Spiked pad study at 50 0 C to show discriminators of groups are indicative of chemical component...

Spiked pad study at 50 0C to show discriminators of groups are indicative of chemical component

Complex Mixture Study

Figure 9 Headspace analysis of four different colognes. The scores plot shows that these complex mixtures had enough variability to be differentiated. The dendrogram for this data set (notshown) also showed how replicates of the same cologne clustered together and were differentthan the other colognes.

Human scent arises from a variety of sources: Secretions from the apocrine, eccrine and sebaceous glands Bacteria “feeding” on these secretions Cellular debris Topical applications (sunscreen, cologne,etc.)

An individual’s chemical profile will be comprised of volatile and semi-volatile compounds and within this profile will be his/her “odorome” which will be a combination of malodorous and pleasant odor components (Figure 2).

Many components of the VSVCP will contain N,S,O functional groups (5-6)

Will be amenable to ionization by gas phase proton/ electron transfer reactions in atmospheric pressure chemical ionization (APCI)

“Odorome” can be affected by (7-13): Diet Health Age Heredity Race

Multivariate statistical analysis techniques are ideally suited for analysis of complex mixtures and classifying samples into categories:

Deal with data on two or more variables measured on a set of objects

Developed to explore the interdependence of variables

Can empirically discover groups with similar spectra (hierarchical cluster analysis, HCA)

Can summarize variation in highly multivariant spectra (principle component analysis, PCA)

Can develop classification rules for predefined groups (discriminant analysis, DA)

Transforms original , intercorrelated variables into anew set of uncorrelated variables

Identifies main data characteristics from interrelated variables

Summarizes multivariate variability efficiently in fewer dimensions

Purpose: Show statistical differences using multivariate analysis between unused scent pads and spiked pads, or pads used to sample items or individuals.

Method: Process data obtained with a thermal desorption atmospheric pressure chemical ionization source coupled to a PE Sciex 365 mass spectrometer using Pirouette, a multivariate data analysis program.

Results: Statistical differences observed between unused pads from different boxes and between unused pads and pads used to sample head space of single component and complex mixtures (colognes) using multivariate analysis.

Trained canines are used in search and rescue operations as well as to track fugitives, missing persons, and for scent identification line-ups. Using scent as forensic evidence assumes that each individual has a unique odor, that the unique odor is stable over time and that a dog can differentiate between odors of different people. Several empirical studies have been performed to determine how well dogs can differentiate odors between people (1-4), yet very little scientific data has been published with respect to the actual identity of chemical components canines are targeting/smelling.

Scent evidence can be found on any item a suspect has touched, worn, or eliminated. Clothing and weapons are easily collected as evidence, but for objects that cannot be removed from the crime scene, a Scent Transfer Unit™ (STU) shown in Figure 1 was developed to collect the scent evidence onto a gauze pad which can be stored until needed. The gauze pad would then be given to a canine who may follow a suspect’s path from a crime scene, place a suspect at a particular scene, match a suspect to a weapon, or identify a suspect in a line-up.

By using thermal desorption atmospheric pressure chemical ionization mass spectrometry (TD/APCI-MS), we can analyze scent pads rapidly, without suffering loss of analyte often encountered with extraction steps in GC/MS. In addition, using multivariate analysis on the acquired data will show how reproducible the scent profiles acquired with the STU are, as well as determine important discriminators in identifying individuals or groups.

1. Schoon, G.A.A. J. Forensic Sci. 1998, 43, 70-75.

2. Schoon, G.A.A. Appl. Anim. Behav. Sci. 1996, 49, 257-267.

3. Schoon, G.A.A.; De Bruin, J.C. Forensic Sci. Int. 1994, 69, 111-118.

4. Brisbin, Jr., I.L.; Austad, S.N. Anim. Behav. 1991, 42, 63-69.

5. Bernier, U.R.; Booth, M.M.; Yost, R.A. Anal. Chem. 1999, 71, 1-7.

6. Zeng, X.; Leyden, J.J.; Lawley, H.J.; Sawano, K.; Nohara, I; Preti G. J. Chem. Ecol. 1991, 17, 1480.

7. Nicolaides, N. Science, 1974, 186, 19-26.

8. Green, S.C.; Stewart, M.E.; Downing, D.T. J. Invest. Dermatol. 1984, 83, 114-117.

9. Smith, K.; Thompson, G.F.; Koster, H.D. Science, 1969, 166, 398-399

10. Haze, S.; Gozu, Y.; Nakamura, S.; Kohno, Y.; Sawano, K.; Ohta, H.; Yamazaki, K. J. Invest. Dermatol. 2001, 116, 520-524.

