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Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC-GC/MS.

Ahmed TM, Bergvall C, Åberg M, Westerholm R - Anal Bioanal Chem (2014)

Bottom Line: The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection.Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs.However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.

View Article: PubMed Central - PubMed

Affiliation: Department of Analytical Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.

ABSTRACT
The objective of this study was to develop a novel analytical chemistry method, comprised of a coupled high-performance liquid chromatography-gas chromatography/mass spectrometry system (LC-GC/MS) with low detection limits and high selectivity, for the identification and determination of oxygenated polycyclic aromatic hydrocarbons (OPAHs) and polycyclic aromatic hydrocarbons (PAHs) in urban air and diesel particulate matter. The linear range of the four OPAHs, which include 9,10-anthraquinone, 4H-cyclopenta[def]phenanthrene-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, was 0.7 pg-43.3 ng with limits of detection (LODs) and limits of quantification (LOQs) on the order of 0.2-0.8 and 0.7-1.3 pg, respectively. The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection. The recoveries of the OPAHs spiked onto glass fiber filters using two different pressurized liquid extraction (PLE) methods were in the ranges of 84-107 and 67-110 %, respectively. The analytical protocols were validated using the following National Institute of Standards and Technology standard reference materials: SRM 1649a (Urban Dust), SRM 1650b (Diesel Particulate Matter), and SRM 2975 (Diesel Particulate Matter, Industrial Forklift). The measured mass fractions of the OPAHs in the standard reference materials (SRMs) in this present study are higher than the values from the literature, except for benzanthrone in SRM 1649a (Urban Dust). In addition to the OPAHs, 44 PAHs could be detected and quantified from the same particulate extract used in this protocol. Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs. However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.

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GC/MS chromatograms (SIM) for the OPAHs in SRM 1649a. SRM 1650b (extracted ions for BaAQ are 258, 230, 222) and SRM 2975
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Fig1: GC/MS chromatograms (SIM) for the OPAHs in SRM 1649a. SRM 1650b (extracted ions for BaAQ are 258, 230, 222) and SRM 2975

Mentions: The same LC–GC/MS method was used for the analysis of OPAHs except that the LC mobile phase was changed to a mixture of hexane and methyl tert-butyl ether (8:2, v/v) with 0.1 % dodecane added, and the time for reversing the flow through the LC column was adjusted depending on the retention time for AQ-D8. The large injection volume is a back flush peak from the LC column monitored using the UV detector to transfer most of the part of interest onto the GC/MS (≥95 % for PAHs and ≥91 % for OPAHs). The MS system was set to acquire data in the selected ion monitoring (SIM) mode. The molecular ion and two analyte-specific fragments were monitored for each OPAH (see Table 2). The peak identities of the OPAHs in the SRM samples were confirmed by the retention times and relative ion ratios compared to the standard solutions. Concentrations of the PAHs and OPAHs in the SRM samples were calculated using the peak areas of the most abundant ions (see Fig. 1) and the relative response factors established from the calibration curves. Glass microfiber filters served as method blanks for the OPAHs and PAHs and were treated in the same manner as the samples throughout the entire analytical procedure.Table 2


Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC-GC/MS.

Ahmed TM, Bergvall C, Åberg M, Westerholm R - Anal Bioanal Chem (2014)

GC/MS chromatograms (SIM) for the OPAHs in SRM 1649a. SRM 1650b (extracted ions for BaAQ are 258, 230, 222) and SRM 2975
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4300434&req=5

Fig1: GC/MS chromatograms (SIM) for the OPAHs in SRM 1649a. SRM 1650b (extracted ions for BaAQ are 258, 230, 222) and SRM 2975
Mentions: The same LC–GC/MS method was used for the analysis of OPAHs except that the LC mobile phase was changed to a mixture of hexane and methyl tert-butyl ether (8:2, v/v) with 0.1 % dodecane added, and the time for reversing the flow through the LC column was adjusted depending on the retention time for AQ-D8. The large injection volume is a back flush peak from the LC column monitored using the UV detector to transfer most of the part of interest onto the GC/MS (≥95 % for PAHs and ≥91 % for OPAHs). The MS system was set to acquire data in the selected ion monitoring (SIM) mode. The molecular ion and two analyte-specific fragments were monitored for each OPAH (see Table 2). The peak identities of the OPAHs in the SRM samples were confirmed by the retention times and relative ion ratios compared to the standard solutions. Concentrations of the PAHs and OPAHs in the SRM samples were calculated using the peak areas of the most abundant ions (see Fig. 1) and the relative response factors established from the calibration curves. Glass microfiber filters served as method blanks for the OPAHs and PAHs and were treated in the same manner as the samples throughout the entire analytical procedure.Table 2

Bottom Line: The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection.Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs.However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.

View Article: PubMed Central - PubMed

Affiliation: Department of Analytical Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.

ABSTRACT
The objective of this study was to develop a novel analytical chemistry method, comprised of a coupled high-performance liquid chromatography-gas chromatography/mass spectrometry system (LC-GC/MS) with low detection limits and high selectivity, for the identification and determination of oxygenated polycyclic aromatic hydrocarbons (OPAHs) and polycyclic aromatic hydrocarbons (PAHs) in urban air and diesel particulate matter. The linear range of the four OPAHs, which include 9,10-anthraquinone, 4H-cyclopenta[def]phenanthrene-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, was 0.7 pg-43.3 ng with limits of detection (LODs) and limits of quantification (LOQs) on the order of 0.2-0.8 and 0.7-1.3 pg, respectively. The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection. The recoveries of the OPAHs spiked onto glass fiber filters using two different pressurized liquid extraction (PLE) methods were in the ranges of 84-107 and 67-110 %, respectively. The analytical protocols were validated using the following National Institute of Standards and Technology standard reference materials: SRM 1649a (Urban Dust), SRM 1650b (Diesel Particulate Matter), and SRM 2975 (Diesel Particulate Matter, Industrial Forklift). The measured mass fractions of the OPAHs in the standard reference materials (SRMs) in this present study are higher than the values from the literature, except for benzanthrone in SRM 1649a (Urban Dust). In addition to the OPAHs, 44 PAHs could be detected and quantified from the same particulate extract used in this protocol. Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs. However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.

Show MeSH