Simultaneous Flame Ionization Research Articles

On the use of quadrupole mass spectrometric detection for flow modulated comprehensive two-dimensional gas chromatography

Flow modulated comprehensive two-dimensional gas chromatography with simultaneous flame ionization detection (FM GC×GC-FID) and quadrupole mass spectrometric detection (FM GC×GC-qMSD) was applied to the analysis of a quantitative reference standard sample covering the C5–C14 hydrocarbon range and a kerosene sample. This study reports the influence of the data acquisition frequency (DAF) of the qMSD on the qualitative and quantitative data. The DAF was varied between 5.27 and 25.45Hz. In GC×GC-qMSD, the characterization of peaks is getting worse with decreasing qMSD frequencies which deteriorate the quality of the 2D contour plots of the separations. It is, however, demonstrated that the improved characterization of the peaks at high qMSD frequencies is combined with loss in sensitivity and in spectral quality. Dependences of a 2D hydrocarbon peak area (∑Ai of all corresponding 2D peaks) on the DAFs show negative slopes which testify the conclusion that the sensitivity of GC×GC-qMSD determinations decreases with the increase of DAF. Consequently, the limits of detection (LOD) and quantification (LOQ) increase with the increase of DAF. Moreover, quality criteria on recorded spectral data also indicate that the lower the DAF is, the higher is the spectral quality.

Identification of Volatiles by Headspace Gas Chromatography with Simultaneous Flame Ionization and Mass Spectrometric Detection

Volatiles are frequently abused as inhalants. The methods used for identification are generally nonspecific if analyzed concurrently with ethanol or require an additional analytical procedure that employs mass spectrometry. A previously published technique utilizing a capillary flow technology splitter to simultaneously quantitate and confirm ethyl alcohol by flame ionization and mass spectrometric detection after headspace sampling and gas chromatographic separation was evaluated for the detection of inhalants. Methanol, isopropanol, acetone, acetaldehyde, toluene, methyl ethyl ketone, isoamyl alcohol, isobutyl alcohol, n-butyl alcohol, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane (Norflurane, HFC-134a), chloroethane, trichlorofluoromethane (Freon®-11), dichlorodifluoromethane (Freon®-12), dichlorofluoromethane (Freon®-21), chlorodifluoromethane (Freon®-22) and 1,2-dichlorotetrafluoroethane (Freon®-114) were validated for qualitative identification by this method. The validation for qualitative identification included evaluation of matrix effects, sensitivity, carryover, specificity, repeatability and ruggedness/robustness.

On the use of ionic liquid capillary columns for analysis of aromatic hydrocarbons in low-boiling petrochemical products by one-dimensional and comprehensive two-dimensional gas chromatography

One-dimensional and comprehensive two-dimensional flow modulated gas chromatography with simultaneous flame ionization and mass spectrometric detection were applied for the identification and quantification of benzene, toluene, ethyl benzene and xylenes (BTEX) as well as of all C9–C11 aromatic hydrocarbons in the low-boiling petroleum products gasoline, reformate and fluid catalytic cracking (FCC) samples. GC×GC experiments were performed on two reversed phase polarity column sets namely SLB-IL100 (25m×250μm i.d.×0.2μm df)+HP-5MS (5m×250μm i.d.×0.25μm df) and SLB-IL111 (30m×250μm i.d.×0.2μm df)+HP-5MS (5m×250μm i.d.×0.25μm df). The one-dimensional GC experiments were carried out on the same ionic liquid columns. The most powerful method is GC×GC on the SLB-111+HP-5MS column combination. Quantitative analysis of individual aromatic hydrocarbons (C6–C11) present in gasoline, reformate and fluid catalytic cracking (FCC) samples was performed by GC×GC-FID using the internal normalization method. Mass spectra obtained by GC×GC-qMSD were used for identification of the aromatic hydrocarbons in these samples.

