Separation of 54 Pahs on an Agilent J&W Select PAH GC Column

Separation of 54 PAHs on an Agilent J&W Select PAH GC Column

Application Note

Author Introduction John Oostdijk Polycyclic aromatic hydrocarbons (PAHs) are compounds that contain two or more Agilent Technologies, Inc. aromatic rings. They are formed during incomplete combustion or pyrolysis of organic matter, industrial processes and cooking and food processing. PAHs are therefore analyzed in environmental and food samples. The difficulty in analyzing PAHs lies in separating PAH isomers. These isomers have the same chemical structure and same ion fragment and therefore cannot be separated by mass spectrometers. The Select PAH capillary column has enhanced selectivity towards PAHs, separating the isomers and enabling accurate PAH analysis. This application note describes an optimized oven program for the Select PAH column. In PAH analysis, there is a difference between the European (EU) and American (EPA) legislation. The legislations both describe a different set of PAHs and address different matrix origins. Table 1 lists the PAH regulated by EU and EPA legislation, including the potential interferences. For this application note, we chose a sample containing 54 PAHs to demonstrate the unique selectivity of the Select PAH. Conditions Peak MW Compound EPA SFC & CAS Technique: GC/MS, Triple Quad 610 EFSA PAHs Column: Select PAH, 30 m x 0.25 mm, df=0.15 µm (part number (15+1) CP7462) 7 154 Acenaphthene X 83-32-9 Sample Conc: approx 0.1-0.3 µg/mL 8 166 Fluorene X 86-73-7 Injection Volume: 1 μL Temperature: 70 °C (0.7 min), 85 °C/min, 180 °C, 3 °C/min, 230 °C (7 9 188 Phenanthrene-d10 1517-22-2 min), 28 °C/min, 280 °C (10 min), 14 °C/min, 350 °C (3 10 178 Phenanthrene X 85-01-8 min) 11 178 Anthracene X 120-12-7 Carrier Gas: Helium, constant flow 2 mL/min 12 202 Fluoranthene X 206-44-0 Injector: 300 °C, Splitless mode, 1 min @ 50 mL/min 13 202 Pyrene X 129-00-0 Detector: Triple Quad, EI in SIM mode, ion source 275°C, transfer 14 216 Benzo[a]fluorene 238-84-6 line 300°C 15 216 Benzo[b]fluorene 243-17-4 16 216 7H-Benzo[c]fluorene X 205-12-9 17 234 Benzo[b]naphto[2,1-d]- 239-35-0 Results and Discussion thiophene 18 226 Benzo[g,h,i]-fluoranthene 203-12-3 Figure 1 shows the separation of all 54 PAH isomers and 19 228 Benzo[c]phenanthrene 195-19-7 Figures 2-6 reveal the finer details. 20 228 Benz[a]anthracene X X 56-55-3 When performing this analysis, there are three sets of 21 226 Cyclopenta[c,d]pyrene X 27208-37-3 peaks that are difficult to resolve. The first set, comprising 22 240 Chrysene-d10 1719-03-5 benzo[a]anthracene, cyclopenta[c,d]pyrene, chrysene and 23 228 Triphenylene 217-59-4 triphenylene, has different masses, m/z 226 and 228. The 24 228 Chrysene X X 218-01-9 compounds with m/z 228 also contain some m/z 226, 25 242 6-Methylchrysene 175-85-7 making it difficult to resolve this set by MS alone. The same 26 242 5-Methylchrysene X 3697-24-3 27 252 Benzo[b]fluoranthene X X 205-99-2 problem occurs when separating indeno[1,2,3-c,d]pyrene, 28 252 Benzo[k]fluoranthene X X 207-08-9 benzo[b]triphenylene and dibenzo[a,h]anthracene with m/z 29 252 Benzo[j]fluoranthene X 205-82-3 276 and 278. The third set of PAH isomers difficult to resolve 30 252 Benzo[a]fluoranthene 203-33-8 are the benzofluoranthenes. These three isomers, benzo[b] 31 252 Benzo[e]pyrene 192-97-2 fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene, 32 252 Benzo[a]pyrene X X 50-32-8 have the same mass and cannot be resolved by MS. 33 264 Perylene-d12 1520-96-3 However, the unique selectivity of Select PAH resolves all the 34 252 Perylene 198-55-0 PAH isomers and enables accurate quantification of all PAHs. 35 268 3-Methylcholanthrene 56-49-5 36 330 9,10-Diphenylanthracene 216-105-1 Peaks 1 and 2 show some tailing, which can be resolved by 37 279 Dibenzo[a,h]acridine 226-36-8 further optimization of the splitless injection conditions. 38 279 Dibenzo[a,j]acridine 224-42-0 39 278 Dibenzo[a,j]anthracene 224-41-9 40 292 Dibenzo[a,h] 13250-98-1 Conclusion anthracene-d14 41 278 Benzo[b]triphenylene 215-58-7 The Select PAH column resolves 54 PAHs in a single GC/ 42 276 Indeno[1,2,3-c,d]pyrene X X 193-39-5 MS run, including the hard to separate PAH isomers. The 43 278 Dibenzo[a,h]anthracene X X 53-70-3 optimized GC oven program performs the run time in less than 44 278 Benzo[b]chrysene 214-17-5 45 minutes. 45 278 Picene 213-46-7 46 276 Benzo[g,h,i]perylene X X 191-24-2 47 276 Dibenzo[def,mno]- 191-26-4 Table 1. Peak Identification for Figure 1 chrysene

