AD-A2 6 5 366;,o. UNCLASSIFIED

...... DISTRI 3UITION

... * .*...... . ............ *

"=-SUFFIELD MEMORANDUM=

NO. 1410

CANADIAN CONTRIBUTOR TO THE 1991 UNITED

NATIONS ROUND ROBIN ANALYTICAL

VERIFICATION EXERCISE

DTICFILECTE

"JUN07 1993..by SU

P.A. D'Agostino, J.R. Hancock, C.A. Boulet, L.R. Provost,C.E. Lough, R.P. Hicken and A.S. Hansen

93-12592

March 1993

DEFENCE RESEARCH ESTABLISHMENT SUFFIELD, RALSTON, ALBERTA

WARNING

"The use of this information is permitted subject toC- oiaodooo f proprietary and patent rights*/Cm, 1

UNCLASSIFIED

SUFFIELD MEMORANDUM NO. 1410

CANADIAN CONTRIBUTION TO THE 1991 UNITED NATIONS

ROUND ROBIN ANALYTICAL VERIFICATION EXERCISE

by

P. A. D'Agostino, J. R. Hancock, C. A. Boulet, L. R. Provost,

C. E. Lough, R. P. Hicken and A. S. Hansen

WARNING i"The use of this information is permitted subject to

recognition of proprietary and patent rights'.

_JNCLASSIFIED

UNCLASSIFIED

TABLE OF CONTENTS

Page(s)

Introduction 1

Experimental 3

Results

a) Painted Panels 7

b) Rubber 8

c) Concrete 10

Discussion 12

Conclusions 14

Tables 15

Figures 18

Annex A Al

Accesion For

NTIS CRAMiDTIC TABUn~announcedjustification ...............-

BY ........... ----

Distribution I

AvailabilitY CodesAvail andJor

Dist Special

UNCLA-SFIEDE

UNCLASSIFIED

ABSTRACT

Nine samples, typical of those taken during inspection of a military facility, were

received by Defence Research Establishment Suffield as part of a United Nations sponsored

international round robin analytical exercise designed to evaluate laboratory capabilities.

This report summarizes Canada's contribution to the round robin analytical verification

exercise. Canada confirmed the presence of all the spiked CW relevant compounds,

including mustard and mustard related compounds following analysis of the provided

samples by capillary column GC-MS, GC-MS/MS, GC-FTIR, GC-FID and GC-FPD.

RtSUM9

Dans le cadre d'un exercice d'analyse, parrain6 par les Nations-Unies et destin6 A

6valuer la capacit6 des laboratoires par analyses inter-laboratoires A l'6chelle internationale,

le Centre de recherche pour la defense de Suffield a re~u neuf 6chantillons caract~ristiques

de ceux pr~lev6s au cours de l'inspection d'installations militaires. On resume, dans ce

rapport, la contribution du Canada A cet exercice de verification analytique. Le Canada a

confirm6 la presence de tous les compos6s utilisables comme agents chimiques qui avaient

W additionn~s aux &chantillons, dont l'yp~rite et les composds apparent~s, apr•s l'analyse

des 6chantillons fournis par CG sur colonne capillaire - SM, par CG-SM/SM, par CG -

IRTF et par CG - DPF.

DRES-SM-1410 UNCLASSIFIED

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INTRODUCTION

Nine samples, typical of those taken during inspection of a military facility, were

received by Defence Research Establishment Suffield (DRES) as part of a United Nations

sponsored round robin analytical exercise. The participating laboratories in Canada,

Australia, China, USSR (2 laboratories), Finland, France, Germany, The Netherlands,

Norway, Sweden, Switzerland, Czech and Slovak Federal Republic, United Kingdom and

United States of America (2 laboratories) were given the samples with no prior knowledge

of their content and were asked to report in a semi-quantitative manner the presence of any

CW relevant compounds.

All participating laboratories received their samples about one week prior to the

exercise and were asked to refrigerate the samples until the official start of the exercise,

October 21, 1991. DRES began analysis of the round robin samples on October 21, 1991

and finished all analyses on October 30, 1991. Solvent extracts of the painted panels (P46,

P47, P48), rubber (R46, R47, R48) and concrete (C46, C47, C48) samples were analysed by

capillary column GC-MS (El and ammonia CI), GC-MS/MS, GC-FMIR, GC-FPD

(simultaneous S/P) and GC-FID. All CW relevant compounds found in the set of nine

samples were confirmed by comparing acquired chromatographic/spectrometric data with

that obtained for authentic standards. Trimethylsilylation was performed on all sample

extracts in order to identify nonvolatile components. All chromatographic analyses were

completed by the five analysts in seven working days (175 man hours). Report writing and

figure preparation was undertaken by two persons on October 31, 1991 and was completed

by November 4, 1991 (3 working days or 50 man hours).