Flow-modulated comprehensive two-dimensional gas chromatography with simultaneous flame ionization and quadrupole mass spectrometric detection

Flow-modulated comprehensive two-dimensional gas chromatography with simultaneous monitoring of the separation by flame ionization (GC×GC-FID) and quadrupole mass spectrometric (GC×GC-qMSD) detection was studied for the analysis of gasoline and kerosene samples. The acquisition frequency of the FID was 100Hz and of the qMSD 18Hz for the mass range m/z 40–300. The instrumental set-up is such that both one-dimensional (GC-FID and GC-qMSD) and two-dimensional separations using the same working conditions can be performed. Gasoline and kerosene samples were analyzed on the column combination HP-5MS (1D)+HP INNOWax (2D). Three modulated peaks were obtained for each hydrocarbon present above 0.1% with ca. 300ms peak width at the base using 6 s modulation times. Modulated peaks in GC×GC-FID were thus characterized by ca. 30 points while those in GC×GC-qMSD method by 6–8 points only. The FID speed is sufficient for reliable quantitative analysis, while the qMSD scan speed is perfectly appropriate for identification purposes. Moreover, in the GC×GC-qMSD method considerably improved quality of uncorrected spectra was obtained, arising from the enhanced separation over one-dimensional GC-MSD analysis. Spectral match qualities of up to 98% were found.

Ethanol Analysis by Headspace Gas Chromatography with Simultaneous Flame-Ionization and Mass Spectrometry Detection

Ethanol is the most frequently identified compound in forensic toxicology. Although confirmation involving mass spectrometry is desirable, relatively few methods have been published to date. A novel technique utilizing a Dean's Switch to simultaneously quantitate and confirm ethyl alcohol by flame-ionization (FID) and mass spectrometric (MS) detection after headspace sampling and gas chromatographic separation is presented. Using 100 μL of sample, the limits of detection and quantitation were 0.005 and 0.010 g/dL, respectively. The zero-order linear range (r(2) > 0.990) was determined to span the concentrations of 0.010 to 1.000 g/dL. The coefficient of variation of replicate analyses was less than 3.1%. Quantitative accuracy was within ±8%, ±6%, ±3%, and ±1.5% at concentrations of 0.010, 0.025, 0.080, and 0.300 g/dL, respectively. In addition, 1,1-difluoroethane was validated for qualitative identification by this method. The validated FID-MS method provides a procedure for the quantitation of ethyl alcohol in blood by FID with simultaneous confirmation by MS and can also be utilized as an identification method for inhalants such as 1,1-difluoroethane.

Application of a multidimensional gas chromatography system with simultaneous mass spectrometric and flame ionization detection to the analysis of sandalwood oil

The production and trade of Indian sandalwood oil is strictly regulated, due to the impoverishment of the plantations; for such a reason, Australian sandalwood oil has been evaluated as a possible substitute of the Indian type. International directives report, for both the genuine essential oils, specific ranges for the sesquiterpene alcohols (santalols). In the present investigation, a multidimensional gas chromatographic system (MDGC), equipped with simultaneous flame ionization and mass spectrometric detection (FID/MS), has been successfully applied to the analysis of a series of sandalwood oils of different origin. A detailed description of the system utilized is reported. Three santalol isomers, (Z)-α-trans-bergamotol, (E,E)-farnesol, (Z)-nuciferol, epi-α-bisabolol and (Z)-lanceol have been quantified. LoD (MS) and LoQ (FID) values were determined for (E,E)-farnesol, used as representative of the oxygenated sesquiterpenic group, showing levels equal to 0.002% and 0.003%, respectively. A great advantage of the instrumental configuration herein discussed, is represented by the fact that identification and quantitation of target analytes are carried out in one step, without the need to perform two separate analyses.

Shock tube study of the decomposition of cyclopentyl radicals

The kinetics of the thermal decomposition of cyclopentyl radicals has been studied in a single-pulse shock tube over a temperature range of 950–1116K and pressures of 2.3–3.4bar. Cyclopentyl radicals were generated by abstraction of H from cyclopentane by H atoms, which were produced by the thermal decomposition of hexamethylethane. Products were analyzed using dual-column gas chromatography under cryogenic conditions with simultaneous flame-ionization and mass-spectrometric detection. The main stable products resulting from the decomposition of cyclopentyl radicals are ethene and cyclopentene. These results are consistent with the interconversion of cyclopentyl and pent-4-en-1-yl radicals. The product branching ratio of ethene to cyclopentene is determined as [ethene]/[cyclopentene]=(8.2±0.7)exp[−(1067±88)/T), where the listed uncertainty (1σ) is from the statistical analysis. The overall accuracy in our measurement of the branching ratio is estimated at about 8% (1σ). In contrast to previous estimates, ring opening of cyclopentyl is found to be faster than ejection of a hydrogen atom. The former reaction is favored by about a factor of three. An RRKM/Master Equation treatment was adopted to assign the rate parameters to elementary reactions. Details of the model and its compatibility with the present and literature results are presented. Kinetic results for the pyrolysis of cyclopentyl and pent-4-en-1-yl radicals have been derived over relevant combustion conditions [0.1–1000bar, 700–1900K].

A Deceptive Pollination System Targeting Drosophilids through Olfactory Mimicry of Yeast

In deceptive pollination, insects are bamboozled into performing nonrewarded pollination. A prerequisite for the evolutionary stability in such systems is that the plants manage to generate a perfect sensory impression of a desirable object in the insect nervous system [1]. The study of these plants can provide important insights into sensory preference of their visiting insects. Here, we present the firstdescription of a deceptive pollination system that specifically targets drosophilid flies. We show that the examined plant (Arum palaestinum) accomplishes its deception through olfactory mimicry of fermentation, a strategy that represents a novel pollination syndrome. The lily odor is composed of volatiles characteristic of yeast, and produces in Drosophila melanogaster an antennal detection pattern similar to that elicited by a range of fermentation products. By functional imaging, we show that the lily odors target a specific subset of odorant receptors (ORs), which include the most conserved OR genes in the drosophilid olfactome. Furthermore, seven of eight visiting drosophilid species show a congruent olfactory response pattern to the lily, in spite of comprising species pairs separated by ∼40 million years [2], showing that the lily targets a basal function ofthe fly nose, shared by species with similar ecological preference.

Cuticular Hydrocarbons as Sex Pheromone of the Bee Colletes cunicularius and the Key to its Mimicry by the Sexually Deceptive Orchid, Ophrys exaltata

Male Colletes cunicularius bees pollinate the orchid, Ophrys exaltata, after being sexually deceived by the orchid's odor-mimicry of the female bee's sex pheromone. We detected biologically active volatiles of C. cunicularius by using gas chromatographic-electroantennographic detection (GC-EAD) with simultaneous flame ionization detection. After identification of the target compounds by coupled gas chromatography mass spectrometry (GC-MS), we performed behavioral tests using synthetic blends of the active components. We detected 22 EAD active compounds in cuticular extracts of C. cunicularius females. Blends of straight chain, odd-numbered alkanes and (Z)-7-alkenes with 21-29 carbon atoms constituted the major biologically active compounds. Alkenes were the key compounds releasing mating behavior, especially those with (Z)-7 unsaturation. Comparison of patterns of bee volatiles with those of O. exaltata subsp. archipelagi revealed that all EAD-active compounds were also found in extracts of orchid labella. Previous studies of the mating behavior in C. cunicularius showed linalool to be an important attractant for patrolling males. We confirmed this with synthetic linalool but found that it rarely elicited copulatory behavior, in accordance with previous studies. A blend of active cuticular compounds with linalool elicited both attraction and copulation behavior in patrolling males. Thus, linalool appears to function as a long-range attractant, whereas cuticular hydrocarbons are necessary for inducing short-range mating behavior.

Development of a simple and sensitive method for the characterization of odorous waste gas emissions by means of solid-phase microextraction (SPME) and GC–MS/olfactometry

A solid-phase microextraction (SPME) method has been developed for the extraction of odorous compounds from waste gas. The enriched compounds were characterized by gas chromatography–mass spectrometry (GC–MS) and gas chromatography followed by simultaneous flame ionization detection and olfactometry (GC–FID/O). Five different SPME fiber coatings were tested, and the carboxen/polydimethylsiloxane (CAR/PDMS) fiber showed the highest ability to extract odorous compounds from the waste gas. Furthermore, parameters such as exposure time, desorption temperature, and desorption time have been optimized. The SPME method was successfully used to characterize an odorous waste gas from a fat refinery prior to and after waste gas treatment in order to describe the treatment efficiency of the used laboratory scale plant which consisted of a bioscrubber/biofilter combination and an activated carbon adsorber. The developed method is a valuable approach to provide detailed information of waste gas composition and complements existing methods for the determination of odors. However, caution should be exercised if CAR/PDMS fibers are used for the quantification of odorous compounds in multi-component matrices like waste gas emissions since the relative affinity of each analyte was shown to differ according to the total amount of analytes present in the sample.