Peak MW Compound EPA SFC & CAS 48 267 7H-Dibenzo[c,g]- 194-59-2 610 EFSA PAHs carbazole (15+1) 49 302 Dibenzo[a,l]pyrene X 191-30-0 1 136 Naphthalene-d8 1146-65-2 50 302 Dibenzo[a,e]pyrene X 192-65-4 2 128 Naphthalene X 91-20-3 51 300 Coronene 191-07-1 3 142 2-Methylnaphthalene 91-57-6 52 302 Benzo[b]perylene 197-70-6 4 142 1-Methylnaphthalene 90-12-0 53 302 Dibenzo[a,i]pyrene X 189-55-9 5 152 Acenaphthylene X 208-96-8 54 302 Dibenzo[a,h]pyrene X 189-64-0 6 164 Acenaphthene-d10 15067-26-2

2 350

TIC °C

60000.00 300

50000.0s e 0 n

o 250 s p e r

40000.0S 0 M 200

30000.00

150 20000.00

100 10000.00

0.00 50 0 5 10 15 20 25 30 35 40 45 Time [min] Figure 1. GC/MS analysis of EU and EPA PAHs on Select PAH column, 30 m x 0.25 mm x 0.15 µm

3 Table 2. Peak Identification for Figure 2

Peak MW Compound EPA 610 CAS Peak MW Compound EPA 610 CAS 1 136 Naphthalene-d8 1146-65-2 5 152 Acenaphthylene X 208-96-8 2 128 Naphthalene X 91-20-3 6 164 Acenaphthene-d10 15067-26-2 3 142 2-Methylnaphthalene 91-57-6 7 154 Acenaphthene X 83-32-9 4 142 1-Methylnaphthalene 90-12-0 8 166 Fluorene X 86-73-7

5 m/z 152 m/z 154 m/z 164 2 m/z 128 m/z 136

1 7

2.35 2.37 2.39 2.41 2.43 2.45 2.47 2.49 2.51 2.53 2.55 3.50 3.55 3.60 3.65 3.70 3.75 3.80 3.85 3.90 70000.00

1+2

60000.00

5 50000.00

40000.00 3

30000.00 8

20000.00

10000.00

0.00 2.00 2.50 3.00 3.50 4.00 4.50 5.00 Figure 2. Details and identification of peaks 1 to 8

4 Table 3. Peak Identification for Figure 3 10 m/z 188 m/z 178 Peak MW Compound EPA 610 CAS 9 188 Phenanthrene-d10 1517-22-2 10 178 Phenanthrene X 85-01-8 11 11 178 Anthracene X 120-12-7 12 202 Fluoranthene X 206-44-0 13 202 Pyrene X 129-00-0

7.10 7.20 7.30 7.40 7.50 7.60 7.70

12 13

5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00

Figure 3. Details and identification of peaks 9 to 13

5 Table 4. Peak Identification for Figure 4 23 m/z 226 m/z 228 Peak MW Compound EPA SFC & CAS m/z 240 610 EFSA PAHs (15+1) 14 216 Benzo[a]fluorene 238-84-6 20 15 216 Benzo[b]fluorene 243-17-4 24 16 216 7H-Benzo[c]fluorene X 205-12-9 17 234 Benzo[b]naphto[2,1-d] 239.35-0 thiophene 18 226 Benzo[g,h,i]fluoranthene 203-12-3 21 19 228 Benzo[c]phenanthrene 195-19-7 22 20 228 Benzo[a]anthracene X X 56-55-3 21 226 Cyclopenta[c,d]pyrene X 27208-37-3 22 240 Chrysene-d10 179-03-5 23 228 Triphenylene 217-59-4 24.00 24.20 24.40 24.60 24.80 25.00 25.20 24 228 Chrysene X X 218-01-9