11. Mitchell, S.C.; Smith, R.L. Drug Metabolism and Disposition, 2001, 29, 517-521.

12. Schaefer, M.L.; Young, D.A.; Restrepo, D. J. Neurosci. 2001,21, 2481-2487.

13. Schaefer, M.L.; Yamazaki, K; Osada, K.; Restrepo, D.; Beauchamp, G.K. J. Neurosci 2002, 22, 9513-9521.

Figure 1 Photograph of the STU device with a sterile gauze (Johnson and Johnson) used to collect scent evidence.

smp03smp02smp01sp1003sp1001sp1002sp1203sp1202sp1201p1303p1302p1301p1201p1001p1203p1101p1202p1003

p1103p1102p1002b14b09b12b13b08b04b03b07b11b06b05b02b10b01

0.00.20.40.60.81.0

Single

CURSORSimilarity: 0.452

NODESimilarity: 0.000Distance: 166.554Descendants: 35

Single


NODE

isovaleric acid

heptanoic acid

virgin pads

lab air

smp03smp02smp01sp1003sp1001sp1002sp1203sp1202sp1201p1303p1302p1301p1201p1001p1203p1101p1202p1003

p1103p1102p1002b14b09b12b13b08b04b03b07b11b06b05b02b10b01

0.00.20.40.60.81.0

Single


NODESimilarity: 0.000Distance: 166.554Descendants: 35

Single


NODE

isovaleric acid

heptanoic acid

virgin pads

lab air

Experiments performed with a thermal desorption atmospheric pressure chemical ionization source coupled to a PE Sciex 365 mass spectrometer (MDS Sciex, Concord, Ontario, Canada).

System optimized for detection of likely odor compounds in both positive and negative ion modes.

“Scent” samples collected on sterile gauze pads (or scent pads, Johnson & Johnson) using the STU.

Neat compounds – headspace analysis

Humans – Will be collecting samples from population including homogeneous groups of individuals (e.g. 40 yr old Caucasian males) and subpopulation for race, gender, and age variations.

Sample from various locations on body

Scent pads are placed in thermal desorption unit (Figure 3) and mass spectra recorded from m/z 30 to m/z 500

Import data into Pirouette (Lite Explore v3.11) Identify similar groups

Identify important discriminators (m/z) for each group

Identify “most discriminating” components in scent profile Tandem mass spectrometry

GC/MS of extracted or thermally desorbed scent pads

Pads from different boxes show variability as well as significant background ions. Less background ions in negative ion mode

Complex mixtures (colognes) can be differentiated using Pirouette, a multivariate analysis program.

Variability can be determined (PCA scores plot) and the source(s) of the variability identified (PCA loading plot). Sampled headspace of isovaleric acid

clustered with pads spiked with isovaleric acid;major discriminators included m/z 101 and 203, (M-H)- and (2M-H)-, respectively.

Sampled headspace of 2-nonenal clustered on the basis of m/z 141 (protonated molecule of 2-nonenal)(not shown).

Further optimize thermal desorption and APCI interface conditions for odorome model compounds.

Explore alternative pads to reduce background.

Refine statistical analysis procedures using existing data sets.

Begin human sampling:

Sampling duration

Sampling areas, articles

Apply discriminant analysis to data sets

Male and female

Young and old

Caucasian, Asian, etc.

SAR acknowledges support through Oak Ridge Institute for Science and Education, Oak Ridge, TN in conjunction with the Federal Bureau of Investigation Counter-terrorism Forensic Science Research Unit (FBI-CTFSRU).

Research sponsored by the Federal Bureau of Investigation through the Work for Others Office, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC.

Authors thank Dr. Dennis Wolf at ORNL for helpful discussions regarding multivariate analysis.

Authors thank John Luke at MSA for loan of thermal desorption equipment.

Authors thank Larry Harris for loan of STU device.

API 365 MS was provided through a Cooperative Research and Development Agreement with MDS Sciex (CRADA ORNL02-0662).

Figure 2 Illustration of human scent composition. Many components of the VSVCP and most odor compounds will contain some functional group, such as N, S, and O.

Optimization of TD/APCI-MS to obtain predominantly molecular ion species

Desorption Of Sterile Gauze Pads

Figure 6 Temperature studies on unused pads (positive ion mode) show slight variations in thermally desorbed components between boxes of pads with same lot numbers and boxes with differentlot numbers.

Scores Plot Loading Plot

bkgndlab airS-147

Factor1

Factor2

Factor3

bkgn01bkgn02bkgn03bkgn04bkgn05bkgn06bkgn07bkgn08bkgn09bkgn10bkgn11bkgn12bkgn13bkgn14bkgn15

p402

p502p503

p504

p601

p602p603

p604p605

p401p501 Factor1

Factor2

Factor3 30 m/z44 m/z51 m/z58 m/z65 m/z72 m/z86 m/z93 m/z100 m/z114 m/z121 m/z128 m/z135 m/z142 m/z156 m/z170 m/z184 m/z198 m/z212 m/z226 m/z240 m/z254 m/z268 m/z282 m/z303 m/z310 m/z317 m/z324 m/z331 m/z338 m/z345 m/z352 m/z359 m/z366 m/z373 m/z380 m/z387 m/z394 m/z401 m/z408 m/z415 m/z422 m/z429 m/z436 m/z443 m/z450 m/z457 m/z464 m/z471 m/z478 m/z485 m/z492 m/z499 m/z31 m/z38 m/z45 m/z52 m/z

59 m/z

66 m/z80 m/z94 m/z108 m/z122 m/z136 m/z150 m/z164 m/z178 m/z192 m/z206 m/z220 m/z234 m/z248 m/z262 m/z276 m/z290 m/z304 m/z311 m/z318 m/z325 m/z332 m/z339 m/z346 m/z353 m/z360 m/z367 m/z374 m/z381 m/z388 m/z395 m/z402 m/z409 m/z416 m/z423 m/z430 m/z437 m/z444 m/z451 m/z458 m/z465 m/z472 m/z479 m/z486 m/z493 m/z500 m/z32 m/z39 m/z46 m/z67 m/z74 m/z88 m/z102 m/z116 m/z

123 m/z

130 m/z137 m/z

144 m/z158 m/z165 m/z

172 m/z179 m/z186 m/z200 m/z214 m/z228 m/z242 m/z256 m/z263 m/z270 m/z284 m/z291 m/z298 m/z305 m/z312 m/z319 m/z326 m/z333 m/z340 m/z347 m/z354 m/z361 m/z368 m/z375 m/z382 m/z389 m/z396 m/z403 m/z410 m/z417 m/z424 m/z431 m/z438 m/z445 m/z452 m/z459 m/z466 m/z473 m/z480 m/z487 m/z494 m/z33 m/z40 m/z47 m/z54 m/z61 m/z

68 m/z82 m/z96 m/z110 m/z124 m/z138 m/z152 m/z166 m/z173 m/z

180 m/z194 m/z208 m/z

215 m/z

222 m/z236 m/z250 m/z264 m/z278 m/z285 m/z292 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z62 m/z76 m/z90 m/z104 m/z118 m/z132 m/z

139 m/z

146 m/z160 m/z174 m/z181 m/z

188 m/z202 m/z216 m/z230 m/z244 m/z258 m/z272 m/z286 m/z293 m/z300 m/z307 m/z314 m/z321 m/z328 m/z335 m/z342 m/z349 m/z356 m/z363 m/z370 m/z377 m/z384 m/z391 m/z398 m/z405 m/z412 m/z419 m/z426 m/z433 m/z440 m/z447 m/z454 m/z461 m/z468 m/z475 m/z482 m/z489 m/z496 m/z35 m/z49 m/z56 m/z63 m/z70 m/z84 m/z91m/z98 m/z112 m/z119 m/z126 m/z133 m/z140 m/z154 m/z168 m/z175 m/z182 m/z196 m/z210 m/z224 m/z238 m/z252 m/z266 m/z280 m/z294 m/z301 m/z308 m/z315 m/z322 m/z329 m/z336 m/z343 m/z350 m/z357 m/z364 m/z371 m/z378 m/z385 m/z392 m/z399 m/z406 m/z413 m/z420 m/z427 m/z434 m/z441 m/z448 m/z455 m/z462 m/z469 m/z476 m/z483 m/z490 m/z497 m/z36 m/z43 m/z

50 m/z64 m/z78 m/z92 m/z106 m/z120 m/z134 m/z148 m/z

155 m/z

162 m/z169 m/z

176 m/z190 m/z197 m/z

204 m/z218 m/z225 m/z

232 m/z246 m/z260 m/z274 m/z281 m/z288 m/z295 m/z302 m/z309 m/z316 m/z323 m/z330 m/z337 m/z344 m/z351 m/z358 m/z365 m/z372 m/z379 m/z386 m/z393 m/z400 m/z407 m/z414 m/z421 m/z428 m/z435 m/z442 m/z449 m/z456 m/z463 m/z470 m/z477 m/z484 m/z491 m/z498 m/z37 m/z79 m/z107 m/z149 m/z163 m/z177 m/z191 m/z205 m/z219 m/z233 m/z247 m/z261 m/z275 m/z289 m/z296 m/z

