxidation products of surfactants by electrospray mass spectrometry and by solid phase microextraction gas chromatography mass spectrometry. 2. Fatty alcohol polyethoxy sulphates

The Fenton reaction for the degradation of surfactants has been investigated and partial degradation products have been identified and characterized by mass spectrometry for the case of fatty alcohol polyethoxy sulphates. The polar water-soluble products were investigated by liquid chromatography/mass spectrometry (LC/MS) with electrospray ionization (ESI), and the volatile products leaving the mixture during the reaction were trapped by means of solid phase microextraction (SPME) and investigated by gas chromatography/mass spectrometry (GC/MS) with electron and chemical ionization. The oxidation leads to the formation of products with hydroxyl and epoxide groups due to insertion of oxygen atoms or with terminal ethoxylic moieties deriving from the loss of the hydrophilic sulphate group. The formation of volatile aldehydes is also observed, corresponding to the fragmentation between hydrocarbon and ethoxylic chains. The extent of mineralization is dependent on peroxide and iron(II) concentrations. Copyright 2000 John Wiley & Sons, Ltd.