Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant (2005)

Chapter: Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot

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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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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.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Suggested Citation: "Appendix C Information on Current Composition of Levenstein Mustard Agent at Blue Grass Army Depot." National Research Council. 2005. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, DC: The National Academies Press. doi: 10.17226/11473.
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Next Chapter: Appendix D Biographical Sketches of Committee Members
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