Complex polycyclic aromatic hydrocarbons from coal · PDF fileComplex polycyclic aromatic hydrocarbons from coal tar on ... The crude tar contains a large number ... Chem., 393, 1697-1707.

Complex polycyclic aromatic hydrocarbons from coal tar on Agilent J&W Select PAH

Application Note

IntroductionCoal tar is a brown or black liquid of high viscosity, which smells of naphthalene and aromatic hydrocarbons and is obtained from the destructive distillation of coal. Formerly, coal tar was obtained as a by-product in manufacturing coal gas. It is now produced in making coke for steel making. The crude tar contains a large number of organic compounds, such as benzene, naphthalene, methylbenzene and phenols, which can be obtained by distillation. The residue is pitch. At one time coal tar was the major source of organic chemicals, most of which are now derived from petroleum and natural gas. Coal tar pitch is mainly used as a binding agent in the production of carbon electrodes, anodes and Sderberg electrodes, for example, by the aluminium industry. It is also used as a binding agent for refractories, clay pigeons, active carbon, coal briquetting, road construction and roofing. Furthermore, small quantities are used for heavy-duty corrosion protection.

The standard coal tar reference material (SRM 1597a, NIST) is a natural, combustion-related mixture of polycyclic aromatic hydrocarbons (PAHs), isolated from a medium crude coke-oven tar and dissolved in toluene. However, PAHs can be difficult to analyze because some of them have the same mass. This makes their separation with GC/MS problematic, and so column selectivity and an optimized oven program are necessary to resolve these PAHs. In this application note, a coal tar sample was analyzed using an optimized oven program for the Select PAH column. As the coal tar sample is intended for use in the evaluation and validation of analytical methods for the determination of PAHs, we can clearly show the performance of the Select PAH with this reference material.

AuthorJohn OostdijkAgilent Technologies, Inc.

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Results and DiscussionThe sample was analyzed directly in full scan and SIM mode. PAHs were analyzed using the same conditions as for a standard with regulated and interfering PAHs, which made their identification possible. Chromatograms with identifications are shown in Figures 1 to 3. It can be seen from Figure 1 that chrysene (66 mg/kg) was separated from triphenylene (12 mg/kg), and benzo[b,k,j]fluoranthene (66, 37 and 41 mg/kg) from benzo[a]pyrene (94 mg/kg). The MS spectrum from chrysene is shown. As well as the molecular ion (M+) m/z 228, other ions such as m/z 226 and m/z 229 were formed. The PAHs were mostly very stable and only low fragment ions were observed, such as m/z 113 and 114 in this mass spectrum.

In addition, a group-type analysis of high molecular weight PAHs was possible, which is shown in Figure 4. PAHs with higher molecular weight (MW>302) were eluted at 350 C due to the maximum programmable column temperature. Many isomers of high molecular weight were in the coal tar sample. Complete separation, however, was not possible on a single column because of the limited separation

ConditionsTechnique: GC/MS, Triple QuadColumn: Select PAH, 30 x 0.25 mm,

df=0.15 m (part number CP7462)

Sample: SRM 1597a, concentration approximately 0.8-21 g/mL (www.nist.gov)

Injection Volume: 0.1 LTemperature: 70 C (0.70 min), 85 C/min,

180 C, 3 C/min, 230 C (7 min), 28 C/min, 280 C (10 min), 14 C/min, 350 C (3 min)

Carrier Gas: Helium, constant flow 2.0 mL/min

Injector: 300 C, Splitless mode, 1 min @ 50 mL/min

Detector: Triple Quad, EI in FS or SIM mode, ion source 275 C, transfer line 300 C

space and the large number of possible configurations of the PAHs. The relatively long run time of 45 min at the maximum programmable temperature of 350 C may affect the column lifetime.

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Figure 1. GC/MS analysis of SRM 1597a (0.1 L) in full scan mode on Select PAH

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BaA

CPP TP

CHR

m/z 228

m/z 226

MS spectrum of Chrysene

100 120 140 160 180 200 220 240m/z

228

226

114

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BbFA

m/z 252

BkFABjFA

BaP

BaA Benzo[a]anthraceneBaP Benzo[a]pyreneBpFA Benzo[b]fluorantheneBkFA Benzo[k]fluorantheneBjFA Benzo[j]fluorantheneCHR ChryseneCPP Cyclopenta[c,d]pyreneTP Triphenylene

Table 1. Peak Indication for Figure 1

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ACL Acenaphthylene (263 mg/kg)

BaA Benzo[a]anthracene (98 mg/kg)

BaP Benzo[a]pyrene (94 mg/kg)

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MS

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350

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TIC SIMTIC SIM 50x zoomed

NA

ACLPHE

FA

BaA

BaP

BghiP

DBaeP

PY

Figure 2. GC/MS analysis of SRM 1597a (0.1 L) in SIM mode on Select PAH. The final part of the chromatogram is enlarged because of the large concentration difference in the sample