Simultaneous Flame Ionization and Absorbance Detection of Volatile and Nonvolatile Compounds by Reversed-Phase Liquid Chromatography with a Water Mobile Phase

A flame ionization detector (FID) is used to detect volatile organic compounds that have been separated by water-only reversed-phase liquid chromatography (WRP-LC). The mobile phase is 100% water at room temperature, without use of organic solvent modifiers. An interface between the LC and detector is presented, whereby a helium stream samples the vapor of volatile components from individual drops of the LC eluent, and the vapor-enriched gas stream is sent to the FID. The design of the drop headspace cell is simple because the water-only nature of the LC separation obviates the need to do any organic solvent removal prior to gas phase detection. Despite the absence of organic modifier, hydrophobic compounds can be separated in a reasonable time due to the low phase volume ratio of the WRP-LC columns. The drop headspace interface easily handles LC flows of 1 mL/min, and, in fact, compound detection limits are improved at faster liquid flow rates. The transfer efficiency of the headspace interface was estimated at 10% for toluene in water at 1 mL/min but varies depending on the volatility of each analyte. The detection system is linear over more than 5 orders of 1-butanol concentration in water and is able to detect sub-ppb amounts of o-xylene and other aromatic compounds in water. In order to analyze volatile and nonvolatile analytes simultaneously, the FID is coupled in series to a WRP-LC system with UV absorbance detection. WRP-LC improves UV absorbance detection limits because the absence of organic modifier allows the detector to be operated in the short-wavelength UV region, where analytes generally have significantly larger molar absorptivities. The selectivity the headspace interface provides for flame ionization detection of volatiles is demonstrated with a separation of 1-butanol, 1,1,2-trichloroethane (TCE), and chlorobenzene in a mixture of benzoic acid in water. Despite coelution of butanol and TCE with the benzoate anion, the nonvolatile benzoate anion does not appear in the FID signal, allowing the analytes of interest to be readily detected. The complementary selectivity of UV-visible absorbance detection and this implementation of flame ionization detection allows for the analysis of volatile and nonvolatile components of complex samples using WRP-LC without the requirement that all the components of interest be fully resolved, thus simplifying the sample preparation and chromatographic requirements. This instrument should be applicable to routine automated water monitoring, in which repetitive injection of water samples onto a gas chromatograph is not recommended.

Pheromone specificity inEriocrania semipurpurella (Stephens) andE. sangii (Wood) (Lepidoptera: Eriocraniidae) based on chirality of semiochemicals

The fifth abdominal segment of femaleEriocrania semipurpurella (Stephens) andE. sangii (Wood) contains a pair of exocrine glands. Hexane extracts of this segment were prepared from both species and analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). For both species, the EAD active peaks were identified as nonan-2-one, (Z)-6-nonen-2-one, and (Z)-6-nonen-2-ol by means of mass spectrometry and comparison of retention indices with those of synthetic standards. Enantiomeric separation of chiral alcohols from the female extracts was achieved by gas chromatographic analysis on a cyclodextrin column. InE. semipurpurella, a mixture of (2S,6Z)-nonen-2-ol and (2R,6Z)-nonen-2-ol (2: I) was found, whereas inE. sangii (2S,6Z)-nonen-2-ol was the predominant enantiomer and only traces of theR enantiomer were indicated by the antennal response. In field tests, a blend of the three compounds was not attractive to conspecific males. A subtractive assay showed that the alcohol in various enantiomeric mixtures was the only attractive compound, whereas addition of (Z)-6-nonen-2-one to the alcohol completely inhibited the attraction of both species. A trapping experiment including a wide range of ratios between theR andS enantiomers showed that baits containing 95-100% of theS enantiomer were attractive to maleE. sangii, whereas males ofE. semipurpurella were attracted to all tested ratios of the enantiomers. However, the response profiles of maleE. semipurpurella differed between populations from southern Sweden, south Finland, and the Kola Peninsula in Russia. In south Sweden males were maximally attracted to a racemic mixture of the alcohols. At the Kola PeninsulaE. semipurpurella was attracted to baits containing 95-100% of theR enantiomer. In south Finland all tested ratios between 0 and 100%R enantiomer trappedE. semipurpurella, but the trap catches appeared to be bimodally distributed with peaks around 15 and 70%R enantiomer. The trapping results suggest the existence of pheromone races or sibling species among the specimens identified asE. semipurpurella.

95/05455 Fluorescence spectroscopic studies of mesophase formation (letter)

Molecular characterization of the kerogen and asphaltene fractions isolated from three oil shales taken at increasing depth from the same deposit was carried out by means of flash pyrolysis-gas chromatography. Pyrolysis products were detected by simultaneous flame ionization detection and sulphur-selective flame photometric detection using a stream splitter at the end of the capillary column. n-Alkanes, n-alk-1-enes and sulphur compounds represent the major pyrolysis products of both kerogen and asphaltene fractions. Organosulphur compounds were only detected in the kerogen fractions and were completely absent from the asphaltene fractions. A sequential removal of thiophenes was observed in the set of kerogens. It is suggested that breakdown of sulphur-sulphur and carbon-sulphur bonds may occur preferentially in the kerogen macromolecule rather than the breakdown of carbon-carbon bonds to give rise to the asphaltenes.

