Håkan Carlsson

On-line coupling of supercritical fluid extraction with high-performance liquid chromatography for the determination of explosives in vapour phases

An analytical method for determining nitroaromatic explosives in vapour phases is presented. Samples were collected by pumping air through glass fibre filters and polyurethane foam adsorbents, and an on-line extraction system combining supercritical fluid extraction (SFE) and high-performance liquid chromatography (HPLC) was developed. This allows analytes to be transferred from the adsorbent to the HPLC system via a porous graphitic carbon trap. When using gradient elution with a suitable mobile phase, most of the nitroaromatic isomers tested were separated. The proposed method is fully automated, allows a complete analysis to be processed in less than 30 min, and it is compatible with most of the organic solvents commonly used as SFE modifiers or additives. The method has been applied to the analysis of real samples obtained from headspace sampling of military-grade 2,4,6-trinitrotoluene and has been shown to constitute a promising alternative for assessing whether areas are mined in landmine-clearing operations.

Dynamic sonication-assisted solvent extraction of organophosphate esters in air samples.

A new system for extracting solid samples based on dynamic sonication-assisted solvent extraction (DSASE) is described. The technique is highly efficient with respect to both time and solvent consumption. In tests reported here, organophosphate esters were extracted from air sampling filters in 3 min with an extraction volume of 600 microL of solvent. Furthermore, it was possible to replace a previously used chlorinated solvent with a halogen-free solvent mixture. The sample was placed in a cartridge through which fresh solvent was pumped continuously. A restrictor connected to the outlet of the cartridge allowed the system to be used at a temperature of 70 degrees C without reaching the boiling point of the solvent. Both spiked and non-spiked native samples were used for the evaluation, which clearly revealed a stronger analyte-matrix interaction in native samples. The DSASE technique was shown to recover larger amounts of organophosphate esters from native samples, compared to a static method. DSASE was applied to air samples collected in a lecture hall and from above a computer monitor.

Determination of organophosphate esters in air samples by dynamic sonication-assisted solvent extraction coupled on-line with large-volume injection gas chromatography utilizing a programmed-temperature vaporizer

An on-line method for the determination of airborne organophosphate esters based on dynamic sonication-assisted solvent extraction and large-volume injection (LVI) gas chromatography with nitrogen-phosphorous detection is introduced. The LVI is performed with a programmed-temperature vaporizer. The entire extracted fraction of 800 microl (hexane-methyl-tert.-butyl ether, 7:3, v/v) is introduced directly into the GC system without any clean-up step following extraction. The extraction and analysis step were completed in less than 15 min. The limit of detection of the investigated organophosphate esters was established to be in the range of 5-32 pg/filter. The correlation coefficients (r2) were investigated in the linear range study of the entire system and established to be approximately 0.9900 for all the investigated organophosphates esters. Applications of the method was demonstrated with the extraction of air samples collected onto glass fiber filters from different indoor environments. Six organophosphate esters were found at the levels 0.4-138 ng/m3.

Clean-up and analysis of carbazole and acridine type polycyclic aromatic nitrogen heterocyclics in complex sample matrices

Abstract A HPLC method for the analysis of polycyclic aromatic nitrogen heterocyclics (PANHs) in complex sample matrices is presented. It isolated and separated carbazole and acridine type PANHs with an absolute recovery of between 79–98%. Open column chromatography is used as an initial step to isolate a PANH fraction. By applying normal-phase liquid chromatography using a dimethylaminopropyl silica stationary phase and utilising back-flush technique it was possible to separate the PANH fraction into two fractions containing acridine type and carbazole type PANHs, respectively. The method applied on a sample of solvent refined coal heavy distillate (SRC II HD). A number of 3–5 ring acridines and carbazoles were identified with GC–electron impact MS and quantified with GC–nitrogen–phosphorous detection. Polycyclic aromatic hydrocarbons (PAHs) were determined in the SRC II HD sample by automated on-line clean-up and analysis of the obtained PAH fraction with coupled LC–GC–flame ionization detection. There was no overlap between the PANH and the PAH fractions with this method, and carbazoles and acridines were efficiently separated.