This report summarizes Canada's contribution to the 3rd United Nations round robin

analytical exercise. Table I lists the CW relevant compounds found during analysis of the

painted ,,•nels, rubber and concrete samples provided for analysis. The Experimental

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portion of this report summarizes the instrumental methods used, the semi-quantitation

methods employed and the detection limits of the methods. The sample handling details,

chromatographic/spectrometric results and compounds identified during analysis of each

sample are provided in the Results section. A summary of the data acquired and the geileral

analytical philosophy followed is presented in the Discussion.

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EXPERIMENTAL

A semi-quantitative estimate of the amount (jg) of CW relevant components in each

sample was calculated using the FID and FPD (S) responses for mustard.

a) Instrumental Conditions

GC-MS Conditions

Country Canada

Mass Spectrometer VG AUTOSPEC-Q

Accclerating Voltage 8 kV

Mass Range/Scan Function 400 - 40 u (0.5 sec/decade)

El (source conditions) 70eV / 200pA / 2 x 10-6 Torr / 200*C

CI (source conditions) 50eV / 300jiA / 8 x 10-5 Torr / 120*C

Detection Limit El: full scanning 0.1-0.5 ng/component

CI: full scanning 0.2-0.5 ng/component

Resolution 1800

GC Parameters

Instrument: Hewlett Packard 5890

Column: J&W 15 m x 0.32 mm ID DB-1701 (0.25 gm)

Carrier Gas: Helium approx. 100 cm/s

Temperature Program: 400C (2 min) then t0*C/min to 280'C (5 to 20 min)

Injection Mode: On-column at 40*C

Comments: 10,000 resolution (250 - 100 u, I sec/decade) used to the confirmmolecular weight of mustard and bis(2-chloroethyl)disulfide.

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___ GC-MS/MS Conditions

Country Canada

Mass Spectrometer VG AUTOSPEC-Q

Accelerating Voltage 8 kV

Quadrupole Mass Range 250 - 50 u (0.5 sec/decade)(daughter experiments)

El (source conditions) 70eV / 200AA / 2 x 10' Torr / 2000 C

CAD Cell 10-6 Torr Argon / 17 eV

Detection Limit Daughter spectrum: 0.5 ng/component

Resolution (sector) 1000

Resolution (quadrupole) unit

GC Parameters

Instrument: Hewlett Packard 5890

Column: J&W 15 m x 0.32 mm ID DB-1701 (0.25 jim)

Carrier Gas: Helium approx. 100 cm/s

Temperature Program: 40*C (2 min) then 10*C/min to 280 *C (5 to 20 min)

Injection Mode: On-column at 40'C

Comments:

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GC-FTIR CONDITIONS

Co'rntry Canada

IR Spectrometer Nicolet 730

Resolution 8 cm-'

Light Pipe Dimensions 15 cm x 1 mm

Detector Type MCT

Scan Rate approx. 2 scans/s

Accumulated nominally 10 scansScans/Spectrum

Wavenumber Range 4000 to 600

Make-up Gas Flow Rate in 0.3 mL/minLight Pipe

Light Pipe Temperature _ 260 C

Detection Limit I1 ng/component (based on a 50 gL injection)

GC Parameters

Instrument: Hewlett Packard 5890

Column: J&W 15 m x 0.25 mm ID DB-1701 (0.25 pm)

Carrier Gas: Helium approx. 20 cm/s

Temperature PIrogram: 40°C then 10*C/min to 250*C (20 min)Injection Mode: On-column at 40°C

Comments:

Large injections (50 AL) using an 8 m retention gap were employed to improve FTIRsensitivity.

Temperature programming was started following complete elution of the solvent(typically 20 minutes following large volume injection).