17 19 20 16 18 24

15.00 17.00 19.00 21.00 23.00 25.00 Figure 4. Details and identification of peaks 14 to 24

6 27 28 29 Table 5. Peak Identification for Figure 5

Peak MW Compound EPA SFC & CAS 610 EFSA PAHs (15+1)

30 25 242 6-Methylchrysene 1705-85-7 26 242 5-Methylchrysene X 3697-24-3 27 252 Benzo[b]fluoranthene X X 205-99-2 28 252 Benzo[k]fluoranthene X X 207-08-9 29 252 Benzo[j]fluoranthene X 205-82-3 30 252 Benzo[a]fluoranthene 203-33-8 31 252 Benzo[e]pyrene 192-97-2 32 252 Benzo[a]pyrene X X 50-32-8 33 264 Perylene-d12 1520-96-3 34 252 Perylene 198-55-0 29.50 29.70 29.90 30.10 30.30 30.50 30.70 30.90 35 268 3-Methylcholanthrene 56-49-5 36 330 9,10-diphenylanthracene 216-105-1

27 29

31 30 32 36 34

26.00 27.00 28.00 29.00 30.00 31.00 32.00 33.00 34.00 35.00 36.00 Figure 5. Details and identification of peaks 25 to 36

7 Table 6. Peak Identification for Figure 6

Peak MW Compound EPA SFC & EFSA CAS Peak MW Compound EPA SFC & EFSA CAS 610 PAHs (15+1) 610 PAHs (15+1) 37 279 Dibenzo[a,h]acridine 226-36-8 46 276 Benzo[g,h,i]perylene X X 191-24-2 38 279 Dibenzo[a,j]acridine 224-42-0 47 276 Dibenzo[def,mno]chrysene 191-26-4 39 278 Dibenzo[a,j]anthracene 224-41-9 48 267 7H-Dibenzo[c,g]carbazole 194-59-2 40 292 Dibenzo[a,h] 13250- 49 302 Dibenzo[a,l]pyrene 191-30-0 anthracene-d14 98-1 50 302 Dibenzo[a,e]pyrene X 192-65-4 41 278 Benzo[b]triphenylene 215-58-7 51 300 Coronene 191-07-1 42 276 Ideno[1,2,3-c,d]pyrene X X 193-39-5 52 302 Benzo[b]perylene 197-70-6 43 278 Dibenzo[a,h]anthracene X X 53-70-3 53 302 Dibenzo[a,i]pyrene X 189-55-9 44 278 Benzo[b]chrysene 214-17-5 54 302 Dibenzo[a,h]pyrene X 189-64-0 45 278 Picene 213-46-7

40 m/z 279 38 m/z 300 37 m/z 278 m/z 302 m/z 276 51 m/z 267 m/z 292 50

43 53 49

46 47 48 54 42 44 52 39 41 45

42.50 43.00 43.50 42.50 44.50 45.00

37.60 38.10 38.60 39.10 39.60 40.10 40.60 41.10

40, 41

50 38, 39 51 49

44 48 45 53 46

42 37 43 54

36.00 37.00 38.00 39.00 40.00 41.00 42.00 43.00 44.00 45.00 46.00

Figure 6. Details and identification of peaks 37 to 54

8 References Anon, (2005) Report Joint FAO/Who Expert Committee on Food Additives, Sixty-fourth meeting, Rome, 8-17 February 2005. Bordajandi LR, et al (2008) Optimisation of the GC-MS conditions for the determination of the 15 EU foodstuff priority polycyclic aromatic hydrocarbons, J. Sep. Sci., 31, 1769-1778. Lerda D, (2009) Polycyclic Aromatic Hydrocarbons (PAHs) Factsheet. European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, JRC 500871. Poster DL, et al. (2006) Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods. Anal. Bioanal. Chem, 386, 859-881. Ziegenhals K, et al. (2008) Fast-GC/HRMS to quantify the EU priority PAH, J. Sep. Sci., 31, 1779-1786.

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This information is subject to change without notice. © Agilent Technologies, Inc. 2010 Published in UK, October 11, 2010 SI-02232