Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Methods for Determination of Benzo(a)pyrene and High Molecular Weight (>300 Da) Polycyclic Aromatic Hydrocarbons in Particulate Matter from Ambient Air and Vehicle Exhausts
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Air pollution with particulate matter (PM) raises considerable concern because of its adverse effects on human health. For this reason, and because the mechanisms of PM toxicity are not fully known, there is an urgent need to determine the chemical constituents of atmospheric PM, especially PM emanating from traffic - a major source of urban PM.

This thesis describes analytical methods that have been developed for determining polycyclic aromatic hydrocarbons (PAHs) in ambient air and vehicle exhaust PM, focusing particularly on benzo(a)pyrene (B(a)P) and the dibenzopyrenes: dibenzo(a,l)pyrene, dibenzo(a,e)pyrene, dibenzo(a,i)pyrene and dibenzo(a,h)pyrene. Trace amounts in complex matrices have been met by coupling parts or the entire clean-up step using liquid chromatography on-line with the analysis step using gas chromatography-mass spectrometry into one automated system.

Application of the methodology, using either ultrasonic assisted extraction (USE) or accelerated solvent extraction (ASE), to a National Institute of Standards and Technology (NIST) urban air standard reference material (SRM) yielded comparable or higher concentrations than the assigned NIST values, validating the approach. However, ASE provided higher extraction yields from diesel particulate SRMs than USE, and ASE of diesel SRMs generally yielded higher concentrations than the corresponding NIST values.

Concentrations of dibenzopyrenes in Stockholm air PM, and gasoline- and diesel-fuelled vehicle emissions (ng/km), are reported for the first time. When adjusted in terms of their relative carcinogenic potencies, the dibenzopyrenes were found to pose greater carcinogenic hazards than B(a)P, indicating that the current use of B(a)P as a marker probably leads to underestimates of the carcinogenicity of PAHs in ambient air.

The developed methods also worked well for analyzing larger molecular weight PAHs: more than 60 and 170 potential PAHs were detected in ambient air PM and diesel PM, respectively.

Place, publisher, year, edition, pages
Stockholm: Department of Analytical Chemistry, Stockholm , 2009. , 97 p.
Keyword [en]
PAH, dibenzopyrene, benzo(a)pyrene, standard reference material, air particulate matter, diesel particulate matter, toxic equivalence factor, ultrasonic assisted extraction, accelerated solvent extraction, automation, online coupling, GC/MC, LC/GC/MS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-29749ISBN: 978-91-7155-920-3 (print)OAI: oai:DiVA.org:su-29749DiVA: diva2:235028
Public defence
2009-10-16, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2009-09-24 Created: 2009-09-11 Last updated: 2009-09-22Bibliographically approved
List of papers
1. Determination of dibenzopyrenes in standard reference materials (SRM) 1649a, 1650, and 2975 using ultrasonically assisted extraction and LC-GC-MS
Open this publication in new window or tab >>Determination of dibenzopyrenes in standard reference materials (SRM) 1649a, 1650, and 2975 using ultrasonically assisted extraction and LC-GC-MS
2006 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 384, no 2, 438-447 p.Article in journal (Refereed) Published
Abstract [en]

A method has been developed for analysis of the highly potent polycyclic aromatic hydrocarbon (PAH) carcinogens dibenzo(a,l)pyrene, dibenzo(a,h)pyrene and dibenzo(a,i)pyrene (molecular weight 302) present in small amounts in diesel and air particulate materials. The method can also be used for analysis of the PAH benzo(a)pyrene, coronene and perylene, for which reference and certified values are available for the Standard Reference Materials used for validation of the method: SRM 1649a (Urban dust) and SRM 2975 (Diesel particulate matter). The only NIST values that have been published for these dibenzopyrene isomers in the analyzed SRMs are reference values for dibenzo(a,i)pyrene and dibenzo(a,h)pyrene in SRM 1649a. The concentrations determined in the SRMs were in good agreement with reported NIST-certified and reference values and other concentrations reported in the literature. The Standard Reference Material 1650 (Diesel particulate matter) was also analyzed. The method could not, however, be validated using this material because certification of SRM 1650 had expired. The method is based on ultrasonically-assisted extraction of the particulate material, then silica SPE pre-separation and isolation, and, separation and detection by hyphenated LC-GC-MS. The method is relatively rapid and requires only approximately 1-5 mg SRM particulate material to identify and quantify the analytes. Low extraction recoveries for the analytes, in particular the dibenzopyrenes, when extracting diesel SRMs 2975 and 1650 resulted, however, in the dibenzopyrenes being present in amounts near their limit of quantifications in these samples. The method’s limit of quantification (LOQ), based on analyses of SRM 1649a, is in the range of 10-77 pg. By use of this method more than 25 potential PAH isomers with a molecular weight of 302 could be separated.

