Determination of nicotine and other minor alkaloids in international cigarettes by solid-phase microextraction and gas chromatography/mass spectrometry

Nicotine, nornicotine, anabasine, and anatabine are the most abundant alkaloids in tobacco. Along with the addictiveness of nicotine, other properties, including their occurrence in tobacco at relatively high concentrations, and as the primary precursors for the highly carcinogenic tobacco-specific nitrosoamines, make these chemicals important from a public health standpoint Therefore, developing a fast and accurate quantitative method to screen large numbers of cigarette samples for these alkaloids was important. This report describes the first use of headspace analysis using solid-phase microextraction combined with gas chromatography/mass spectrometry for the unambiguous detection of tobacco alkaloids. Detection and confirmation of each analyte isestablished by both chromatographic retention times and the ratio of reconstructed ion chromatogram peak areas from characteristic quantitation ion and confirmation ion. Twenty-eight cigarette brands from 14 countries were analyzed. Surprisingly, the minor alkaloids' response factors varied considerably among different styles of cigarettes. Accurate quantification was achieved using a three-point standard addition protocol. The standard addition approach was essential to obtain accurate measurements by minimizing matrix effects that would otherwise have contributed to quantitation bias. Significant differences in the alkaloid profiles were measured in the different cigarette brands. These results strongly suggest that such differences reflect variations associated with blend compositions, tobacco quality, and manufacturing practices.     

Identification of uncommon plant metabolites based on calculation of elemental compositions using gas chromatography and quadrupole mass spectrometry

Unknown compounds in polar fractions of Arabidopsis thaliana crude leaf extracts were identified on the basis of calculations of elemental compositions obtained from gas chromatography/low-resolution quadrupole mass spectrometric data. Plant metabolites were methoximated and silylated prior to analysis. All known peaks were used as internal references to construct polynomial recalibration curves of from raw mass spectrometric data. Mass accuracies of 0.005 +/- 0.003 amu and isotope ratio errors of 0.5 +/- 0.3% (A + 1/A), respectively, 0.3 +/- 0.2% (A + 2/A), could be achieved. Both masses and isotope ratios were combined when the elemental compositions of unknown peaks were calculated. After calculation, compound identities were elucidated by searching metabolic databases, interpreting spectra, and, finally, by comparison with reference compounds. Sum formulas of more than 70 peaks were determined throughout single GC/MS chromatograms. Exact masses were confirmed by high-resolution mass spectrometric data. More than 15 uncommon plant metabolites were identified, some of which are novel in Arabidopsis, such as tartronate semialdehyde, citramalic acid, allothreonine, or glycolic amide.     

Determination of polycyclic aromatic hydrocarbons with molecular weight 300 and 302 in environmental-matrix standard reference materials by gas chromatography/mass spectrometry

An analytical approach based on gas chromatography/ mass spectrometry (GC/MS) is presented for the measurement of polycyclic aromatic hydrocarbons with molecular weight (MW) 300 and 302 in environmental samples. Three different GC stationary phases [5% and 50% phenyl methylpolysiloxane and dimethyl (50% liquid crystalline) polysiloxane] were compared, and retention indexes (RI) are given for 23 individual MW 302 isomers. Identification of MW 300 and 302 isomers in four environmental-matrix Standard Reference Materials (SRMs) (SRM 1597, coal tar extract; SRM 1648 and SRM 1649a, air particulate matter; and SRM 1941, marine sediment) was based on the comparison of RI data and mass spectra from authentic standards. Dibenzo[a,l]pyrene, which is of considerable interest because of its high carcinogenicity, was identified and quantified in the four environmental-matrix SRMs. A total of 23 isomers of MW 302 and four isomers of MW 300 were quantified in four different environmental-matrix SRMs, and the results are compared to previously reported results based on liquid chromatography with fluorescence detection.     

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.     

Separation of cisplatin and its hydrolysis products using electrospray ionization high-field asymmetric waveform ion mobility spectrometry coupled with ion trap mass spectrometry

Cisplatin and its mono- and dihydrated complexes have been separated using a high-field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer interfaced with electrospray ionization (ESI) and ion trap mass spectrometry (ITMS). The addition of helium to the nitrogen curtain/carrier gas in the FAIMS device improved both the sensitivity and selectivity of the electrospray analysis. Introduction of a three-component mixture as curtain/carrier gas, nitrogen, helium, and carbon dioxide, resulted in further improvements to sensitivity. Compared with conventional ESI-MS, the background chemical noise in the ESI-FAIMS-ITMS spectrum was dramatically reduced, resulting in over 30-fold improvement in the signal-to-noise ratio for cisplatin. Analytical results were linear over the concentration range 10-200 ng/mL for intact cisplatin with a corresponding detection limit determined of 0.7 ng/mL with no derivatization or chromatographic separation prior to analysis.     

