Page:NIOSH Manual of Analytical Methods - 9109.pdf/24

 METHAMPHETAMINE. . . on Wipes by SPE: METHOD 9109, Issue 1, dated 17 October 2011 - Page 24 of 33

TABLE 11 (continued). Gas chromatographic retention times for heptafluorobutyryl and trimethylsilyl derivatives of selected drugs of abuse, precursors, and potential adulterants(1) GC Peak No.

Compound

Derivative Form(2)

Notes(3)

Retention Time Minutes(4)

Relative Retention Time (5)

(6)

Ions (Significant m/z)(7) 1’

2’ (7)

3’ (7)

79

N-Methyl pseudoephedrine

O-TMS-

Pri.deriv.

9.66

0.7535

0.9718

72

73 [13]

163 [5]

80

Morphine

O-HFB-O’-TMS-

Minor peak

19.97

1.5577

2.0091

340

324 [28]

341 [25]

81

Morphine

O,O’-bis-TMS-

Pri.deriv.

82

Nicotine

parent

83

Norpseudoephedrine (Cathine)

N-HFB-O-TMS-

84

Norpseudoephedrine (Cathine)

N-HFB-N,O-bis-TMS-

OS artifact

11.26

0.8783

1.1328

179

180 [18]

312 [10]

85

Oxycodone (OxyContin®)

TMS-

Pri.deriv.

21.66

1.6895

2.1791

387

388 [30]

372 [30]

86

Phencyclidine (PCP)

parent

Major peak

15.62

1.2184

1.5714

200

242 [35]

243 [25]

87

Phencyclidine (PCP)

N-HFB-dehydro-

Artifact

19.85

1.5484

1.9970

91

159 [60]

280 [10]

88

Phencyclidine-D5 (I$)(9)

parent

Major peak

15.59

1.2161

1.5684

205

96 [42]

246 [25]

89

Phencyclidine-D5 (I$)(9)

N-HFB-dehydro-

Artifact

19.83

1.5468

1.9950

96

164 [65]

280 [10]

(12)

Pri.deriv.

21.08

1.6443

2.1207

429

414 [50]

401 [35]

8.86

0.6911

0.8913

84

133 [35]

162 [18]

10.39

0.8105

1.0453

179

180 [18]

240 [18]

90

Phenethylamine

N-HFB-

Pri.deriv.

8.58

0.6693

0.8632

104

91 [60]

169 [15]

91

Phenethylamine(8)

N-HFB-N-TMS-

Pri.deriv.

9.51

0.7418

0.9567

298

105 [40]

220 [10]

92

Phentermine

N-HFB-

Pri.deriv.

8.72

0.6802

0.8773

254

132 [12]

214 [8]

93

4-Phenyl-1-butylamine (I$)

N-HFB-

Pri.deriv.

11.47

0.8947

1.1539

91

104 [25]

176 [22]

94

Phenylephrine(8)

N-HFB-O,O’-bis-TMS-

Pri.deriv.

13.94

1.0874

1.4024

267

268 [25]

240 [12]

95

Phenylpropanolamine

N-HFB-O-TMS-

Pri.deriv.

10.49

0.8183

1.0553

179

180 [18]

240 [18]

96

Phenylpropanolamine

N-HFB-N,O-bis-TMS-

OS artifact

11.01

0.8588

1.1076

179

180 [18]

312 [10]

(8)

(8) (9)

97

N-Propyl amphetamine (I$)

N-HFB-

Pri.deriv.

11.05

0.8619

1.1117

282

240 [85]

118 [20]

98

Pseudoephedrine

N-HFB-O-TMS-

Pri.deriv.

11.68

0.9111

1.1751

179

254 [15]

73 [75]

99

Theophylline

parent

Major peak

15.50

1.2090

1.5594

237

252 [57]

223 [14]

100

Trifluoromethylphenyl piperazine

N-HFB-

Pri.deriv.

13.76

1.0733

1.3843

200

229 [70]

172 [73]

(9)

(8) (10)

(1) Actual retention times may vary depending on individual GC column and GC conditions. Gas chromatographic and mass spectrometer conditions used as on p. 9109-1. (2) Derivative form. HFB = heptafluorobutyryl derivative. TMS = trimethylsilyl derivative. N- = attachment to nitrogen atom. O- = attachment to oxygen atom. Not all forms are presented. Trifluoroacetyl derivatives are not presented. Underivatized compounds are identified as a “parent” compound. Parent compounds that have poor chromatographic peak shapes under the conditions used are not presented. Spectra for the derivatives are given in the Backup Data Report (Appendix-II). [2] (3) Major and minor peaks are identified where two or more forms are possible. In some cases two major peaks may exist. Pri.deriv. = Primary derivative, a major peak. The major peak or the primary derivative should be used for quantitation. OS artifact = Oversilylation artifact [18]. Oversilylation artifacts occur where a primary amine is substituted with both a heptafluorobutyryl and a trimethylsilyl group. Under the specified conditions of extraction and derivatization these remain as minor components and are of little concern. (4) Retention times are not the same as in Table 6 or Figures 1 and 2 in this method since these data were obtained on a different instrument. Relative retention times should be approximately the same. (5) Retention time relative to 4,4’-dibromooctafluorobiphenyl. (6) Retention time relative to the heptafluorobutyryl derivative of methamphetamine. (7) Significant ions that can be used for quantification and qualitative identification are given. The base peaks are not necessarily included, especially if they are low mass (<100 AMU). Numbers in brackets indicate the approximate relative abundance of the secondary (2’) and tertiary (3’) ions relative to the primary (1’) ion and not necessarily to the base peak of each mass spectrum. Relative abundance varies with different tuning criteria and cleanliness of the mass spectrometer source. The 1’ or 2’ ions are recommended for quantification. All ions are selected as much as possible above m/z 100 to avoid interference from low mass co-eluting interferences. The 2’ and 3’ ions are selected as much as possible for nearness to the primary ion to minimize false negatives from skewing of spectra as the mass spectrometer source becomes contaminated with use. Ubiquitous ions (e.g., m/z 73, 91, and 169) are avoided as much as possible. (8) Intentional or unintentional adulterants. For example, phentermine may be added to MDMA and caffeine added to methamphetamine intentionally. Chlorpheniramine is an unintentional adulterant when pseudoephedrine containing chlorpheniramine is used as a methamphetamine precursor. (9) (I$) = Internal standard. The best results are obtained using internal standards that are deuterated analogs of the target analyte, or those that are chemically and structurally similar to the target analytes. (10) Typical “club drugs” (piperazine analogs as ecstasy substitutes, ketamine and flunitrazepan as predatory drugs). (11) 4-Bromo-2,5-DMPEA = 4-Bromo-2,5-dimethoxyphenethylamine (Nexus). (12) Presence of (+)-norephedrine, N-methylpseudoephedrine and/or N-methylephedrine in pseudoephedrine or ephedrine indicates extracts of Ephedra spp. as source of methamphetamine precursor. Presence of amphetamine and N,N-dimethylamphetamine in methamphetamine final product also suggests the same source. [19, 20, 21]

Method rev. 1.1.1

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition