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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
Appendix C
Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot
Tables C-1 through C-5 provide a summary overview of what is known about the current condition of the Levenstein mustard agent (H) in the U.S. chemical stockpile, including that in the projectiles stored at Deseret Chemical Depot.1 This form of mustard agent has degraded from what was originally about 70 percent pure mustard agent (liquid) and 30 percent (liquid) impurities into a mixture that is, on average, 70 percent solids and 30 percent liquid.
1
E-mail communication from Yu-Chu Yang, ACWA, on April 12, 2005, to Robert A. Beaudet, committee chair.
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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
TABLE C-1 Composition of Liquid H (Levenstein Mustard), 16-42 wt% (Average = 31 wt%) of Agent Fill in the 10 155-mm H Projectiles Tested During Munitions Washout System Testinga,b
Compound Name
Structure
Gas Chromatograph/Mass Spectrometry—Chemical Ionization (GC/MS–CI) (area%)
Nuclear Magnetic Resonance (NMR) (wt%)
Volatile impurities
Neat
CD3CN Solvent
1-Butene
0.067 (0.040-0.12)
2-Chlorobutane
0.034 (0.020-0.070)
Diethyl ether
0.084 (0.030-0.20)
0.24 (0.070-0.40)
Chloroform
0.037 (0.010-0.12)
HD and degradation compounds
1,2-Dichloroethane
ClCCCl
1.7 (1.1-2.6)
2.0 (1.4-2.9)
1,4-Dithiane
3.0 (2.0-3.6)
0.92 (0.45-1.2)
Ethylene sulfide (Thiirane)
0.036 (0.020-0.060)
Bis(2-chloroethyl) sulfide (HD)
ClCCSCCCl
81 (78-84)
78 (74-81)
1,2-Bis(2-chloroethylthio)ethane (Q)
ClCCSCCSCCCl
7.9 (6.6-9.4)
10.2 (8.7-12)
C3/C4 HD analogs/impurities
2.0 (1.4-2.8)
Bis(3-chloropropyl) sulfide
0.24 (0.20-0.30)
2-Chloroethyl-4-chlorobutyl sulfide
0.83 (0.70-1.0)
2-Chloroethyl-2-chlorobutyl sulfide
0.059 (0.030-0.080)
2-Chloropropyl-3-chloropropyl sulfide
0.41 (0.30-0.50)
2-Chloroethyl-3-chloropropyl sulfide
0.27 (0.20-0.30)
Linear polysulfides of HD
Bis(2-chloroethyl) disulfide, HS2
ClCC-S-S-CCCl
1.4 (0.80-2.4)
0.3 (0.14-0.41)
2-(Chloroethylthio) ethyl-2-chloroethyl disulfide
ClCCSCC-S-S-CCCl
0.18 (0.090-0.30)
Bis(2-chloroethyl) trisulfide, HS3
ClCC-S-S-S-CCCl 0.77
(0.20-1.5)
0.55 (0.27-0.95)
Bis(2-chloroethyl) tetrasulfide, HS4
ClCCS4CCCl
0.89 (0.53-1.5)
Bis(2-chloroethyl) polysulfide, HSx
ClCCSxCCCl
1.1 (0.45-2.0)
Cyclic polysulfides
1,2,3-Trithiolane
0.63 (0.20-1.4)
1,2,5-Trithiepane (7-membered ring)
0.77 (0.50-1.1)
1,2,3,4-Tetrathiane
0.21 (0.050-0.40)
1,2,3,4,5-Pentathiepane (7-membered ring)
0.16 (0.030-0.30)
Cyclic sulfonium ion
S-(2-chloroethyl)-1,4-dithianium ion
0.89 (0.31-1.6)
Total
99.78
97.09
aResults are the average and range for seven samples.
bGas chromatography/thermal conductivity detector quantitative results for HD using an internal standard were 84.6 wt% (81.8-87.7).
