9/27/2017 1 Adventures in Analysis of Peroxide Explosives HO OOH OOH HOO O HOO O OOH H 3 C C CH 3 O O O O C O C O H 3 C H 3 C CH 3 CH 3 N CH 2 H 2 C H 2 C O O O O O O CH 2 CH 2 H 2 C N TATP HMTD Methyl Ethyl Ketone Peroxides Jimmie C. Oxley University of Rhode Island [email protected]; 401-874-2103 PhD Students: Kevin Colizza Lindsay McLennan Alex Yeudakimau Professors: Jimmie Oxley & Jim Smith This work is supported by the U.S. Department of Homeland Security but views & conclusions are those of the authors alone. Studies with Peroxide Explosives Hair as forensic evidence Safe Scent Canine Training Aids Methods: Gentle Destruction of Peroxides 450 g TATP digested in 25 min
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100 μM TATP in 10mM potassium phosphate buffer incubated 37°C for 60 min in 1.5 mL Eppendorf snap-cap tube
HN
N
N
N
hexamine N(CH3)3 HN(CH3)2
dimethylformamide
methylformamide
ethylenimine
1-methyl-1H-1,2,4-triazole
NH
O
NH
O
N,N'-methylenebis(formamide)
TATP headspace
DimethylformamideEthylenimine
Methylformamide
trimethylamine
HMTD Headspace
To make safe scent aids, headspace signature must be determined
The headspace of TATP contains only TATP. The scent aid must be TATP
The headspace of HMTD contains mainly decomposition products. These non‐explosives make up the odor.
9/27/2017
3
TATP vs DADP FormationHO
C
OOH
H3C CH3
C
H3C CH3
O
+ H2OH2O2
HOO
C
OOH
H3C CH3
C
H3C CH3
O
+ +
1:1:1 acetone:HP:acid (8.6 mmol) rt
50% HP (g) water (mL)
96.5% sulfuric acid
(g) % TATP % DADP
0.59 0.25 0.88 100
0.59 0.50 0.88 7.6 92
0.59 0.75 0.88 81 19
0.59 1.0 0.88 100
+ H2O2H2O
High [acid] low [water]
+H2O
C
O
H3CCH3
O
C
CH3
OOH
H3C
C
H3C CH3
O
H O O H
H+
HO
C
OOH
H3C CH3
HO
C
O
H3CCH3
O
C
CH3
OH
H3C
HO
C
O
H3CCH3
O
C
CH3
OOH
H3C
HP
H3C
C
CH3
O O
O O
C
H3C CH3
HP
HOO
C
OOH
H3C CH3
HOC
OOH
H3C CH3
HOO
C
O
H3CCH3
O
C
CH3
OOH
H3C
HOO
C
O
H3CCH3
O
C
CH3
O
H3C
O
C
CH3
OH
H3C
H O O H
H+
OO
C
O
OC
O
O
C
CH3H3C
CH3
CH3
H3C
H3C
aceto
ne
+ H2O
acetone
+ H2O
+ H2O
HP
I
II
III
IV
V
DADP
TATP
HOC
OOH
H3C CH3
No acid required
Acid andhigh [water]
Acid
Acid andhigh [water]
Hig
h a
cid
lo
w w
ate
r
Acid andhigh [water]
Acid andhigh [water]
Acid andhigh [water]
Low [water]
HMTD has little vapor pressure; its odor is decomposition productsMay 2013 HMTD (250mg in glass vial) exploded as chemist picked it up. As explosives start to decompose, they become more sensitive because porosity increases,
HMTD already has lower thermal stability than any military explosive (DSCexo 200-300oC) & even most HME. Friction & ESD sensitivities are high.
& density decreases. Pores introduce heterogeneity which increases sensitivity.