73 m/z87 m/z101 m/z115 m/z129 m/z143 m/z157 m/z171 m/z185 m/z199 m/z213 m/z227 m/z241 m/z255 m/z269 m/z283 m/z297 m/z53 m/z60 m/z

81 m/z95 m/z109 m/z151 m/z193 m/z207 m/z

221 m/z

235 m/z249 m/z277 m/z75 m/z89 m/z103 m/z117 m/z131 m/z145 m/z159 m/z187 m/z201m/z229 m/z243 m/z257 m/z271 m/z299 m/z55 m/z69 m/z83 m/z

97m/z111 m/z125 m/z153 m/z167 m/z195 m/z209 m/z223 m/z237 m/z251 m/z265 m/z279 m/z

42 m/z

77 m/z

105 m/z

147 m/z161 m/z189 m/z203 m/z217 m/z231 m/z245 m/z259 m/z273 m/z287 m/z

57 m/z71 m/z85 m/z99 m/z113 m/z127 m/z141 m/z

183 m/z

211 m/z239 m/z253 m/z267 m/z

Factor1

Factor2

Factor3RT01RT02RT03RT04RT05RT06RT07

RT08RT09RT10RT11RT12

RT13RT14RT15

RT16RT17RT18RT19

RT20RT21

p101p102

p103p104

p105p106p107p108

p109

p110p201

p202p203

p204p205

p206

p207

p208p209

p210

p301

p302

p303p304

p305

RT22RT23RT24 Factor1

Factor2

Factor3

30 m/z

37 m/z

44 m/z51 m/z58 m/z65 m/z72 m/z79 m/z86 m/z93 m/z100 m/z107 m/z114 m/z


198 m/z205 m/z212 m/z219 m/z

226 m/z233 m/z240 m/z247 m/z254 m/z261 m/z268 m/z275 m/z282 m/z289 m/z296 m/z303 m/z310 m/z317 m/z324 m/z331 m/z338 m/z345 m/z352 m/z359 m/z366 m/z373 m/z380 m/z387 m/z394 m/z401 m/z408 m/z415 m/z422 m/z429 m/z436 m/z443 m/z450 m/z457 m/z464 m/z471 m/z478 m/z485 m/z492 m/z499 m/z31 m/z38 m/z45 m/z52 m/z59 m/z

66 m/z80 m/z87 m/z

94 m/z

101 m/z

108 m/z

115 m/z

122 m/z

129 m/z

136 m/z

143 m/z

150 m/z

157 m/z

164 m/z

171 m/z

178 m/z

185 m/z

192 m/z199 m/z

206 m/z213 m/z

220 m/z227 m/z

234 m/z241 m/z248 m/z255 m/z262 m/z269 m/z276 m/z283 m/z290 m/z297 m/z304 m/z311 m/z318 m/z325 m/z332 m/z339 m/z346 m/z353 m/z360 m/z367 m/z374 m/z381 m/z388 m/z395 m/z402 m/z409 m/z416 m/z423 m/z430 m/z437 m/z444 m/z451 m/z458 m/z465 m/z472 m/z479 m/z486 m/z493 m/z500 m/z32 m/z39 m/z46 m/z53 m/z

60 m/z


137 m/z144 m/z151 m/z158 m/z165 m/z172 m/z179 m/z186 m/z193 m/z200 m/z207 m/z214 m/z


110 m/z

117 m/z

124 m/z

131 m/z

138 m/z

145 m/z

152 m/z

159 m/z

166 m/z

173 m/z

180 m/z187 m/z

194 m/z201m/z

208 m/z

215 m/z

222 m/z229 m/z236 m/z243 m/z250 m/z257 m/z264 m/z271 m/z278 m/z285 m/z292 m/z299 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z

55 m/z

62 m/z69 m/z76 m/z83 m/z90 m/z97m/z

104 m/z111 m/z118 m/z125 m/z

132 m/z

139 m/z

146 m/z153 m/z


49 m/z56 m/z63 m/z70 m/z77 m/z84 m/z91m/z98 m/z

105 m/z

112 m/z

119 m/z

126 m/z

133 m/z

140 m/z

147 m/z

154 m/z161 m/z

168 m/z175 m/z

182 m/z

189 m/z

196 m/z203 m/z

210 m/z

217 m/z

224 m/z

231 m/z

238 m/z245 m/z252 m/z259 m/z266 m/z273 m/z280 m/z287 m/z294 m/z301 m/z308 m/z315 m/z322 m/z329 m/z336 m/z343 m/z350 m/z357 m/z364 m/z371 m/z378 m/z385 m/z392 m/z399 m/z406 m/z413 m/z420 m/z427 m/z434 m/z441 m/z448 m/z455 m/z462 m/z469 m/z476 m/z483 m/z490 m/z497 m/z36 m/z43 m/z50 m/z57 m/z64 m/z71 m/z