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GC-FPD CONDITIONS

Country: Canada

Instrument: Varian 3700

Column: J&W 15m x 0.53mm ID DB-1701(1.0 4m))

Detector: FPD (simultaneous S/P)

Carrier Gas: Helium 40 cm/s

Temperature Program: 50°C (2 min) then 10°C/min to 2800C(5 to 20 min)

Injection Mode Flash vaporization at 150°C

Detection Limit FPD (S) 1 ng/componentFPD (P) 20 pg/component

GC-FID Conditions

Country: Canada

Instrument: Hewlett Packard 5890

Column: J&W 15in x 0.32mm ID DB-1701(0.25 gm)

Detector: FID

Carrier Gas: Helium approx. 40 cm/s

Temperature Program: 40°C (2 min) then 10°C/min to 280'C(5 to 20 min)

Injection Mode On-column at 40°C

Detection Limit 0.5 ng/component

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RESULTS

a) Painted Panels (P46, P47, P48)

Sample Handling

The plastic pouches containing the glass bottles were cut with scissors and the glass

bottle removed. The first panel extracted, P47, was removed and the foil removed with

disposable tweezers. Paint panel P47 was then placed in the bottom of a 100 mL glass

beaker containing 7 mL of hexane. The panel was extracted by ultrasonic vibration for 5

minutes and the hexane removed and cone,.ntrated by nitrogen blowdown to I mL prior to

analysis. Paint panels P46 ard P48 were treated identically with the exception that 10 ml-

of hexane was used for extraction.

Trimethylsilylation (TMS) was performed by combining 100 gL bis(trimethylsilyl)-

trifluoroacetamide (BSTFA), 100 jiL pyridine and 300 j.L of hexane extract (P46) in a 1.8

mL screw-capped (Teflon lined) glass vial. Paint panel P46 was re-extracted by ultrasonic

vibration (5 min) with 7 ml. of acetonitrile and the extract was concentrated to 300 tsL by

nitrogen blowdown. Trimethylsilylation (TMS) was performed by combining 100 ,L BSTFA,

100 )uL pyridine and 300 ,L of this second extract in a 1.8 mL screw-capped (Teflon lined)

glass vial. Samples were heated for 20 minutes at 60'C prior to analysis. Analysis of both

samples was performed' immediately after cooling to minimize degradation.

Results

Figures 1 and 2 illustrate capillary column GC-FID and GC-MS (El) chromatograms

obtained during analysis of 1 ),L aliquots of the hexane extract of P46, P47 and P48. Figures

3 and 4 illustrate El-MS for the three CW relevant compounds, esquimustard, bis[(2-

UNCLASSIFILD

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chloroethylthio)ethyllether and 2-chloroethyl (2-chloroethoxy)ethyl sulfide found in the

hexane extracts of P46 and P48. P47 did not contain compounds of CW relevance and

appears to be a control. The molecular weight of each of these sulfur vesicants wcre

confirmed by the presence of (M+ Nf- 4)4 ions during amrnonia Cl-MS analysis (Figures 5

and 6). Additional MS/MS data were obtained by acquiring the daughter spectra of m/z 123

(an ion common to sulfur vesicants) for sesquimustard, 2-chhoroethyl (2-chloroethoxy)ethyl

sulfide and bis[(2-chloroethylthio)ethyl]ether 'Figures 7 and 8). The presence of sulfur in

each of these vesicants was confirmed during GC-FPD (S) (Figure 9) and MFIR spectra

were obtained for all three compounds (Figure 10).

Sesquimustard, 2-chloroethyl (2-chloroethoxy)ethyl sulfide and bis[(2-

chloroethylthio)ethyl]ether chromatographic/spectrometric data were confirmed with

available authentic standards. No CW relevant compounds were detected during analysis of

either trimethylsilyl extract.

b) Rubber (R46, R47, R48)

Sample Handling

The plastic pouches containing the glass bottles were cut with scissors and the glass

bottle removed. Each rubber sample was removed and the foil removed with disposable

tweezers. Rubber samples were then placed back into the shipment bottle and extracted bv

ultrasonic vibration for 5 minutes with 12 mL of acetonitr'le. The acetonitrile extract wals

removed and concentrated by nitrogen blowdown to 0.5 mt Dichloromethane (4.5 mL) was

added to the acetonitrile extract (final volume of 5 mL.) prior to analysis to improve

chromatographic performance.

Two mL of the 5 mL volume (above) were concentrated to 300AL and this

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concentrate was used for trimethylsilylation. Trimethylsilylation was performed by combining

100 AL BSTFA, 100 AL pyridine and the 300 AL extract (R46) in a 1.8 niL. screw-capped

(Teflon lined) glass vial. This sample was heated for 20 minutes at 60'C prior to analysis.