Determination of linear alkylbenzenesulfonates and their degradation products in soils by liquid chromatography-electrospray-ion trap multiple-stage mass spectrometry

Linear alkylbenzenesulfonates (LAS) (C(10)-C(13)) and their degradation products, sulfophenyl carboxylate compounds (SPCs) (C(2)-C(6), C(8), C(11)), have been extracted from soil samples with methanol, isolated, concentrated by solid-phase extraction, and determined by liquid chromatography/negative ion electrospray quadrupole ion-trap tandem mass spectrometry (MS(n)). The ion fragmentation processes and pathways were studied in detail by MS, MS(2), and MS(3). Upon collision-induced dissociation, the deprotonated molecules of LASs render the ethylene-substituted benzenesulfonate ion (m/z 183), the fragmentation of which gave the intense signal at m/z 119, corresponding to the ethylene-substituted phenoxide ion formed by the loss of sulfur dioxide. The fragmentation pattern of SPCs shows that, for the analytes of large carbon atom chains (>5C), the neutral loss of water is favored whereas for those of short carbon atoms chain, the loss of carbon dioxide is more frequent. Multiple reaction monitoring using isolation only for MS and using isolation and fragmentation for MS(2) and MS(3) were used to identify and quantify each compound. The three MS modes have been validated in terms of sensitivity, selectivity, and precision, showing that each MS stage used reduces sensitivity 10 times. Recoveries from soil were higher than 65% at LOQ level for all the analytes tested, except for C(2)-C(4) SPCs by any MS mode, with relative standard deviation lower than 19%. The utility of the method is demonstrated by successfully quantifying real samples treated with these products. Quantification limits for the methodology developed in this work ranged from 0.5 to 50 microg kg(-1) by MS, from 2 to 400 microg kg(-1) by MS(2), and from 20 to 4000 microg kg(-1) by MS(3). Concentration levels of LASs and SPCs-ranging from 0.1 to 15 mg kg(-1)-were found in soil samples amended with sludges, thus indicating their input and persistence in the soil compartment.     

Stop-flow programmable selectivity with a dual-column ensemble of microfabricated etched silicon columns and air as carrier gas

A series-coupled ensemble of microfabricated GC columns made by dry reactive ion etching of silicon substrates is evaluated for use with pneumatic selectivity enhancement techniques for targeted pairs of volatile organic compounds. Each column is 3.0 m long with a 150 miceom wide by 240 microm deep cross section. Dynamic coating was used to prepare a nonpolar column with a dimethyl polysiloxane stationary phase and a moderately polar column with a trifluoropropylmethyl polysiloxane stationary phase. Each column generates 5000-6000 theoretical plates. The columns are operated in series with the nonpolar column connected to a split inlet, the polar column connected to a flame ionization detector, and a valve connected between the column junction point and the inlet to the first column. When the valve is closed, the effluent from the first column passes directly into the second column. When the valve is open, both ends of the first column are at the inlet pressure, and flow stops in this column while increased flow is obtained in the second column. For analyte pairs that are separated by the first column but coelute from the column ensemble, the valve is opened for a few seconds after the first component of the pair has passed into the second column but the second component is still in the first column. The result is enhanced separation of the pair in the ensemble chromatogram. Relatively thick cross-linked stationary-phase films are used to increase retention for volatile compounds. The combination of air carrier gas and stationary-phase film thickness in the range 1-2 microm requires the use of relatively low average carrier gas velocities (typically less than 10 cm/s) for adequate resolving power of the column ensemble. Selectivity enhancement under isothermal conditions for a 14-component mixture of volatile organic compounds is demonstrated where neither of the columns alone nor the column ensemble without selectivity enhancement could obtain a complete separation.     

Determination of alkyltrimethylammonium chlorides in river water by gas chromatography/ion trap mass spectrometry with electron impact and chemical ionization

This work describes a modified method to analyze alkyltrimethylammonium chlorides (ATMACs) in river water samples. The proposed method involves adding solid potassium iodide to water sample (pH adjusted to 10.0) as a counterion to enhance the extraction of ATMAC residues by dichloromethane liquid-liquid extraction. The iodide-ATMA+ ion pairs were demethylated to their corresponding nonionic alkyldimethylamines (ADMAs) by thermal decomposition in a GC injection port. The corresponding ADMAs were then identified and quantitated by gas chromatography/ion trap mass spectrometry (GC/MS) in electron impact and low-pressure positive ion chemical ionization (PICI) modes. A relatively high abundance of ADMAs was detected at a demethylation temperature above 300 degrees C in the injection port. Experimental results indicate that the proposed method is precise and sensitive in ATMACs analysis and allows quantitation at < or = 0.01 microg/L in 500 mL of the water samples. The enhanced selectivity of quasi-molecular ion chromatograms of C12-C18-ADMA, obtained using methanol PICI-MS, enables ATMAC residues to be identified at trace levels in environmental samples. Recovery of the ATMACs in various spiked water samples ranged from 70 to 94% while RSD ranged from 3 to 12%. The concentrations of total measured ATMAC residues in river water samples ranged from nondetectable to 1.24 microg/L.     