BghiP Benzo[g,h,i]perylene (51 mg/kg)

DBaeP Dibenzo[a,e]pyrene (9 mg/kg)

FA Fluoranthene (327 mg/kg)

NA Naphthalene (1030 mg/kg)

PHE Phenanthrene (454 mg/kg)

PY Pyrene (240 mg/kg)

Table 2. Peak Indication for Figure 2

Table 3. Peak Identification for Figure 3

ATR Anthanthrene (Dibenzo[def,mno]chrysene)

BaFA Benzo[a]fluorantheneBaFL Benzo(a)fluoreneBaP Benzo[a]pyreneBbCHR Benzo[b]chryseneBbFA Benzo[b]fluorantheneBbFL Benzo(b)fluoreneBbNTP Benzo(b)naphto(2,1-d)thiophene

BbPer Benzo[b]peryleneBbTP Benzo[b]triphenyleneBcFL 7H-benzo[c]fluoreneBeP Benzo[e]pyreneBghiP Benzo[g,h,i]peryleneBjFA Benzo[j]fluorantheneBkFA Benzo[k]fluorantheneCor CoroneneDBahA Dibenzo[a,h]anthracene

DBaeP Dibenzo[a,e]pyreneDBahP Dibenzo[a,h]pyreneDbaiP Dibenzo[a,i]pyreneDBalP Dibenzo[a,l]pyreneIP Indeno[1,2,3-c,d]pyrene6MC 6-Methylchrysene5MC 5-MethylchrysenePer PerylenePic Picene

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Figure 3. GC/MS analysis of SRM 1597a (0.1 L) in SIM mode on Select PAH. Some examples of critical separations are shown: A. Benzofluorenes, B. Methylchrysenes, C. Benzofluoranthenes and isomers, D. Dibenzoanthracenes and isomers, E. Dibenzopyrenes and isomers, F. Benzo[b]naphtho[ ] thiophene isomers

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m/z 216

BaFL

BbFL

BcFL

AA

825.72725.6262

m/z 242

6MC

5MC

BB

29.7 30.2 30.7 31.2 31.7 32.2 32.7

m/z 252

BbFA

BkFABjFA

BaFA

BeP

BaP

Per

CC

38.2 38.7 39.2 39.7 40.2 40.7

m/z 278m/z 276

BbTP

IP

DBahA BbCHRPic

ATR

BghiP

DD

42.3 42.8 43.3 43.8 44.3 44.8

m/z 300m/z 302

DBalP+coelution

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Cor

BbPer

DBaiP

DBahP

EE

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m/z 234BbNTP

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F

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Figure 2B

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0 10 20 30 40 50 60 70 80 90Time [min]

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TIC SIMm/z 302 (zoomed 5x)m/z 326 (zoomed 20x)m/z 350 (zoomed 100x)m/z 374 (zoomed 500x)

m/z 374, eg C30H14

m/z 350, eg C28H14

m/z 326, eg C26H14

m/z 302, eg C24H14

Figure 4. GC/MS analysis of SRM 1597a (1 L) in SIM mode on Select PAH

ConclusionThe Select PAH column separated target PAHs in a complex mixture of coal tar in a single run with a runtime of 45 min. For eluting higher MW PAHs, a longer run time is necessary.

ReferencesBeekman M., Boersma, A.H.R. and. Sijm, D.T.H.M. (2008) Coal-tar pitch high temperature (CTPHT), transitional arrangements and way forward under REACH. REACH-SEA report of scoping study. Report 601780001/2008. National Institute for Public Health and the Environment, The Netherlands.

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.

Gmez-Ruiz JA and Wenzl T, (2009) Evaluation of gas chromatography columns for the analysis of the 15+1 EU-priority polycyclic aromatic hydrocarbons (PAHs). Anal. Bioanal. Chem., 393, 1697-1707.

Lerda D, (2009) Polycyclic Aromatic Hydrocarbons (PAHs) Factsheet. European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, JRC 500871.

NIST. Standard Reference Material 1597a, Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar. National Institute of Standards and Technology, Gaithersburg, MD, USA.

Poster DL, Schantz, M.M., Sander, L.C. and Wise, S.A. (2006) Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods. Anal. Bioanal. Chem, 386, 859-881.

Sander LC and Wise SA, (1997) Polycyclic Aromatic Hydrocarbon Structure Index, NIST Special Publication. http://www.cstl.nist.gov/acd/839.02/pah/sp922_Search.htm. National Institute of Standards and Technology, Gaithersburg, MD, USA. Wenzl T, Simon R, Kleiner J and Anklam E, (2006) Analytical methods for polycyclic aromatic hydrocarbons (PAHs) in food and the environment needed for new food legislation in the European Union. Trends in Anal. Chem., 25(7), 716-725.

Ziegenhals K, Hubschmann HJ, Speer K and Jira W, (2008) Fast-GC/HRMS to quantify the EU priority PAH, J. Sep. Sci., 31, 1779-1786.

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