78 m/z85 m/z

92 m/z

99 m/z

106 m/z

113 m/z

120 m/z

127 m/z

134 m/z

141 m/z

148 m/z

155 m/z

162 m/z

169 m/z

176 m/z

183 m/z

190 m/z197 m/z


73 m/z

T = 23 oC

T = 50 oC

virgin pads,

3 different boxes

virgin pads,

3 different boxes

Scores Plot Loading Plot

bkgndlab airS-147

Factor1

Factor2

Factor3

bkgn01bkgn02bkgn03bkgn04bkgn05bkgn06bkgn07bkgn08bkgn09bkgn10bkgn11bkgn12bkgn13bkgn14bkgn15

p402

p502p503

p504

p601

p602p603

p604p605

p401p501 Factor1

Factor2

Factor3 30 m/z44 m/z51 m/z58 m/z65 m/z72 m/z86 m/z93 m/z100 m/z114 m/z121 m/z128 m/z135 m/z142 m/z156 m/z170 m/z184 m/z198 m/z212 m/z226 m/z240 m/z254 m/z268 m/z282 m/z303 m/z310 m/z317 m/z324 m/z331 m/z338 m/z345 m/z352 m/z359 m/z366 m/z373 m/z380 m/z387 m/z394 m/z401 m/z408 m/z415 m/z422 m/z429 m/z436 m/z443 m/z450 m/z457 m/z464 m/z471 m/z478 m/z485 m/z492 m/z499 m/z31 m/z38 m/z45 m/z52 m/z

59 m/z


123 m/z

130 m/z137 m/z

144 m/z158 m/z165 m/z

172 m/z179 m/z186 m/z200 m/z214 m/z228 m/z242 m/z256 m/z263 m/z270 m/z284 m/z291 m/z298 m/z305 m/z312 m/z319 m/z326 m/z333 m/z340 m/z347 m/z354 m/z361 m/z368 m/z375 m/z382 m/z389 m/z396 m/z403 m/z410 m/z417 m/z424 m/z431 m/z438 m/z445 m/z452 m/z459 m/z466 m/z473 m/z480 m/z487 m/z494 m/z33 m/z40 m/z47 m/z54 m/z61 m/z


180 m/z194 m/z208 m/z

215 m/z

222 m/z236 m/z250 m/z264 m/z278 m/z285 m/z292 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z62 m/z76 m/z90 m/z104 m/z118 m/z132 m/z

139 m/z

146 m/z160 m/z174 m/z181 m/z

188 m/z202 m/z216 m/z230 m/z244 m/z258 m/z272 m/z286 m/z293 m/z300 m/z307 m/z314 m/z321 m/z328 m/z335 m/z342 m/z349 m/z356 m/z363 m/z370 m/z377 m/z384 m/z391 m/z398 m/z405 m/z412 m/z419 m/z426 m/z433 m/z440 m/z447 m/z454 m/z461 m/z468 m/z475 m/z482 m/z489 m/z496 m/z35 m/z49 m/z56 m/z63 m/z70 m/z84 m/z91m/z98 m/z112 m/z119 m/z126 m/z133 m/z140 m/z154 m/z168 m/z175 m/z182 m/z196 m/z210 m/z224 m/z238 m/z252 m/z266 m/z280 m/z294 m/z301 m/z308 m/z315 m/z322 m/z329 m/z336 m/z343 m/z350 m/z357 m/z364 m/z371 m/z378 m/z385 m/z392 m/z399 m/z406 m/z413 m/z420 m/z427 m/z434 m/z441 m/z448 m/z455 m/z462 m/z469 m/z476 m/z483 m/z490 m/z497 m/z36 m/z43 m/z


155 m/z

162 m/z169 m/z

176 m/z190 m/z197 m/z

204 m/z218 m/z225 m/z


73 m/z87 m/z101 m/z115 m/z129 m/z143 m/z157 m/z171 m/z185 m/z199 m/z213 m/z227 m/z241 m/z255 m/z269 m/z283 m/z297 m/z53 m/z60 m/z

81 m/z95 m/z109 m/z151 m/z193 m/z207 m/z

221 m/z

235 m/z249 m/z277 m/z75 m/z89 m/z103 m/z117 m/z131 m/z145 m/z159 m/z187 m/z201m/z229 m/z243 m/z257 m/z271 m/z299 m/z55 m/z69 m/z83 m/z

97m/z111 m/z125 m/z153 m/z167 m/z195 m/z209 m/z223 m/z237 m/z251 m/z265 m/z279 m/z