Determination of alkylbenzyldimethylammonium chlorides in river water and sewage effluent by solid-phase extraction and gas chromatography/mass spectrometry

This study presents a modified method to analyze alkylbenzyldimethylammonium chlorides (ABDACs) in river water and sewage effluent. The method involves mixed samples with linear alkylbenzenesulfonates (LAS) as a counterion to enhance the extraction of ABDAC residues from an RP-18 solid-phase cartridge by formation of hydrophobic ion-pair complexes. The ABDACs were then eluted with methanol-ethyl acetate (1:1, v/v) and formed to their corresponding alkyldimethylamines by the Hofmann degradation with potassium tert-butoxide. The alkyldimethylamines were then identified and quantitated by gas chromatograph/mass spectrometry (GC/MS). The results indicate that, in the presence of LAS, debenzylation of ABDACs occurs selectively at a temperature higher than 90 degrees C to produce the corresponding nonionic alkyldimethylamines. The method proposed herein provides a high precision and sensitivity for ABDACs, to quantitation at < or =0.1 microg/L in 500 mL of the water samples. The average recovery of ABDAC spiked water samples was 95% with relative standard deviations (RSD, n = 7) of 9%. The RSDs of three replicate environmental sample analyses ranged from 5 to 11%. Direct HPLC method was applied to evaluate the GC/MS method, and compatible results were observed.     

Characterization of lignin by gas chromatography and mass spectrometry using a simplified CuO oxidation method

An efficient and high-throughput method to characterize lignin in environmental samples using alkaline CuO oxidation and capillary gas chromatography with mass detection is presented. Monomeric lignin phenols released during oxidation were selectively extracted using a polymer-based solid phase sorbent rather than liquid phase extraction. Sample size and matrix were found to influence lignin phenol yields. Increasing the sample size to an organic carbon content ≥1.5 mg of C minimizes phenol oxidation losses, and the addition of glucose as a sacrificial carbon source helped minimize oxidation losses in samples with <5 mg of organic carbon.     

Determination of parabens and triclosan in indoor dust using matrix solid-phase dispersion and gas chromatography with tandem mass spectrometry

A simple sample preparation method for the determination of four parabens and triclosan in indoor dust is presented. Analytes were extracted from the sample and isolated from interfering species using the matrix solid-phase dispersion technique. After that, they were silylated and determined by gas chromatography combined to tandem mass spectrometry (GC/MS/MS). The influence of several factors on the yield and selectivity of the extraction was evaluated in detail. Under final working conditions, samples (0.5 g) were mixed with the same amount of anhydrous sodium sulfate and dispersed on 1.25 g of C18. This blend was transferred to the top of a polypropylene cartridge containing 2 g of Florisil. After removing less polar species with 10 mL of dichloromethane, analytes were recovered using 10 mL of acetonitrile. This extract was concentrated to 1 mL, derivatized, and injected in the GC/MS/MS system. Derivatization was carried out at 45 degrees C in 5 min using 100 microL of N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide. Quantification limits from 0.6 to 2.6 ng/g and absolute recoveries between 80 and 114% were achieved. Analysis of dust samples demonstrated the presence of the target species in indoor dust from private houses. The highest average concentration (702 ng/g) corresponded to triclosan.     

Determination of lysergic acid diethylamide (LSD), iso-LSD, and N-demethyl-LSD in body fluids by gas chromatography/tandem mass spectrometry.

Procedures for detection and quantitation of lysergic acid diethylamide (LSD), iso-LSD, and N-demethyl-LSD by capillary chromatography/tandem mass spectrometry (GC/MS/MS) are presented. Several methods for derivatization, sample introduction, and ionization, in combination with mass spectrometry/mass spectrometry (MS/MS), have been evaluated for overall ionization efficiency and product-ion sensitivity and specificity. Fragmentation pathways derived from low-energy collision-induced dissociation (CID) spectra of protonated LSD, and the protonated trimethylsllyl derivatives of LSD (LSD-TMS) and deuterium-labeled analogs of LSD, have been proposed. Principal dissociations primarily involve the amide and piperidine-ring moieties in which losses of CH3 radical, CH3NH2, CH3NCH2, diethylamine, diethylformamide, and N,N-diethylpropenamide from MH+ are observed. Positive-ion ammonia chemical ionization and subsequent MS/MS analysis of the protonated molecules (MH+) of the trimethylsilyl (TMS) derivatives of LSD, iso-LSD, and N-demethyl-LSD provide a high degree of specificity for identification of these compounds in urine or blood at low-pg/mL concentrations. Negative-ion chemical ionization and GC/MS/MS analysis of the molecular anion (M-) of the trifluoroacetyl (TFA) derivative is well suited for trace-level identification of N-demethyl-LSD, a metabolite of LSD.