dry HMTD
HMTD+2uLH2O
0
10
20
30
40
50
60
70
80
90
100
'1 week
Humidity 0
29%
74.50%
100%
Week 1 Week 2 Week 4
29
75
100
May 2013Jan 2015
171oC
142oC
9/27/2017
4
Mass Identity amount
1 73 L DRY & HUMID
2 75 L
MATCHED TO AUTHENTIC SAMPLE; MAINLY SEEN IN HUMID CONDITIONS
3 103 M
MATCHED TO AUTHENTIC SAMPLE; MAINLY SEEN IN HUMID CONDITIONS
4 88 S
5 84, 102 L
MATCHED TO AUTHENTIC SAMPLE; DRY CONDITIONS
6 116 L DRY CONDITIONS
7 178 SBOTH IN DRY &
HUMID CONDITIONS
8 140 M
MATCHED TO AUTHENTIC
SAMPLE; MAINLY SEEN IN HUMID OR
ACIDIC CONDITIONS
9 208 L
10 143 S
11 171 L
MATCHED TO AUTHENTIC SAMPLE; MAINLY SEEN IN HUMID CONDITIONS
12 157 SMAINLY SEEN IN DRY CONDITIONS
[M+H]+ Identity amount
1 74.06004 L C3H8ON
2 103.0501 L
C3H7O2N2 MATCHED TO AUTHENTIC
SAMPLE
3 106.0499 S C3H8O3N
4 117.0659 L C4H9O2N2
5 117.1022 L C5H13ON2
6 120.0768 S C3H10O2N3
7 133.0608 S C4H9O3N2
8 141.1131 L C6H13N4
9 144.0768 M C5H10O2N3
10 145.0608 M C5H9O3N2
11 155.1289 M C7H15N4
12 157.1083 L C6H13ON4
NH
N
O O
13 158.0923 L C6H12O2N3
14 160.0717 L C5H10O3N3
15 172.0712 L
C6H10O3N3 MATCHED TO AUTHENTIC
SAMPLE
16 172.1078 S C7H14O2N3
17 174.0873 M C6H12O3N3
18 174.1235 S C7H16O2N3
19 185.1032 S C7H13O2N4
20 201.0982 L C7H13O3N4
21 205.0931 S C6H13O4N4
22 207.0611 TMDDD M C6H11O6N2
23 209.0768 HMTD M C6H13O6N2
GC-MSLC-MS R1-A.1LC‐MS GC‐MS
HMTD Decomposition Products
C6N4H12 + 6 H2O2 + 6 OCH2 2 C6N2H12O6 + 6 H2O
C6N4H12 + 3 H2O2 1 C6N2H12O6 + 2 NH3
With added formaldhyde reaction is fasterYield 130% based on 1 HMTD : 1 hexamine;
70% based on 2 HMTD : 1 hexamine
9/27/2017
5
13C is incorporated in HMTD with added 13COH2 under formation conditions.
N O
O
O
O
O
O
N13COH2
209 210 211 212 213 214m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Relative Abundance
211.0837
210.0804
212.0871
209.0771
213.0904
214.1553
209.0771C6H13O6N2
+
210.0804C5
13CH13O6 N2+
211.0837C4
13C2H13O6N2+
212.0871C3
13C3H13 O6N2+
213.0904C2
13C4H13O6N2+
HMTD
141.0 141.5 142.0 142.5 143.0 143.5m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Relativ
e A
bundance
141.1136C 6 H13 N4
142.1169C 5 13C H13 N4
143.1202C 4 13C 2 H13 N4
141.2977140.9294
Hexamine
142.1169 C5
13CH13 N4+
Should be ~6.5 % relative to 12CIs about 20%
143.1202 C4
13C2H13 N4+
Should be ~0.2% relative to 12CIs about 1.6%
NN
N
N
141.1136 C6H13N4
+ Some 13C also appeared in remaining hexamine
N O
O
O
O
O
O
N
{ }
141 142 143 144 145 146 147m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bunda
nce
141.1135C 6 H13 N4
145.1016C 6 H13 15N4
142.1169C 3 H16 O3 N3
146.1049C 2 H15 O3 N 15N3144.0656
C 6 H10 O3 N143.0815
C 6 H11 O2 N2 145.3487141.3505 144.8547140.8770
H2O2 + citric acid{ }
202 204 206 208 210 212 214 216 218 220m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive A
bunda
nce
210.0739C 6 H13 O6 N 15N
209.0769C 6 H13 O6 N2
211.0710C 6 H13 O6 15N2
205.1548C 9 H21 O3 N2
208.0583C 6 H11 O6 N 15N
212.0745C 2 H15 O9 N 15N
202.1438C 10 H20 O3 N
217.0972C 12 H13 O2 N2
219.1704C 10 H23 O3 N2
206.1582C 4 H22 O5 N4
15N15N
15N
15N
+
15N15N
15N
15N
Mechanism where hexamine breaks down is supported
Formation Mechanism Evidence
15N label scrambled during HMTD formation, but no scrambling in starting materials observed.
9/27/2017
6
NH
CH H
HO OHH+
H2NC
H H
OOHNH
CH H
H+
O OH2N NH2
O OH2N NH2
O OHO OH
NHHN
O O
O O
O OHO OH
N O
O
O
O
O
O
N
2
DHMP
4H2O O
H H4 +
NH
CH H
2 + NH32
O
H H
2 HO OH+ OO
HOOH
2X
Mechanism for HMTD Formation involves C & N scrambling
This is curious since ACN has a lower proton affinity than most of the analytes.