Place, publisher, year, edition, pages
Heidelberg, Germany: Springer-Verlag, 2006
Keyword
Dibenzopyrenes, LC-GC-MS, PAH, SRM 1649a, SRM 1650, SRM 2975
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-29579 (URN)10.1007/s00216-005-0192-5 (DOI)
Available from: 2009-09-09 Created: 2009-09-07 Last updated: 2017-12-13Bibliographically approved
2. Identification and Determination of Highly Carcinogenic Dibenzopyrene Isomers in Air Particulate Samples from a Street Canyon, a Rooftop, and a Subway Station in Stockholm
Open this publication in new window or tab >>Identification and Determination of Highly Carcinogenic Dibenzopyrene Isomers in Air Particulate Samples from a Street Canyon, a Rooftop, and a Subway Station in Stockholm
2007 (English)In: Environmental Science & Technology, ISSN 0013-936X, Vol. 41, no 3, 731-737 p.Article in journal (Refereed) Published
Abstract [en]

This study presents determined levels of the highly carcinogenic dibenzopyrene isomers dibenzo(a,l)pyrene, dibenzo(a,e)pyrene, dibenzo(a,i)pyrene, and dibenzo(a,h)pyrene as well as three other polycyclic aromatic hydrocarbons (PAHs)benzo(a)pyrene, perylene and coronenein ambient particulate material samples from a street canyon, a rooftop, and an underground subway station in Stockholm, Sweden. To our knowledge, these are the first reported determinations of dibenzopyrene isomers in air particles from either Stockholm or a subway station. Taking into account both concentration and toxic equivalence factors (TEFs), the PAH with the highest carcinogenic potency in the analyzed samples was dibenzo(a,l)pyrene, and the sum carcinogenic potency of the determined dibenzopyrenes was about 1−4 times higher than that of benzo(a)pyrene in the analyzed samples. These findings indicate that it is important to analyze the dibenzopyrene isomers as well as benzo(a)pyrene; the common approach of using benzo(a)pyrene as an indicator substance could lead to underestimates of the potential carcinogenic potency of PAHs in ambient air. The results also indicate that the relative carcinogenic potency of the determined dibenzopyrenes and benzo(a)pyrene in air particles from Stockholm is similar to that of air particles sampled in Washington in 1976−1977, despite general improvements in air quality in the intervening period. However, more data are needed to characterize temporal variations in dibenzopyrene levels in locations such as subway stations, suburbs, road tunnels, and metropolitan areas. There is also a need to identify and characterize both stationary and mobile PAH sources with respect to emission of dibenzopyrene isomers.

Place, publisher, year, edition, pages
Washington DC, USA: ACS Publishing, 2007
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-10789 (URN)10.1021/es062232p (DOI)000244002800020 ()
Available from: 2009-09-09 Created: 2008-01-07 Last updated: 2009-09-16Bibliographically approved
3. Determination of 252-302 Da and tentative identification of 316-376 Da polycyclic aromatic hydrocarbons in Standard Reference Materials 1649a Urban Dust and 1650b and 2975 Diesel Particulate Matter by accelerated solvent extraction-HPLC-GC-MS.
Open this publication in new window or tab >>Determination of 252-302 Da and tentative identification of 316-376 Da polycyclic aromatic hydrocarbons in Standard Reference Materials 1649a Urban Dust and 1650b and 2975 Diesel Particulate Matter by accelerated solvent extraction-HPLC-GC-MS.
2008 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 391, no 6, 2235-2248 p.Article in journal (Refereed) Published
Abstract [en]

We have assessed and compared the extraction recoveries of polycyclic aromatic hydrocarbons (PAHs) with molecular weights of 252, 276, 278, 300 and 302 from diesel particulate matter (PM) and urban air particles using ultrasonically-assisted extraction and accelerated solvent extraction methods, and evaluated the effects of sample and treatment parameters. The results show that accelerated solvent extraction can extract PAHs more efficiently from diesel PM than ultrasonically assisted extraction. They also show that PAHs are more difficult to extract from diesel PM than from urban air particles. Using toluene and maximum instrumental settings (200 ºC, 3000 psi and five extraction cycles) with 30 min static extraction times > 85 % of the analytes were estimated to be extracted from the diesel particles, but four extraction cycles with just 5 min static extraction times under these conditions seems to be sufficient to extract > 95 % of the analytes from the urban air particles. The accelerated solvent extraction method was validated using Standard Reference Materials (SRM) 1649a, Urban Dust, SRM 2975 and SRM 1650a, Diesel Particulate Matter, from the US National Institute of Standards and Technology (NIST). PAH concentrations determined by on-line high performance liquid chromatography-gas chromatography-mass spectrometry following the developed accelerated solvent extraction method were generally higher than the certified and reference NIST values and concentrations reported in the literature (e.g. the estimated concentration of benzo(a)pyrene in SRM 2975 was 15-fold higher than the NIST-certified value), probably because the extraction recoveries were higher than in previous studies. The developed accelerated solvent extraction method was used to analyze high molecular weight PAHs (Mw>302) in the investigated SRMs, and more than 170 (SRM 1649a), 80 (SRM 1650b) and 60 (SRM 2975) potential high molecular weight PAHs were tentatively identified in them, with molecular weights (depending on the SRM sample analysed) of 316, 326, 328, 340, 342, 350, 352, 366, 374 and 376. This is, to our knowledge, the first study to tentatively report PAHs with molecular weights of 316, 326, 328, 342, 350, 352, 366 and 374 in diesel particulate matter. GC-MS chromatograms obtained in selected ion monitoring mode (extracted ions for the above mentioned m/z) and full-scan mass spectra of tentatively identified high molecular weight PAHs are shown in the electronical supplementary material.

