Curie-point pyrolysis gas chromatography/mass spectrometry in the identification of paint media

Curie-point pyrolysis gas chromatography/mass spectrometry has been applied to different model paint samples containing proteinaceous (egg yolk) and oily (linseed oil) media. Results of pyrolysis at 610°C are highly reproducible, and among the different pyrolysis products some compounds diagnostic for the different binders have been identified. The application of the method to real samples, i.e. from the oil painting ‘Ritratto’ by Giuseppe Nogari (1669–1763) and from the tempera paint on the ligneous roof of S. Giobbe church (16th century) in Venice, proves its effectiveness in the identification of binding media.     

四元共聚物的热裂解色谱-质谱分析

报道了2－丁烯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸辛酯四元共聚物在不同裂解温度下的热裂解行为。用热裂解色谱－质谱分析方法，研究了裂解温度对裂解产物的影响，并讨论了四元共聚物的热裂解规律。     

Study of the mechanism of polysulfone decomposition by pyrolysis/gas chromatography and pyrolysis/gas chromatography/mass spectrometry

Both co- and terpolysulfones have been flash-pyrolyzed at high temperature followed by separation and identification of the products by gas chromatography and/or gas chromatography/mass spectrometry. As expected, most of the products were the corresponding olefin and SO₂. Additionally, higher molecular weight products, including aromatics, and olefin isomerization products, were produced. Mechanisms for initiation and formation of the higher molecular weight products are presented which include the back reaction of intermediate free radicals to abstract hydrogen or to form C? C bonds followed by expulsion of SO₂. The free-radical intermediates formed by the SO₂ expulsion undergo transformations to give the aromatic products. No breakdown products were found with either O or S present, nor was SO₂H found.     

The characterisation of plastic used in a Gabo sculpture

The Nylon line used in a sculpture by the artist Naum Gabo has been investigated. The sculpture at the Tate Gallery in London shows signs of degradation and there is interest in determining the best replacement material in order to extend the life of the sculpture. Thermal analysis was employed to identify the original polyamide used in the artwork. The tensile properties of the degraded Nylon from the sculpture were compared with those of unaged Nylon and poly(vinylidene fluoride) (PVDF), identified as a potential replacement material. PVDF was proposed as the preferred replacement for the sculpture.     

Investigation of some vinyl polymers by pyrolysis—gas chromatography—mass spectrometry

Although much has been published on the thermal degradation behaviour and products of vinyl polymers, the possibilities of using gaschromatography—mass spectrometry in the investigation of pyrolysate composition have much to offer.Results for poly(vinyl chloride), poly(vinyl acetate), polystyrene and poly(α-methyl-styrene) homopolymers and styrene—acrylonitrile copolymer obtained by pyrolysis—gas chromatography—mass spectrometry are presented. Numerous additional fragments not previously specified have been determined. The possible mechanisms of their origin as regards the polymer chain structure are discussed.     

Towards identification of traditional European and indigenous Australian paint binders using pyrolysis gas chromatography mass spectrometry

We report a pyrolysis GC–MS method capable of analysing Indigenous Australian and European binders typically used in the manufacture of culturally important painted works. Eleven different traditional European binders and ten different Indigenous Australian binders were examined. The method allows discrimination between highly complex and impure lipid, resin, polysaccharide, wax, and protein-based binders. Each was found to have characteristic pyrolysis products that were unique to the binder material, demonstrating the potential for differentiation of these binders on Australian Aboriginal artworks towards identification and conservation of cultural heritage.     

The examination of some vinyl acetate/olefin copolymers by pyrolysis gas chromatography mass spectrometry.

A study of the thermal degradation of some vinyl acetate/olefin copolymers reveals that side chain scissions at the backbone and scissions within the side chains themselves yield fragments which are apparently characteristic of the parent olefin.     

The mechanisms of thermal degradation of polymethyl acrylate using pyrolysis gas chromatography mass spectrometry

The pyrolysis of polymethyl acrylate is reported with identification of the major pyrolysis products. The mechanism involving random homolytic scission of the chain followed by a series of intermolecular and intramolecular transfer reactions as proposed by Cameron and Kane and extended by Haken, Ho, and Houghton is further developed. Reaction mechanisms are postulated for all of the products produced and ion fragmentation mechanisms for the various spectra produced are shown. The paper also forms the basis for a study of the homologous alkyl polyacrylates, both straight and branched chain esters being considered these having not been previously extensively studied.     