Polar interaction between nitrile and analyte causes formation of neutral aggregatePolarization
R groups block site of ionizationWhen analyte in cis configuration
Analysis with electron donating (-NH2), electron withdrawing (-Br) and steric (trimethyl) nitriles support this mechanism.
Peroxides in cis formation have large dipole.
TATP and HMTD are forced into cis configuration
Large, linear peroxides cannot form cis isomer without self-steric interaction
DHP3 and DHP4 were not affected by ACN
Addition of heat (HESI) showed significant effect for DHP3 not DHP4!
Peroxide Detection
O
O
HO
O O
O O
OH
O
OO
OO
HO
O
O
OH
O
MEKP DHP3
MEKP DHP4
Proposed Mechanism for Ion Suppression by ACN
Rapid Communications in Mass
Spectrometry 2016, 27(1), 1796‐1804.
9/27/2017
9
Full Scan of HMTD in MeOH/H2O—why two 207 peaks?
207.0 207.5 208.0 208.5 209.0 209.5
m/z
0
20
40
60
80
100
0
20
40
60
80
100R
elat
ive
Abu
ndan
ce207.0979 209.0771
208.1011207.0621
209.0772
207.0980
NL: 7.12E5
HMTD_100%MeOH_Infuse_APCI_3june2014#8-41 RT: 0.06-0.29 AV: 34 T: FTMS + p APCI corona Full ms [150.00-500.00]
NL: 6.39E5
hmtd_10%meoh_90%water_infuse_apci_3june2014#6-35 RT: 0.05-0.25 AV: 30 T: FTMS + p APCI corona Full ms [150.00-500.00]
207.0617
100% MeOH
10% MeOH
[HMTD+H++MeOH-H2O2]+
ΔPPM = 1.70
[HMTD-H2+H]+
ΔPPM = 2.60
C6H13O6N2
[HMTD+H]+
ΔPPM = 1.40
C7H15O5N2
C6H11O6N2
HMTD infused in CD3OD/D2O or CH318OH/H2O
[HMTD+D++CD3OD+-D2O2]+
ΔPPM = 0.67
[HMTD+H]+
ΔPPM = 0.91(non-deuterated solvent impurity)
[HMTD+D]+
ΔPPM = 1.24
All peroxide hydrogens → lost from the solvent!
209.1022
209.0774
207.0 207.5 208.0 208.5 209.0m/z
0
20
40
60
80
100
120
Rel
ativ
e A
bund
ance
[HMTD+H]+
ΔPPM = 2.82
[HMTD+H++Me18OH-H2O2]+
ΔPPM = 1.96
All peroxide oxygens → lost from HMTD
210.1165
210.0834
209.2 209.4 209.6 209.8 210.0 210.20
20
40
60
80
100
Rel
ativ
e A
bund
ance
209.0770
CD3OD/D2O
CH318OH/H2O
C7H12D3O5N2+
C6H12DO6N2+
C7H15O418ON2
+
C6H13O6N2+
9/27/2017
10
Proposed Mechanism for Formation of (A) Protonated HMTD or (B) Alcohol‐Bonded Species
[M+H]+
m/z = 209.0768
R m/zH- 193.0819
CH3- 207.0976CH3CH2- 221.1132C2H6CH2- 235.1289
C4H9- 249.1445C6H11- 275.1601C8H17- 305.2071
Rapid Comm Mass Spectrometry 2015, 29(1), 74-80. Oxygens lost from HMTDHydrogens lost from solvent
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
0 2 4 6 8
% M
ethan
ol in M
obile P
hase
m/z
89.
0597
/240
.144
2 In
ten
sity
Rat
io
Time (min)
Increase of m/z 89.0597 relative to m/z 240.1442 with increasing MeOH
Post-column addition TATP in MeOH/water into LC flow of std gradient (10 mM NH4OAc/MeOH) monitoring ratio of m/z 89.0597 to m/z 240.1442 with increasing methanol.
Which mass & column for best detection limits? With ammonium modifier present → 240.1442 (TATP-NH4
+) or 89.0597 (C4H9O2+)?
TATP elution time on PFP column
TATP elution time on C18 column
~65% MeOH
~85% MeOH
Gradient
9/27/2017
11
NL:1.96E6
88 90 92 94 96 98 100 102 104m/z
05
101520253035404550556065707580859095
100
Rel
ativ
e A
bund
ance
97.0776
91.0400
105.0556
89.0608
95.098488.0530
103.0764
98.117294.0589 101.060792.0434 104.0716
or
or
92.0795
O
OH
O
D3C CD3
OO
D3C CD3
O
OH
O
Direct infusion (20 μL/min) of TATP (5 μg/mL), d18-TATP (5 μg/mL) & MEKP (10 μg/mL) in 90% MeOH/10% 10 mM NH4OAc. Only m/z 88-105 shown; incorporated ROH in red.
