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PHIiLIP MORRIS INCORPORATED I N'TER-0FF (CE CQRRES!"ONDEli'CE RICHMOND, YIRGIINIA G. Baker, R. 0. Kinser . 'Gas Chromatographic Behavior of N-Nitrosoanatabine Observation of an unexpectedly low thermal energy analyzer (tea) butanone (NNK). sonornicotine (NNN) and 4-(N-methyl-N-nitrosamino)-1-(3-pyridyl)-1-• .response to N-nitrosoanatabine (NAtB) prompted a gc/tea and gc/ms study .of the chromatographic behavior of three nitrosamines: NAtB, N-nitro- The gc/tea datal pointed' to the following observations: (1) 'When , NNK were equivalent. expected response was observed for NAtB regardless of the column used in the analysis. -The peak areas for equimollar injections of NNN and response (or corresponding peak area). However, only 50% of the injections of NNN, NNK and NAtB should produce a comparable tea decreased and (2) after approximately one-half dozen injections the expected results for NNN, NNK were observed'. Theoretically equimolar a new gc column (1.9m x 2.0mm ID glass column packed withi3% SP-22'50 on 100/120 Supelcoport) was installied, all the nitrosamine responses were simiilar.to those used in the gc/tea analysis of nitrosamines. A 156, as the base peak. The above spectrum obtained under gc/ms conditions. is consistent with identification as a bipyridyl isomer. The gc conditions of an ion at m/z 159 (the base peak-in NAtB); and the presence of a m/z of a parent ion at m/z 189; the absence of any significant abundance literature reports. The biiggest differences noted included: the absence NAtB.2 However, when the gc was used as the ms inlet, the spectrum obtained differed significantly from both the probe spectrum and When the sample was admitted iinto the ms via the probe, the spectrum obtained corresponded to that found in the literature for -- An X6D3NX sample spiked with NNN, NNK, NAtB was analyzed by gc/eims. GC/MS data were collected on this sample and on standards of NNN, NNK and NAtB. Since previous work had indicated that NAtB might be de- - composing to form a bipyridyl compound, several bipyridyl isomers (2,4',2,2' and 2,3' bipyridyl)'' were also analyzed. The mass spectra and retention times obtained on the standards of NNN, NNK and' NAtB were Fompared with those from the X6D3NX sample spiiked with NNN, NNK and NAtB. The three nitrosamines were identified in the X6D3NX sample. 6' x 1/8" OD glass column was packed with 3% SP-2250 on 100/120 meshi Supelcoport.- The analysis was programmed from 175-240 at 6°/min. The spectrum obtained by gc/ms showed that NAtB was not reaching the ms source. Decomposition of NAtB either on column, in the injection port or in the gc/ms or gc/tea interfaces would explain these gc/ms results (and' possibl-y the gc/tea data).

The elution order observed inithe gc/ms analysis was as follows: NNN, analysis. '~ NAtB and' NNK. This correlated with the elution order noted in the gc/tea The NAtB ms obtained by gc/ms after several injections is in fairly analyzed matched that of the NAtB standard. .in all the NAtB spectra, the retention time of none of the bipyridyls 156 of significant intensity (:,45% Relative Abundance (R.A.)) was noted good agreement with that obtained by probe/ms. Although an ion at m/z These experiments suggest that the diminished NAtB response observed -system and/or the gc/ms or gc/tea interfaces. in the tea was due to partia.l decomposition of NAtB in the:chromatographic References 1. Hoffmann,Dietri.ch; Adams, John D.; Brunnemann, Klaus D.; Hecht, lmh ; Baker, P. G. Notebook No. 7545 Tobacco Products.'.'Cancer Research 39, 2505-2509, July 1979. Stephen S. Assessment of Tobacco-Specific N-Nitrosamines in . McKay, C. Kinser, R. D. cc: Mr. W. F. Kuhn Dr. T. S. Osdene Mr. B. Carpenter Mr. J. Charles Attachment Notebook No. 7477 Notebook No. 7476 ~I's'4AL- Z) ,2 L'~- ~

TABLE I COMPARISON OF THE MASS SPECTRA OF NAtB 78 80.' . 92 1 Literature* 53.7 .30.4 46.0 ., 58.9 74.2 ~ 72. Values 45.5 GC/MS 26.5 2.3 BK 3.0 1.2. 25.6 Values , GC/MS 25.9 2.6 BK 3.3 1.4 28.3 Values *e. f. Reference 2 BK - ions present at background levels (<1%) ND - no ions detected