Place, publisher, year, edition, pages
Heidelberg, Germany: Springer-Verlag, 2008
Keyword
ASE, PAH, Dibenzopyrene, HMW PAH, SRM 1649a, SRM 1650b, SRM 2975
National Category
Chemical Sciences
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-29584 (URN)10.1007/s00216-008-2182-x (DOI)000257200200029 ()
Available from: 2009-09-09 Created: 2009-09-07 Last updated: 2017-12-13Bibliographically approved
4. Determination of highly carcinogenic dibenzopyrene isomers in particulate emissions from two diesel- and two gasoline-fuelled light-duty vehicles
Open this publication in new window or tab >>Determination of highly carcinogenic dibenzopyrene isomers in particulate emissions from two diesel- and two gasoline-fuelled light-duty vehicles
2009 (English)In: Atmospheric Environment, ISSN 1352-2310, E-ISSN 1873-2844, Vol. 43, no 25, 3883-3890 p.Article in journal (Refereed) Published
Abstract [en]

Emission factors of particulate-bound Polycyclic Aromatic Hydrocarbons (PAHs) including benzo(a)pyrene and, for the first time, the highly carcinogenic dibenzo(a,l)pyrene, dibenzo(a,e)pyrene, dibenzo(a,i)pyrene and dibenzo(a,h)pyrene have been determined in exhausts from two diesel- (DFVs) and two gasoline-fuelled light-duty vehicles (GFVs) operated in the Urban (AU), Rural Road (AR) and Motorway (AM) transient ARTEMIS driving cycles. The obtained results showed the DFVs to emit higher amounts of PAHs than the GFVs per km driving distance at low average speed in the AU driving cycle, while the GFVs emitted higher amounts of PAHs than the DFVs per km driving distance at higher average speeds in the AR and AM driving cycles. Furthermore, the study showed an increase in PAH emissions per km driving distance with increasing average speed for the GFVs with the opposite trend found for the DFVs. The GFVs generated particulate matter with higher PAH content than the DFVs in all three driving cycles tested with the highest concentrations obtained in the AR driving cycle. Dibenzo(a,l)pyrene was found to be a major contributor to the potential carcinogenicity accounting for 58–67% and 25–31% of the sum added potential carcinogenicity of the measured PAHs in the emitted particulate matter from the DFVs and GFVs, respectively. Corresponding values for benzo(a)pyrene were 16–25% and 11–40% for the DFVs and GFVs, respectively. The DFVs displayed higher sum added potential carcinogenicity of the measured PAHs than the GFVs in the AU driving cycle with the opposite trend found in the AR and AM driving cycles. The findings of this study show the importance of including the dibenzopyrenes in vehicle exhaust chemical characterizations to avoid potential underestimation of the carcinogenic activity of the emissions. The lower emissions and the lower sum added potential carcinogenicity of the measured PAHs found in this study for the GFVs compared to the DFVs in the AU driving cycle indicate the GFVs to be preferred in dense urban areas with traffic moving at low average speeds with multiple start and stops. However, the obtained results suggest the opposite to be true at higher average speeds with driving at rural roads and motorways. Further studies are, however, needed to establish if the observed differences between GFVs and DFVs are generally valid as well as to study the effects on variations in vehicle/engine type, ambient temperature, fuel and driving conditions on the emission factors.

Keyword
Regulated emissions, Particle emissions, Unregulated emissions, Gasoline, Diesel, Light-duty vehicles, PAH, Benzo(a)pyrene, Dibenzopyrenes, Dibenzo(a, l)pyrene, Toxic Equivalency Factor, TEF
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-29585 (URN)10.1016/j.atmosenv.2009.04.055 (DOI)000268851600010 ()
Available from: 2009-09-09 Created: 2009-09-07 Last updated: 2017-12-13Bibliographically approved

Open Access in DiVA

No full text

Search in DiVA

By author/editor
Bergvall, Christoffer
By organisation
Department of Analytical Chemistry
Analytical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 508 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf