LAAN-J-MS-E033
GCMS Gas Chromatograph Mass Spectrometer Analysis of Polycyclic Aromatic Hydrocarbons Using GC-MS 33
Introduction
Polycyclic aromatic hydrocarbons (PAHs) are byproducts of burning fuels, such as mineral oils, and are known to be carcinogenic, mutagenic, and teratogenic. These compounds are regulated in many countries as harmful pollutants in environmental water and the atmosphere. In Japan, the "Measuring method manual for toxic air pollutants" and "Measuring method manual for polycyclic aromatic hydrocarbons (PAHs) in exhaust gas emissions" were revised in March 2011. In addition, environmental
standards, including fine particle regulations (PM2.5) and fine particles, can include PAHs. Consequently, there is an increasing need to measure PAHs. This application datasheet introduces an example of measuring 36 PAHs. Analysis Conditions and Results
Table 1 shows the analysis conditions and Fig. 1 shows the total ion current chromatogram. Figure 2 (Page 2) shows enlarged chromatogram sections for PAHs with 4, 5, and 6 rings.
Table 1: Analysis Conditions
GC-MS ：GCMS-QP2010 Ultra [GC] [MS] Column ：Rtx-35 (length 30 m, 0.32 mm I.D., df=0.25 µm ) Interface temperature ：300℃ Inlet mode ：Splitless Ion source temperature ：230℃ Vaporizing chamber temp：300℃ Solvent elution time ：3.5min Column oven temperature：90℃ (2min) →(5℃/min)→320℃(12min) Data sampling time ：4.5 – 60min Carrier gas ：Helium Measurement mode ：Scan Control mode ：Constant linear velocity (43.7cm/sec) Mass range ：m/z 45-450 High pressure injection ：150kPa (1.5min) Event time ：0.3sec Purge flow rate ：3mL/min Injection rate ：1.0 µL
(x10,000,000) TIC 7 1.00 26,27 1 11 18 16,17 31 10 0.75 28 25 22,23 29 24 30 13 20 0.50 4 14 2 3 5 19 8 12 32 34 35 6 33 36 21 0.25 9 15
10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 Fig. 1: Total Ion Current Chromatogram of 36 PAHs 1.Naphthalene, 2.Biphenyl 3.Acenaphthylene 4.Acenaphthene 5.Fluorene 6.Dibenzothiophene 7.Phenanthrene 8.Anthracene 9.4H- Cyclopenta[def]phenanthrene 10.Fluoranthene 11.Pyrene 12.Benzo[ghi]fluoranthene 13.Benzo[c]phenanthrene 14.Benzo[a]anthracene 15.Cyclopenta[cd]pyrene 16,17.Chrysene & Triphenylene 18.Benzo[b]fluoranthene 19.Benzo[k]fluoranthene 20.Benzo[j]fluoranthene 21.Benzo[a]fluoranthene 22.Benzo[e]pyrene 23.Benzo[a]pyrene 24.Perylene 25.Dibenz[a,j]anthracene 26.Dibenz[a,c]anthracene 27.Indeno[1,2,3-cd]pyrene 28.Dibenz[a,h]anthracene 29.Benzo[b]chrysene 30.Picene 31.Benzo[ghi]perylene 32.Anthanthrene 33.Dibenzo[b,k]fluoranthene 34.Dibenzo[a,h]pyrene 35.Coronene 36.Dibenzo[a,e]pyrene 33
(x10,000,000) 1.75 TIC 226.00 (3.00) 1.50 228.00 (3.00) 16,17 1.25
1.00 13 14 0.75 12 15 0.50
0.25
0.00 34.0 34.5 35.0 35.5 36.0 36.5 37.0 37.5 38.0 12.Benzo[ghi]fluoranthene 13.Benzo[c]phenanthrene 14.Benzo[a]anthracene 15.Cyclopenta[cd]pyrene 16,17.Chrysene&Triphenylene
(x10,000,000) 1.25 TIC 252.00 (3.00) 18 1.00
22 23 24 0.75 20 19 0.50 21
0.25
0.00 40.5 41.0 41.5 42.0 42.5 43.0 43.5 44.0 18.Benzo[b]fluoranthene 19.Benzo[k]fluoranthene 20.Benzo[j]fluoranthene 21.Benzo[a]fluoranthene 22.Benzo[e]pyrene 23.Benzo[a]pyrene 24.Perylene
(x10,000,000) TIC 1.50 276.00 (3.00) 278.00 (3.00) 2627 1.25 31 28 25 29 1.00 30
0.75 32
0.50
0.25
46.0 46.5 47.0 47.5 48.0 48.5 49.0 49.5 25.Dibenz[a,j]anthracene 26.Dibenz[a,c]anthracene 27.Indeno[1,2,3-cd]pyrene 28.Dibenz[a,h]anthracene 29.Benzo[b]chrysene 30.Picene 31.Benzo[ghi]perylene 32.Anthanthrene 26 and 27 can be resolved between m/z 276 and 278.
Fig. 2: Enlarged Chromatograms Upper: 4-Ring Section (retention time 33.5 to 38.0 minutes); Middle: 5-Ring Section (retention time 40.5 to 44.5 minutes); Lower: 6-Ring Section (retention time 45.5 to 49.5 minutes)
Summary
Because there are so many PAH isomers, separation by column is more important than separation by mass. Of the 36 polycyclic aromatic hydrocarbons, the Rtx-35 column can separate all except chrysene and triphenylene. Therefore, it enables separating PAHs with a wide range of boiling points.
For Research Use Only. Not for use in diagnostic procedures. Shimadzu Corporation (“Shimadzu”) reserves all rights including copyright in this publication. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to, or arising out of the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice. First Edition: November 2011