Infusion of TATP, d18-TATP & MEKP in CH3OH in to APCI Source
OO
OHO
OO
What is Mass 89.0597? C4H9O2+ is unlikely fragment!
OO
O
O
O
O +3H
-2CH3
d18-TATP produced m/z 95 C4H3D6O2
+ not m/z 98 C4D9O2+
and m/z 92 C4H6D3O2
+
NL: 2.63E6
88 90 92 94 96 98 100 102104
m/z05
101520253035404550556065707580859095
100
Rel
ativ
e A
bund
ance
91.0651
105.0807
89.0609
97.102793.0693
103.0765102.1289
104.0967
88.1132 100.076895.0985
96.0881
94.0662 101.097292.0684 99.081590.0925 98.1173
88.0531
96.0632
91.0401
97.0777
105.0557
D3C CD3
18OO
D3C
18O
OH
O
18OO
O
OH
O
93.0443
Direct Infusion (20 μL/min) of TATP (5 μg/mL), d18-TATP (5 μg/mL) and MEKP (10 μg/mL) in 90% Me18OH/10% 10 mM NH4OAc. Only m/z 88-105 are shown for resolution purposes.
Infusion of TATP, d18-TATP & MEKP in CH318OH into the APCI source
18OO
OO
Lower gas flow promoted the formation of 95 and 92. Higher flow favored [M+NH4]+ and 97 formation. Lower gas flow may mean more time to react with MeOH in the discharge region or more time in the heated region of ceramic tube.
9/27/2017
12
m/z = 88.0519
TATP formation of m/z 89.0597 (corresponds to MEKP m/z 103.0754)
m/z = 89.0597
Proposed mechanism of gas phase formation of m/z 89 for TATP or 103 for MEKP & m/z 88 for MEKP or m/z 74 for TATP
MEKP formation of m/z 88.0519 (corresponds to TATP m/z 74.0362)
+ +
++
+
RT:0.00 - 8.01
0 1 2 3 4 5 6 7 8Time (min)
0
20
40
60
80
1000
20
40
60
80
1000
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
1002.07
4.80
4.80
4.802.09
RT:0.00 - 8.01
0 1 2 3 4 5 6 7 8
Time (min)
0
20
40
60
80
1000
20
40
60
80
1000
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
1004.88
2.11
4.88
4.88
4.88
2.11
Krawczyk suggested converting HMTD to TMDDD would improve detectable, but…. We attempted to form in-situ by injecting HMTD (100 ng) onto 5cm PFP column with APCIsource & raising temperature 210°C 300°C. More TMDDD formed, but not enough.
We observed HMTD always had TMDDD contamination.
TMDDD TMDDDHMTD
m/z 207.0611
HMTD
m/z 207.0975
m/z 209.0768
m/z 224.0877
210°C 300°C
6.9e47.0e4
1.0e6 1.4e6
0
7.3e6 5.8e6
3.1e6 2.5e6
3.1e5
4.2e62.2e5
HN
O O O
O O O
N
TMDDD
TMDDD unaffected by temperature rise. HMTD formation of TMDDD is affected by temperatureNumbers by peaks are area counts.
9/27/2017
13
HMTD infused with MeNH2 produced different peaks in APCI & ESI.
ESI+_HMTDinACNwMeNH2_10ugmL_11nov2016_161024142316 #13T: FTMS + p ESI Full ms [60.00-600.00]
100 150 200 250 3000
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Relative Abu
ndance
238.1032
220.1365
113.1071
161.1646
72.0803
171.1490
191.0661287.0807
279.1593
90.0910
310.
ESI
APCI+_HMTDinMeOHwMeNH2_10ugmL_11nov2016_161024142T: FTMS + p APCI corona Full ms [100.00-600.00]
150 200 250 3000
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Relative Abu
ndan
ce
248.2218
240.1188
209.0766145.0605
163.0711114.0910
195.0874
279.1588
310.
APCI
240.1188
238.1032
209.0766
220.1365
Could an amine replace ammonium in aiding detection of HMTD?
HN
OO
O
O OO
N
H2N
oror
Could detection of HMTD be improved by in-situ formation of TMDDD & interaction with amine? Thus, HMTD with post-column addition of EtNH2
RT: 0.00 - 8.00
0 1 2 3 4 5 6 7 8Time (min)
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
4.01
4.04
4.09
4.12
4.184.53
4.01
3.99 4.03
4.07
4.10
3.94
4.183.863.561.59 2.940.86 1.90
1.87 1.881.84
1.911.961.79
1.74 2.002.031.40
1.29 2.051.07
2.13
3.20 3.172.25 4.07 4.090.97 7.18
NL: 1.43E6m/z= 209.0731-209.0810 F: FTMS + p ESI Full ms [100.00-500.00] MS HMTD_20ugmL_PostColEtNH2_ESI_15nov2016_3
NL: 1.09E6m/z= 254.1263-254.1432 F: FTMS + p ESI Full ms [100.00-500.00] MS HMTD_20ugmL_PostColEtNH2_ESI_15nov2016_3
NL: 3.11E6m/z= 252.1131-252.1258 F: FTMS + p ESI Full ms [100.00-500.00] MS HMTD_20ugmL_PostColEtNH2_ESI_15nov2016_3
RT: 0.00 - 7.50
0 1 2 3 4 5 6 7Time (min)
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
0
20
40
60
80
100
Rel
ativ
e A
bund
ance
3.44
3.59 3.76 4.19 4.67 5.633.233.44
3.47
3.403.52
3.64 3.744.20 5.03 5.341.911.69 3.20 5.66
3.453.47
3.401.761.00 3.560.93
1.821.07 3.72 3.75
NL: 1.04E7m/z= 209.0721-209.0815 F: FTMS + p APCI corona Full ms [80.00-280.00] MS HMTD_20ugmL_PostColEtNH2_APCI_15nov2016_4
NL: 1.70E7m/z= 254.1286-254.1398 F: FTMS + p APCI corona Full ms [80.00-280.00] MS HMTD_20ugmL_PostColEtNH2_APCI_15nov2016_4
NL: 8.57E5m/z= 252.1131-252.1235 F: FTMS + p APCI corona Full ms [80.00-280.00] MS HMTD_20ugmL_PostColEtNH2_APCI_15nov2016_4
APCI ESI
209.0768 209.0768
254.1340254.1340
252.1190 252.1190
HN
OO
O
O O O
N
TMDDD TMDDDHMTD HMTD
1.0 e7
1.7 e7
8.6 e5
1.4 e6
1.0 e6
8.1 e6
Numbers in blue are peak area counts.
Formed TMDDD
contamination contaminationdecomposition decompositionRetention time Retention time
Note: HMTD is best observed by APCI, and TMDDD in ESI.
9/27/2017
14
APCI+_HMTD_IPamine2mM_14feb2017_1 #72-103 RT: 1.81-2.66 AV: 28 NL: 1.65E5T: FTMS + p APCI corona Full ms2 [email protected] [55.00-400.00]
2-nitroaniline 347.1197 NR -0.28(2-aminoethyl)trimethylammonium 311.1925 NR na
* Triethylamine forms an adduct to HMTD with no observable chemical reactionNR-no reaction, na-not available
Amines infused with HMTD into APCI source
If amine reacted with HMTD, the quaternary amine would make a charged product
• TMDDD forms intense adducts with amines in ESI source• Adduct formation was confirmed since no fragments were detected for TMDDD + amine• When mass of amine was > 50 amu → detected fragment was only the ionized amine
• HMTD formed products with basic amines; these gave abundant MS fragments• Fragments suggest incorporation of the amine into the HMTD structure• Intensity of the product is related to the amine basicity• Triethylamine only forms an adduct with HMTD.
• Trimethylamine, 2-nitroaniline, (2-aminoethyl)trimethyl ammonium, & choline did not form covalent products with HMTD.
N
O O
O O O
N
N R
H H
N R
HN
O O
OO O O
N
H
N
R
HH
H
H
N
O O
O O
N
N R
H
HOOH
N
O O
O O
N
N R
H
11
12
13
19
14 16
17
HN
O O
O O
N
OOH2
15
Thoughts on Mechanism for the Fragmentation of the HMTD/amine Product in CID
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9/27/2017
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1. TATP is extremely volatile, even in solution, but in headspace TATP is intact, unlike HMTD where the headspace is decomposition products.
2. ACN in MP of LC‐MS suppresses charge for some peroxides & ketones.3. TATP and HMTD react with MeOH in gas phasefor TATP this results in LC‐MS peak at 89 indicating addition of 1 or 2 MeOHfor HMTD this results in 207
4. Reactions of TATP or HMTD with ROH can be used to lower detection limits but variable results will be obtained if LC‐MS analytical conditions are changed.Analytical conditions include