Identification of a novel moth sex pheromone inEriocrania cicatricella (Zett.) (Lepidoptera: Eriocraniidae) and its phylogenetic implications

Extracts from different body parts of adult femaleEriocrania cicatricella (Zett.) were tested for electrophysiological activity on conspecific male antennae. Extracts from the Vth abdominal segment, containing a pair of exocrine glands, elicited the largest electroantennographic response when compared to extracts of other body parts. Female extracts were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). The EAD active peaks were identified as (Z)-4-hepten-2-one, (2R)-heptane-2-ol, and (2R)-(Z)-4-hepten-2-ol by coinjection on a gas chromatography and by comparison of mass spectra with those of synthetic standards. In field tests, a blend of these three pheromone components was highly attractive to conspecific males, and a subtractive assay confirmed that the unsaturated alcohol is the major pheromone component, whereas no definite behavioral activity could be assigned to the ketone or the saturated alcohol. A bait containing the two alcohols withS-configuration was attractive to maleE. sparrmannella (Bosc), whereas no males ofE. cicatricella were found in these traps. The sex pheromone compounds inE. cicatricella are chemically similar to pheromones reported in Trichoptera and they are produced in homologous glands.

Pheromonal secretions from glands on the 5th abdominal sternite of hydropsychid and rhyacophilid caddisflies (Trichoptera)

Extracts of different body parts of adult Trichoptera were tested for electrophysiological activity. Extracts of the IVth and Vth abdominal sternites of femaleHydropsyche angustipennis, Rhyacophila nubila, andR. fasciata, containing a paired exocrine gland, elicited significant electroan-tennographic responses when tested on conspecific male antennae. The paired gland occurs also in males of all the species, and inH. angustipennis, extracts from males were more active than female extracts when tested on male antennae. Female and male extracts from all species were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). EAD-active peaks in female extracts, stimulating male antennae, were identified inH. angustipennis as nonan-2-one; and inR. nubila andR. fasciata as heptan-2-one, heptan-2-ol, nonan-2-one, and nonan-2-ol. EAD-active components from maleH. angustipennis stimulating male antennae were octan-2-one, nonan-2-one (major peak), (Z)-6-nonen-2-one, decan-2-one, and a methylbranched decan-2-one. Female extracts and synthetic mixtures of compounds identified from femaleH. angustipennis andR. fasciata were tested for attractivity in the field. High catches with control traps obscured the results, but a synthetic mixture of the four identified compounds was significantly attractive and not different from female extracts for attracting maleR. fasciata. InH. angustipennis, a synthetic six-component male blend, in which nonan-2-one was the major component, attracted significant numbers of male and femaleH. angustipennis. Extracts of maleR. nubila andR. fasciata contained acetophenone and hexanoic and octanoic acids but did not have any electrophysiological or behavioral activity on either male or female antennae of conspecifics. The occurrence of a female sex pheromone inRhyacophila and an aggregation pheromone inHydropsyche corresponds to earlier described differences in mating behaviors in the Rhyacophilidae and Hydropsychidae.

Pheromone differences between sibling taxaDiachrysia chrysitis (linnaeus, 1758) andD. tutti (Kostrowicki, 1961) (Lepidoptera: Noctuidae)

The noctuid sibling taxaDiachrysia chrysitis s. str. andD. tutti, of yet uncertain taxonomic status, have previously been shown to possess differences in morphology and to be attracted to different mixtures of the two presumed pheromone components (Z)-5-decenyl acetate and (Z)-7-decenyl acetate. TypicalD. tutti males (clearly broken forewing marking) are known to respond to a 2: 100 mixture of the two isomers, whereasD. chrysitis males (unbroken marking) are attracted to a 100: 10 mixture. We investigated female pheromone production and male electroantennographic (EAG) response inDiachrysia families raised in the laboratory from field-collected gravid females. Extracts of individual females from typicalD. tutti andD. chrysitis families were subjected to gas chromatography with simultaneous flame ionization and electroantennographic detection. All females produced mixtures of Z5- and Z7-10:OAc, but femaleD. chrysitis produced predominantly Z5-10:OAc and the antennae of their brothers responded more strongly to the Z5 peak than to the Z7-10:OAc peak, whereas the opposite was true forD. tutti families. The pheromone components were shown to be biosynthesized from hexadecanoic and tetradecanoic acid, respectively by Z11-desaturation followed by chain shortening, reduction, and acetylation. The EAG responses of males trapped with the typicalD. tutti andD. chrysitis blends, as well as with an intermediate blend, were investigated. Males trapped with theD. tutti mixture almost exclusively had a clearly broken wing marking and showed strongest EAG response to Z7-10:OAc. The intermediate blend and theD. chrysitis mixture gave more mixed catches, but with a prevalence of males with an unbroken (or almost unbroken) wing marking and with a higher mean response to Z5-10:OAc. Some males with typicalD. tutti EAG responses were attracted in the field to theD. chrysitis pheromone. In the flight tunnel someD. chrysitis males were attracted also to theD. tutti mixture. This indicates that cross attraction may take place between the two taxa under natural conditions.