Coupled LC‐GC‐NPD for Determination of Carbazole‐Type PANH and Its Application to Personal Exposure Measurement

This thesis is based on studies in which the suitability of various gas chromatography (GC) injection techniques was examined for the determination of polybrominated diphenyl ethers (PBDEs) and carbazoles, two groups of compounds that are thermally labile and/or have high boiling-points. For such substances, it is essential to introduce the samples into the GC system in an appropriate way to avoid degradation and other potential problems. In addition, different types of gas chromatographic column system and mass spectrometric detectors were evaluated for the determination of PBDEs.Conventional injectors, such as splitless, on-column and programmed temperature vaporizing (PTV) injectors were evaluated and optimized for determination of PBDEs. The results show on-column injection to be the best option, providing low discrimination and high precision. The splitless injector is commonly used for “dirty” samples. However, it is not suitable for determination of the high molecular weight congeners, since it tends to discriminate against them and promote their degradation, leading to poor precision and accuracy. The PTV injector appears to be a more suitable alternative. The use of liners reduces problems associated with potential interferents such as polar compounds and lipids and compared to the hot splitless injector, it provides gentler solvent evaporation, due to its temperature programming feature, leading to low discrimination and variance.Increasing the injection volume from the conventional 1-3 µL to >50 µL offers two main benefits. Firstly, the overall detection and quantification limits are decreased, since the entire sample extract can be injected into the GC system. Secondly, large volume injections enable hyphenation of preceding techniques such as liquid chromatography (LC), solid phase extraction and other kinds of extraction. Large-volume injections were utilized and optimized in the studies included in this thesis.With a loop-type injector/interface large sample volumes can be injected on-column providing low risk of discrimination against compounds with low volatility. This injector was used for the determination of PBDEs in air and as an interface for the determination of carbazoles by LC-GC. Peak distortion is a frequently encountered problem associated with this type of injector that was addressed and solved during the work underlying this thesis.The PTV can be used as a large volume injector, in so-called solvent vent mode. This technique was evaluated for the determination of PBDEs and as an interface for coupling dynamic sonication-assisted solvent extraction online to GC. The results show that careful optimization of the injection parameters is required, but also that the PTV is robust and yields reproducible results.PBDEs are commonly detected using mass spectrometry in electron capture negative ionization (ECNI) mode, monitoring bromine ions (m/z 79 and 81). The mass spectrometric properties of the fully brominated diphenyl ether, BDE-209, have been investigated. A high molecular weight fragment at m/z 486/488 enables the use of 13C-labeled BDE-209 as an internal surrogate standard.

PARTICULATE AND SEMIVOLATILE ASSOCIATED ALIPHATIC HYDROCARBON EXHAUST EMISSION FROM HEAVY DUTY DIESEL VEHICLES

The exhaust emissions from two heavy duty diesel vehicles running on eight different fuel compositions were investigated regarding their content of high molecular weight (≥ C12) aliphatic/ olefinic hydrocarbons. It was concluded that the emitted amount of semi‐volatile associated aliphatic hydrocarbons (range C12‐C22) depend on the fuel used in the engines and that these emissions mainly consisted of uncombusted fuel components. It was also found that uncombusted engine lubrication oil was the main constituent of the emitted particulate associated aliphatic hydrocarbons (C17‐C40). These constituted between 58% and 95% of the total emissions of the high molecular weight aliphatic compounds. Emission factors for the total of high molecular aliphatic hydrocarbons (C12‐C40) were demonstrated to be in the range of 15–100 mg/km. Some individual aliphatic hydrocarbons with cocarcinogenic effects were identified and quantified in both particulate and semi‐volatile phases of the exhaust. Multivariate data analysis...