Application of pyrolysis–mass spectrometry and pyrolysis–gas chromatography–mass spectrometry with electron-ionization or resonance-enhanced-multi-photon ionization for characterization of crude oils

A novel analytical system for gas-chromatographic investigation of complex samples has been developed, that combines the advantages of several analytical principles to enhance the analytical information. Decomposition of high molecular weight structures is achieved by pyrolysis and a high separation capacity due to the chromatographic step provides both an universal as well as a selective and sensitive substance detection. The latter is achieved by simultaneously applying electron ionization quadrupole mass spectrometry (EI-QMS) for structural elucidation and [1 + 1]-resonance-enhanced-multi-photon ionization (REMPI) combined with time-of-flight mass spectrometry (ToFMS). The system has been evaluated and tested with polycyclic aromatic hydrocarbon (PAH) standards. It was applied to crude oil samples for the first time. In such highly complex samples several thousands of compounds are present and the identification especially of low concentrated chemical species such as PAH or their polycyclic aromatic sulfur containing heterocyclic (PASH) derivatives is often difficult. Detection of unalkylated and alkylated PAH together with PASH is considerably enhanced by REMPI–ToFMS, at times revealing aromatic structures which are not observable by EI-QMS due to their low abundance. On the other hand, the databased structure proposals of the EI-QMS analysis are needed to confirm structural information and isomers distinction. The technique allows a complex structure analysis as well as selective assessment of aromatic substances in one measurement. Information about the content of sulfur containing compounds plays a significant role for the increase of efficiency in the processing of petroleum.     

Characterization of sulfonated azo dyes and aromatic amines by pyrolysis gas chromatography/mass spectrometry

Sixteen sulfonated and unsulfonated azo dyes as well as eleven sulfonated and unsulfonated aromatic amines were analyzed and qualitatively characterized by means of pyrolysis gas chromatography/mass spectrometry at different temperatures. Aniline and aminonaphthalene were found to be the dominant pyrolysis products of sulfonated aromatic amines and dyes. Azo dye and dye class specific key compounds such as benzidine, vinyl-p-base and 4-aminoazobenzene could be identified by pyrolysis gas chromatography/mass spectrometry of commercial acid, cationic, direct, reactive and solvent dyes. 500 degrees C was the optimal pyrolysis temperature for most of the pyrolyzed compounds. The method was applied to a dried sample of a textile wastewater concentrate from a dyeing process. Reactive azo dyes of the group of Remazol dyes and anthraquinone dyes could be identified as the major compounds of the sample. The finding of caprolactam (a printing additive) suggests that the wastewater contained effluent from a process of heat-activated printing with reactive dyes. p-Chloraniline, a banned aromatic amine, was identified. Chemical reduction of the wastewater sample prior to pyrolysis resulted in the release of volatile aromatic amines and aided the classification of several products of pyrolysis.     

Cluster chemical ionization for improved confidence level in sample identification by gas chromatography/mass spectrometry

Upon the supersonic expansion of helium mixed with vapor from an organic solvent (e.g. methanol), various clusters of the solvent with the sample molecules can be formed. As a result of 70 eV electron ionization of these clusters, cluster chemical ionization (cluster CI) mass spectra are obtained. These spectra are characterized by the combination of EI mass spectra of vibrationally cold molecules in the supersonic molecular beam (cold EI) with CI-like appearance of abundant protonated molecules, together with satellite peaks corresponding to protonated or non-protonated clusters of sample compounds with 1-3 solvent molecules. Like CI, cluster CI preferably occurs for polar compounds with high proton affinity. However, in contrast to conventional CI, for non-polar compounds or those with reduced proton affinity the cluster CI mass spectrum converges to that of cold EI. The appearance of a protonated molecule and its solvent cluster peaks, plus the lack of protonation and cluster satellites for prominent EI fragments, enable the unambiguous identification of the molecular ion. In turn, the insertion of the proper molecular ion into the NIST library search of the cold EI mass spectra eliminates those candidates with incorrect molecular mass and thus significantly increases the confidence level in sample identification. Furthermore, molecular mass identification is of prime importance for the analysis of unknown compounds that are absent in the library. Examples are given with emphasis on the cluster CI analysis of carbamate pesticides, high explosives and unknown samples, to demonstrate the usefulness of Supersonic GC/MS (GC/MS with supersonic molecular beam) in the analysis of these thermally labile compounds. Cluster CI is shown to be a practical ionization method, due to its ease-of-use and fast instrumental conversion between EI and cluster CI, which involves the opening of only one valve located at the make-up gas path. The ease-of-use of cluster CI is analogous to that of liquid CI in ion traps with internal ionization, and is in marked contrast to that of CI with most other standard GC/MS systems that require a change of the ion source.     

Molecular criteria for discriminating museum Asian lacquerware from different vegetal origins by pyrolysis gas chromatography/mass spectrometry

This paper focuses on the identification of several chemical markers of vegetal species of Oriental lacquers with the aim at providing a methodology consistent with sampling restrictions necessarily applied in the field of cultural heritage. The method proposed is based on rapid and easy single step thermally assisted hydrolysis–methylation (THM) pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analysis that can be carried out with a minimum amount of matter (typically 10 μg for a sample collected on a museum or an archaeological object).     

Solid-phase microextraction gas chromatography/mass spectrometry: a new method for species identification of truffles

This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts.     

Determination of polychlorodibenzo-p-dioxins and polychlorodibenzofurans by gas chromatography/tandem mass spectrometry and gas chromatography/triple mass spectrometry in a quadrupole ion trap

The determination of tetra- to octachlorodibenzo-p-dioxins and tetra- to octachlorodibenzofurans (PCCD/Fs) by high-resolution gas chromatography/tandem mass spectrometry (HRGC/MS/MS) and high-resolution gas chromatography/triple mass spectrometry (HRGC/MS(3)) in a quadrupole ion trap, equipped with an external ion source, is presented. MS/MS involves a typical four-step process, namely ionization, parent ion isolation, collision-induced dissociation (CID) and mass analysis of the daughter ions. For the MS(3) experiment, the MS/MS scan function is used with the addition of selected daughter ion isolation, their CID and the mass analysis of second-generation product ions called 'grand-daughter ions.' For both methods, the energies necessary for the CID of the 17 PCDD/Fs were determined and optimized using multiple scan functions with different CID amplitudes. The CID efficiency, defined as the signal ratio of fragment ions detected from the major dissociation channels to molecular ions isolated, was 1.15-2.40 V for parent ion dissociation (MS/MS) and 1.05-1.50 V for daughter ion dissociation (MS(3)) and for all the chloro congeners. The same sensitivity (1 pg microl(-1)) can be reached with both the MS/MS and MS(3) methods and linear responses were obtained between 1 and 100 pg microl(-1) injected.     

Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

Pyrolysis oils have attracted a lot of interest, as they are liquid energy carriers and general sources of chemicals. In this work, gas chromatography with flame ionization detector (GC-FID) and two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) techniques were used to provide both qualitative and quantitative results of the analysis of three different pyrolysis oils. The chromatographic methods and parameters were optimized and solvent choice and separation restrictions are discussed. Pyrolysis oil samples were diluted in suitable organic solvent and were analyzed by GC×GC-TOFMS. An average of 300 compounds were detected and identified in all three samples using the ChromaToF (Leco) software. The deconvoluted spectra were compared with the NIST software library for correct matching. Group type classification was performed by use of the ChromaToF software. The quantification of 11 selected compounds was performed by means of a multiple-point external calibration curve. Afterwards, the pyrolysis oils were extracted with water, and the aqueous phase was analyzed both by GC-FID and, after proper change of solvent, by GC×GC-TOFMS. As previously, the selected compounds were quantified by both techniques, by means of multiple point external calibration curves. The parameters of the calibration curves were calculated by weighted linear regression analysis. The limit of detection, limit of quantitation and linearity range for each standard compound with each method are presented. The potency of GC×GC-TOFMS for an efficient mapping of the pyrolysis oil is undisputable, and the possibility of using it for quantification as well has been demonstrated. On the other hand, the GC-FID analysis provides reliable results that allow for a rapid screening of the pyrolysis oil. To the best of our knowledge, very few papers have been reported with quantification attempts on pyrolysis oil samples using GC×GC-TOFMS most of which make use of the internal standard method. This work provides the ground for further analysis of pyrolysis oils of diverse sources for a rational design of both their production and utilization process.     

气相色谱-质谱联用法测定水果中4,6-二硝基邻甲酚

利用气质联用（GC-MS）技术建立了水果中4,6-二硝基邻甲酚（DNOC）的测定方法。以二氯甲烷提取水果样品中DNOC残留,并使用N-（特丁基二甲基硅）-N-甲基三氟乙酰胺对提取DNOC残留进行衍生化,利用GC-MS选择离子模式（SIM）测定残留DNOC衍生化产物,在苹果和梨中DNOC的添加回收率在70％～110％之间,相对标准偏差RSD〈9％（n=10）,方法的检出限为10μg/kg。     

Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization

The explosive triacetone triperoxide (TATP) has been analyzed by gas chromatography/mass spectrometry (GC/MS) and sub-nanogram detection limits are reported by ammonia positive ion chemical ionization (PICI), electron ionization (EI) and methane negative ion chemical ionization (NICI). Analysis by methane PICI and ammonia NICI gave detection limits in the low nanogram range. Analyses were carried out on (linear) quadrupole and ion trap instruments. Analysis of TATP by PICI using ammonia reagent gas is the preferred analytical method, producing low limits of detection as well as an abundant (greater than 60% of base peak) diagnostic adduct ion at m/z 240 corresponding to [TATP + NH4]+. Isolation of the [TATP + NH4]+ ion with subsequent collision-induced dissociation (CID) produces extremely low abundance product ions at m/z values greater than 60, and the m/z 223 ion corresponding to [TATP + H]+ was not observed. Density functional theory (DFT) calculations at the B88LYP/DVZP level indicate that dissociation of the complex to form NH4+ and TATP occurs at energies lower than peroxide bond dissociation, while protonation of TATP leads to cleavage of the ring structure. These results provide a method for pico-gram detection levels of TATP using commercial instrumentation commonly available in forensic laboratories. As a point of comparison, a detection limit of 15 ng was obtained by flame ionization detection.