Flash pyrolysis-gas chromatography of the kerogen and asphaltene fractions isolated from a sequence of oil shales

Molecular characterization of the kerogen and asphaltene fractions isolated from three oil shales taken at increasing depth from the same deposit was carried out by means of flash pyrolysis-gas chromatography. Pyrolysis products were detected by simultaneous flame ionization detection and sulphur-selective flame photometric detection using a stream splitter at the end of the capillary column. n-Alkanes, n-alk-1-enes and sulphur compounds represent the major pyrolysis products of both kerogen and asphaltene fractions. Organosulphur compounds were only detected in the kerogen fractions and were completely absent from the asphaltene fractions. A sequential removal of thiophenes was observed in the set of kerogens. It is suggested that breakdown of sulphur-sulphur and carbon-sulphur bonds may occur preferentially in the kerogen macromolecule rather than the breakdown of carbon-carbon bonds to give rise to the asphaltenes.

Retention index monitoring of compounds of chemical defence interest using thermal desorption gas chromatography

Retention index monitoring using thermal desorption gas chromatographic analysis was developed as a method for the verification of compounds of chemical defense interest in environmental matrices. Gas chromatography retention indices were determined by loading solid adsorbent packed sampling tubes initially with the target compounds and subsequently wih a series of n-alkane probes. The resulting chromatographic performance and gas chromatography retention indices were shown to be independent of the tube loading method. A database of gas chromatography retention indices for chemical warfare agents and simulants was compiled and, in conjunction with simultaneous flame ionization and flame photometric detection, applied to the identification of triethyl phosphate, tributyl phosphate and diethyl malonate in water and soil samples.

Capillary gas chromatography of steroidal alkaloids from solanaceae : Retention indices and simultaneous flame ionization/nitrogen-specific detection

A capillary gas chromatography method for identification and quantification of Solanum and Lycopersicon C 27-steroidal alkaloids (SAs) was developed. Hydrogen was used as the carrier gas to achieve a relatively short analysis duration. Simultaneous flame ionization and nitrogen-specific detection (FID and NPD) enabled unambiguous differentiation between SAs and closely related non-nitrogen-containing compounds, such as sterols and steroidal sapogenins. Calibration plots for FID and NPD were linear for all individual SAs tested. The NPD/FID response ratios appeared to be an aid in identification and characterization of the compounds. Tuber samples of Solanum species varied in contents of solanidine glycosides from 600 to 6220 mg kg −1 fresh weight. Because of these larger differences, identification by retention times was not possible, but retention indices were sufficiently reproducible even for identification of the closely eluting Δ5- and 5α-aglycone pair solanidine and demissidine. Although, SAs are not usually easily quantified by capillary gas chromatography, quantitative analyses can be done routinely provided sufficient attention is paid to the accuracy and precision of the sample injection.

Sample integrity of trace level volatile organic compounds in ambient air stored in SUMMA® polished canisters

Sets of new and used SUMMA® polished stainless steel canisters were tested for storage stability of volatile organic compounds (VOCs). Evacuated canisters were filled at a controlled rate with ambient air containing added concentrations of 15 VOCs (14 chlorinated, one brominated) at < 2 ppbv. Concentrations of VOCs in each canister were then periodically determined during 7-day or 30-day storage periods using simultaneous flame ionization and electron capture detection. No initial decreases in concentrations of target compounds were observed. Statistical analysis of data showed that the relative standard deviation of concentrations of most VOCs in each canister set was 10% or less during the storage periods. For the 7-day tests, the mean change in concentration per day was within ± 3.2 %. These canisters appear suitable as an alternative to other sampling techniques, at least for most of the compounds tested here.