42 m/z

77 m/z

105 m/z


57 m/z71 m/z85 m/z99 m/z113 m/z127 m/z141 m/z

183 m/z

211 m/z239 m/z253 m/z267 m/z

Factor1

Factor2

Factor3RT01RT02RT03RT04RT05RT06RT07

RT08RT09RT10RT11RT12

RT13RT14RT15

RT16RT17RT18RT19

RT20RT21

p101p102

p103p104

p105p106p107p108

p109

p110p201

p202p203

p204p205

p206

p207

p208p209

p210

p301

p302

p303p304

p305

RT22RT23RT24 Factor1

Factor2

Factor3

30 m/z

37 m/z

44 m/z51 m/z58 m/z65 m/z72 m/z79 m/z86 m/z93 m/z100 m/z107 m/z114 m/z


198 m/z205 m/z212 m/z219 m/z

226 m/z233 m/z240 m/z247 m/z254 m/z261 m/z268 m/z275 m/z282 m/z289 m/z296 m/z303 m/z310 m/z317 m/z324 m/z331 m/z338 m/z345 m/z352 m/z359 m/z366 m/z373 m/z380 m/z387 m/z394 m/z401 m/z408 m/z415 m/z422 m/z429 m/z436 m/z443 m/z450 m/z457 m/z464 m/z471 m/z478 m/z485 m/z492 m/z499 m/z31 m/z38 m/z45 m/z52 m/z59 m/z

66 m/z80 m/z87 m/z

94 m/z

101 m/z

108 m/z

115 m/z

122 m/z

129 m/z

136 m/z

143 m/z

150 m/z

157 m/z

164 m/z

171 m/z

178 m/z

185 m/z

192 m/z199 m/z

206 m/z213 m/z

220 m/z227 m/z


60 m/z


137 m/z144 m/z151 m/z158 m/z165 m/z172 m/z179 m/z186 m/z193 m/z200 m/z207 m/z214 m/z


110 m/z

117 m/z

124 m/z

131 m/z

138 m/z

145 m/z

152 m/z

159 m/z

166 m/z

173 m/z

180 m/z187 m/z

194 m/z201m/z

208 m/z

215 m/z

222 m/z229 m/z236 m/z243 m/z250 m/z257 m/z264 m/z271 m/z278 m/z285 m/z292 m/z299 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z

55 m/z

62 m/z69 m/z76 m/z83 m/z90 m/z97m/z

104 m/z111 m/z118 m/z125 m/z

132 m/z

139 m/z

146 m/z153 m/z


49 m/z56 m/z63 m/z70 m/z77 m/z84 m/z91m/z98 m/z

105 m/z

112 m/z

119 m/z

126 m/z

133 m/z

140 m/z

147 m/z

154 m/z161 m/z

168 m/z175 m/z

182 m/z

189 m/z

196 m/z203 m/z

210 m/z

217 m/z

224 m/z

231 m/z


78 m/z85 m/z

92 m/z

99 m/z

106 m/z

113 m/z

120 m/z

127 m/z

134 m/z

141 m/z

148 m/z

155 m/z

162 m/z

169 m/z

176 m/z

183 m/z

190 m/z197 m/z


73 m/z

T = 23 oC

T = 50 oC

virgin pads,

3 different boxes

virgin pads,

3 different boxes

Factor1

Factor2

Factor3

tommy1tommy2

tommy3

tommy4

tommy5

armani01armani02armani03

david01

david02david03

david04

david05

pad1501pad1502

pad1503pad1504pad1505tearose1tearose2

tearose3

tearose4

tearose5

m/z

100 200 300 400 500

rel.

abun

d.

0

50

100

m/z

100 200 300 400 500

rel.

abun

d.

0

50

100

m/z

100 200 300 400 500

rel.

ab

und

.

0

50

100

m/z

100 200 300 400 500

rel.

abun

d.

0

50

100

Aramis

Davidoff

Tea Rose

Tommy

3D Scores P lot

m/z

100 200 300 400 500

rel.

ab

und

.

0

50

100

virgin pad

Factor1

Factor2

Factor330 m/z37 m/z44 m/z51 m/z58 m/z65 m/z72 m/z79 m/z86 m/z93 m/z100 m/z



45 m/z52 m/z

59 m/z

66 m/z73 m/z80 m/z87 m/z94 m/z

101 m/z

108 m/z115 m/z122 m/z136 m/z143 m/z150 m/z


220 m/z

227 m/z

234 m/z

241 m/z248 m/z255 m/z262 m/z269 m/z276 m/z283 m/z290 m/z297 m/z304 m/z311 m/z318 m/z325 m/z332 m/z339 m/z346 m/z353 m/z360 m/z367 m/z374 m/z381 m/z388 m/z395 m/z402 m/z409 m/z416 m/z423 m/z430 m/z437 m/z444 m/z451 m/z458 m/z465 m/z472 m/z479 m/z486 m/z493 m/z500 m/z32 m/z39 m/z46 m/z53 m/z

60 m/z

67 m/z74 m/z81 m/z88 m/z95 m/z

102 m/z

109 m/z116 m/z123 m/z130 m/z137 m/z144 m/z151 m/z158 m/z165 m/z172 m/z179 m/z186 m/z193 m/z200 m/z207 m/z214 m/z221 m/z228 m/z235 m/z242 m/z249 m/z256 m/z263 m/z270 m/z277 m/z284 m/z291 m/z298 m/z

305 m/z

312 m/z319 m/z326 m/z333 m/z340 m/z347 m/z354 m/z361 m/z368 m/z375 m/z382 m/z389 m/z396 m/z403 m/z410 m/z417 m/z424 m/z431 m/z438 m/z445 m/z452 m/z459 m/z466 m/z473 m/z480 m/z487 m/z494 m/z33 m/z40 m/z47 m/z54 m/z

61 m/z

68 m/z

75 m/z82 m/z89 m/z96 m/z103 m/z110 m/z

117 m/z

124 m/z

131 m/z138 m/z145 m/z152 m/z159 m/z166 m/z173 m/z180 m/z187 m/z194 m/z201m/z208 m/z215 m/z222 m/z229 m/z

236 m/z


299 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z55 m/z62 m/z69 m/z76 m/z83 m/z90 m/z97m/z104 m/z111 m/z118 m/z125 m/z

132 m/z

139 m/z146 m/z153 m/z160 m/z


77 m/z

84 m/z91m/z

98 m/z105 m/z

112 m/z119 m/z126 m/z133 m/z140 m/z

147 m/z

154 m/z161 m/z168 m/z175 m/z

182 m/z189 m/z196 m/z

203 m/z


50 m/z

57 m/z64 m/z71 m/z

78 m/z

85 m/z

92 m/z

99 m/z106 m/z113 m/z120 m/z127 m/z

134 m/z


204 m/z


129 m/z259 m/z162 m/z

important discriminators for this cluster


Factor1

Factor2

Factor3

b01b02b03b04b05b06b07b08b09

b10b11b12b13b14

smp01smp02

smp03

p1001p1002p1003p1101p1102p1103p1201p1202p1203

p1301p1302

p1303

sp1001

sp1002

sp1003

sp1201

sp1202sp1203

m/z 101 (M-H)-

m/z 203 (2M-H)-

isovaleric acid

Pads spiked with isovaleric acid

pad spiked withheptanoic acid

Pads after sampling chamberwith isovaleric acid

Factor1

Factor2

Factor330 m/z37 m/z44 m/z51 m/z58 m/z65 m/z72 m/z79 m/z86 m/z93 m/z100 m/z



45 m/z52 m/z

59 m/z

66 m/z73 m/z80 m/z87 m/z94 m/z

101 m/z

108 m/z115 m/z122 m/z136 m/z143 m/z150 m/z


220 m/z

227 m/z

234 m/z


60 m/z

67 m/z74 m/z81 m/z88 m/z95 m/z

102 m/z

109 m/z116 m/z123 m/z130 m/z137 m/z144 m/z151 m/z158 m/z165 m/z172 m/z179 m/z186 m/z193 m/z200 m/z207 m/z214 m/z221 m/z228 m/z235 m/z242 m/z249 m/z256 m/z263 m/z270 m/z277 m/z284 m/z291 m/z298 m/z

305 m/z

312 m/z319 m/z326 m/z333 m/z340 m/z347 m/z354 m/z361 m/z368 m/z375 m/z382 m/z389 m/z396 m/z403 m/z410 m/z417 m/z424 m/z431 m/z438 m/z445 m/z452 m/z459 m/z466 m/z473 m/z480 m/z487 m/z494 m/z33 m/z40 m/z47 m/z54 m/z

61 m/z

68 m/z

75 m/z82 m/z89 m/z96 m/z103 m/z110 m/z

117 m/z

124 m/z

131 m/z138 m/z145 m/z152 m/z159 m/z166 m/z173 m/z180 m/z187 m/z194 m/z201m/z208 m/z215 m/z222 m/z229 m/z

236 m/z


299 m/z306 m/z313 m/z320 m/z327 m/z334 m/z341 m/z348 m/z355 m/z362 m/z369 m/z376 m/z383 m/z390 m/z397 m/z404 m/z411 m/z418 m/z425 m/z432 m/z439 m/z446 m/z453 m/z460 m/z467 m/z474 m/z481 m/z488 m/z495 m/z34 m/z41m/z48 m/z55 m/z62 m/z69 m/z76 m/z83 m/z90 m/z97m/z104 m/z111 m/z118 m/z125 m/z

132 m/z

139 m/z146 m/z153 m/z160 m/z


77 m/z

84 m/z91m/z

98 m/z105 m/z

112 m/z119 m/z126 m/z133 m/z140 m/z

147 m/z

154 m/z161 m/z168 m/z175 m/z

182 m/z189 m/z196 m/z

203 m/z


50 m/z

57 m/z64 m/z71 m/z

78 m/z

85 m/z

92 m/z

99 m/z106 m/z113 m/z120 m/z127 m/z

134 m/z


204 m/z


129 m/z259 m/z162 m/z



Factor1

Factor2

Factor3

b01b02b03b04b05b06b07b08b09

b10b11b12b13b14

smp01smp02

smp03

p1001p1002p1003p1101p1102p1103p1201p1202p1203

p1301p1302

p1303

sp1001

sp1002

sp1003

sp1201

sp1202sp1203

m/z 101 (M-H)-

m/z 203 (2M-H)-

isovaleric acid

Pads spiked with isovaleric acid

pad spiked withheptanoic acid

Pads after sampling chamberwith isovaleric acid

Figure 4Mass spectra of the headspace analysis of isovaleric acid and 2-nonenal in positive ion mode under identical conditions. Some fragmentation is observed and more “odorous” compounds must be characterized in both positive and negative ion before the “best” conditions for each mode are finalized.

Figure 5 Comparison in positive and negative ion mode of a scent pad used to sample a glass slide spotted with isovaleric acid (Desorption temperature at 40 oC). Chemical noise from the pad overshadows the protonated molecule at m/z 103. Less chemical noise in negative ion mode shows strong (M-H)- at m/z 101.

time

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Re

lativ

e A

bu

nd

an

ce

0

20

40

60

80

100

m/z

40 60 80 100 120 140 160 180

Re

lativ

e A

bu

nd

an

ce

0

20

40

60

80

100

isovaleric acidmw = 102temp: 100 oC

m/z 103

m/z 61

time

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Re

lativ

e A

bu

nd

an

ce

0

20

40

60

80

100

m/z

40 60 80 100 120 140 160 180

Re

lativ

e A

bu

nd

an

ce

0

20

40

60

80

100

m/z 81m/z 123

m/z 141

2-nonenalmw = 140temp = 100 oC

m/z 159

m/z

50 100 150 200 250 300

Re

lativ

e In

tens

ity

0

20

40

60

80

100

m/z

50 100 150 200 250 300

Re

lativ

e In

tens

ity

0

20

40

60

80

100

Negative ion modePositive ion mode

m/z 101

(M-H)-

m/z 103

(M+H)+

100 102 104 106 108

Figure 7 Scores plot on left shows several clusters. One associated with background air (yellow cluster on bottom) and one with unused pads (lower right cluster). The orange cluster in the bottom left represents pads spiked with heptanoic acid and the clusters at the top represent isovaleric acid spiked onto pads (blue) and pads used to sample a chamber with isovaleric acid (yellow). The loading plot on the right shows that the principle discriminators for the clusters are indeed the molecular species for isovaleric acid (top cluster) and heptanoic acid (bottom left).

Figure 8 The resulting dendrogram from the HCA analysis of this data set shows that the pads spiked with isovaleric acid (sp#) and the pads used to sample the chamber of isovaleric acid (smp#) are more similar to one another than either the heptanoic acid spiked pads or unused pads.

Figure 3 Scent pad being placed into thermal desorption unit.

pleasantodor

malodor

“odorome”

pleasantodor

malodor

“odorome”

Rapid Mass Spectral Acquisition and Statistical Analysis for Determination of Scent DiscriminatorsKeiji G. Asano1, Gary J. Van Berkel1, Scott A. Ramsey2, and Brian A. Eckenrode3

1Oak Ridge National Laboratory, Oak Ridge, TN, 2Michigan State University, East Lansing, MI, 3Federal Bureau of Investigation, Quantico, VA

RESULTS AND DISCUSSIONMULTIVARIATE ANALYSISHUMAN SCENT

EXPERIMENTAL

REFERENCES

BACKGROUND

OVERVIEW SUMMARY

FUTURE WORK

ACKNOWLEDGEMENTS

Spiked pad study at 50 0 C to show discriminators of groups are indicative of chemical component...

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Transcript of Spiked pad study at 50 0 C to show discriminators of groups are indicative of chemical component...