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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
TABLE C-2 Composition of H Heels, 58-84 wt% (Average = 69 wt%) of Agent Fill in the 10 155-mm Projectiles Tested During Munitions Washout System Testinga,b
Compound Name
Structure
GC/MS–CI Analysis of CH2Cl2 Extract (area%)
NMR Analysis of Three Extracts (wt%)
HD and degradation compounds
CHCl3 Extract
1,4-Dithiane
10 (7.4-15)
1.3 (0.64-2.9)
1,4-Thioxane
0.23 (0.10-0.50)
Bis(2-chloroethyl) sulfide (HD)
ClCCSCCCl
58 (52-64)
28 (10- 37)
1,2-Bis(2-chloroethylthio)ethane (Q)
ClCCSCCSCCCl
17 (14-20)
4.1 (0.99-5.5)
Bis(2-chloroethyl) sulfoxide
0.46 (0.20-0.60)
1,4-Dithiane-1-oxide
0.80 (0.30-1.6)
2-Chloroethyl vinyl sulfide
ClCC-S-CH=CH2
0.33 (0.020-0.60)
Bis[(2-chloroethylthio)ethyl] sulfide
ClCCSCC-S-CCSCCCl
2.6 (1.4-4.3)
(2-chloroethylthio)ethyl vinyl sulfide
ClCCSCCSCH=CH2
2.2 (1.5-2.9)
C3/C4 HD analogs/impurities
Bis(3-chloropropyl) sulfide
0.13 (0.050-0.20)
2-Chloroethyl-4-chlorobutyl sulfide
0.71 (0.60-0.80)
2-Chloroethyl-2-chlorobutyl sulfide
0.057 (0.040-0.080)
2-Chloropropyl-3-chloropropyl sulfide
0.29 (0.12-0.40)
2-Chloroethyl-3-chloropropyl sulfide
0.18 (0.11-0.30)
Linear polysulfides
Bis(2-chloroethyl) disulfide, HS2
ClCC-S-S-CCCl
0.29 (0.15-0.50)
2-(Chloroethylthio) ethyl 2-chloroethyl disulfide
ClCCSCC-S-S-CCCl
0.41 (0.30-0.50)
Bis(2-chloroethyl) trisulfide, HS3
ClCC-S-S-S-CCCl
0.86 (0.40-1.2)
Cyclic sulfides and polysulfides
2-Methyl-1,3-dithiolane
0.050 (one sample)
1,2,3-Trithiolane
1.0 (0.40-2.2)
1,2,5-Trithiepane (7-membered ring)
2.1 (1.1-4.4)
1,4,7-Trithionane
0.12 (0.080-0.15)
1,2,3,4-Tetrathiane
0.18 (0.080-0.40)
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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
Compound Name
Structure
GC/MS–CI Analysis of CH2Cl2 Extract (area%)
NMR Analysis of Three Extracts (wt%)
1,2,3,4,5-Pentathiepane (7-membered ring)
0.15 (0.080-0.30)
2-Methyl-1,3-dithiolane
0.050 (one sample)
1,4,7,10,13-pentathiacyclopentadecane
0.26 (0.070-0.90)
1,4,7,10-tetrathiacyclododecane
0.49 (0.14-1.0)
Elemental sulfur
Sulfur S6
0.10 (0.040-0.15)
Sulfur S8
6.0 (one sample)
Unknown MW
118 0.18 (0.11-0.30)
Cyclic thioethers
1-oxa-4,7,10,13-tetrathiacyclopentadecane
0.080 (0.060-0.10)
1-oxa-4,7,10-trithiacyclododecane
0.41 (0.30-0.50)
1-oxa-4,7-dithionane
0.30 (0.070-0.70)
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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
Compound Name
Structure
GC/MS–CI Analysis of CH2Cl2 Extract (area%)
NMR Analysis of Three Extracts (wt%)
Cyclic sulfonium ion
CH3CN Extract
S-(2-chloroethyl)-1,4-dithianium ion
36 (27-48)
Cyclic sulfonium dication
H2O Extract
1,4-Dithioniabicyclo[2.2.2]octane dication
1.4 (0.70-2.7)
Total
99.81
70.8c
a Results are the average and range for seven samples.
bUsing n-hexane extraction and an internal standard, gas chromatography/thermal conductivity detector quantitative measurements gave 13 wt% (5.47-18.4 wt%) HD.
cThe main elements in the residual were iron and sulfur.
TABLE C-3 Liquid Chromatography–Electrospray Ionization–Mass Spectrometry Analysis of 14 Solid H Samplesa
Name
Structure
Relative Intensity (%)
Range
Average
S-(2-chloroethyl)-1,4-dithianium ion [30843-67-5]
64.2-96.8
87.8
Bis[2-(1,4-dithianium)-S-ethyl] sulfide
0.7-25.8
6.9
S-(5-chloro-3-thiapentyl)-1,4-dithianium ion
2.0-7.7
4.1
1,2-Bis[1-(1,4-dithianium)]ethane <
0.1-3.3
1.2
aSamples were extracted into 50 vol% methanol-water solutions.
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Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant
TABLE C-4 Liquid Chromatography–Electrospray Ionization–Mass Spectrometry Analysis of Solids (Filtered from Liquid H Samples)a
Compound Name
Structure
Relative Intensity (%)
Sample 003A
Sample 033A
S-(2-chloroeethy)-1,4-dithianium ion
41.6
58.0
S-(5-chloro-3-thiapentyl)-1,4-dithianium ion
51.6
42.0
S-(8-chloro-3,6-dithiapentyl)-1,4-dithianium ion
6.8
Below detection limit
aAn aliquot of 25 μL of each liquid H sample was added to 250 μL CH2Cl2. Solutions were filtered using Gelman 0.45-μm GHF acrodisc syringe filters and the filters rinsed with additional CH2Cl2. Methanol/water (50/50, 1 mL) was then passed through each filter to dissolve and elute CH2Cl2-insoluble residue. Methanol/water solution was analyzed by liquid chromatography-electrospray ionization-mass spectrometry on October 1, 2003.
TABLE C-5 Estimated Total Iron Contents in Liquid and Solid Phases of H Mustard Agent Fill in 155-mm Projectilesa,b
Phase
Solid in Munition (wt%)
Total Iron (wt%)
Liquid
1.0 (0.59-1.4)
Solid
69 (58-84)
6.6 (2.1-9.8)
aThe total measured iron in the agent fill of the 155-mm projectiles is 4.92 weight percent.
bBy inductively coupled plasma-mass spectrometry.
Representative terms from entire chapter:
agent fill