Analysis was performed immediately after cooling to minimize degradation.

Results

Figures 11 and 12 illustrate capillary column GC-FID and GC-MS (ElI)

chromatograms obtained during analysis of I ,uL aliquots of the hexane extract of R46, R47

and R48. Figure 13 illustrates El-MS for the two CW relevant compounds, mustard and

bis(2-chloroethyl)disulfide found in the acetonitrile extracts of R46 and R47. R48 did not

contain compounds of CW relevance and appears to be a control. The exact mass of the

molecular ion for both compounds was determined at 10,000 resolution during GC-MS (ElI)

analysis.

Compound Calc. Mass Measured Difference

Mustard 157.9724 157.9720 0.4 mmu

bis(2-chloroethyl)disulfide 189.9444 189.9462 1.8 mmu

Additional MS/MS data were obtained by acquiring the daughter spectrum of m/z 123 (an

ion common to sulfur vesicants) for mustard (Figures 14 and 15). The presence of sulfur in

each of these compounds was confirmed during GC-FPD (S) (Figure 16) and FTIR data

were obtained for mustard (Figure 17).

No CW relevant compounds were detected during analysis of the trimethylsilyl

extract. The second acetonitrile extract of R46 (used for TMS study) contained about 80%

as much mustard and his(2-chloroethyl)disulfide as the first which suggests difficult recovery

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of these compounds from this tvpe of rubber with acetonitrile. Multiple extractions would

be required for complete recovery.

Mustard and bis(2-chloroethyl)disu lfide chromatographic/spectrometric data were

confirmed with available authentic standards.

c) Concrete (C46, C47, C48)

Sample handling

The plastic pouches containing the glass bottles were cut with scissors and the glass

bottle removed. Each concrete sample was removed and the foil removed with disposable

tweezers. Concrete samples were then placed back into the shipment bottle and extracted

by ultrasonic vibration for 5 minutes with 15 mL of acetonitrile. The acetonitrile extract was

removed and concentrated by nitrogen blowdown to 0.5 mL. Dichloromethane (4.5 mL) was

added to the acetonitrile extract (final volume of 5 mL) prior to analysis to improve

chromatographic performance.

Two mL of the 5 mL volume (above) were concentrated to 300ML and this

concentrate was used for trimethylsilylation. Trimethylsilylation was performed by combining

100 AL BSTFA, 100 ML pyridine and the 300 plL extract (C48) in a 1.8 mL screw-capped

(Teflon lined) glass vial. This sample was heated for 20 minutes at 60'C prior to analysis.

Analysis was performed immediately after cooling to minimize degradation.

Results

Figures 18 and 19 illustrate capillary column GC-FID and GC-MS (El)

chromatograms obtaineo during analysis of I ML aliquots of the acetonitrile extracts of C46,

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C47 and C48. Figure 20 illustrates EI-MS for one of the two CW relevant compounds,

thiodiglycol, found in the acetonitrile extracts of C47 and C48. The second compound,

thiodiglycol sulfone, was not discernable above the chemical background during El-MS. The

molecular weight and presence of each of the compounds was confirmed by the presence

of (M+H)' and/or (M+NH 4)+ ions during GC-MS (ammonia CI) analysis (Figure 21).

Additional MS/MS data were obtained by acquiring the daughter spectrum of m/z 122

(molecular ion) for thiodiglycol (Figures 22 and 23) and the daughter spectrum of m/z 111

for thiodiglycol sulfone (Figures 24 and 25).

Figures 26 and 27 illustrate capillary column GC-FID and GC-MS (El)

chromatograms obtained during analysis of I pL aliquots of the derivatized acetonitrile

extract of C46, C47 and C48. Figure 28 illustrates El-MS for the di-TMS derivatives of

thiodiglycol and thiodiglycol sulfone found in the acetonitrile extracts of C47 and C48. C46

did not contain compounds of CW relevance and appears to be a control. The molecular

weight of each of the derivatives was confirmed by the presence of (M+H)+ and

(M+NH4 )4 ions during GC-MS (ammonia CI) analysis (Figures 29 and 30).

The presence of sulfur in each of these compounds and their di-TMS derivatives was

confirmed during GC-FPD (S) (Figures 31 and 32) and FTIR data were obtained for

thiodiglycol, thiodiglycol sulfone and their di-TMS derivatives (Figures 33 and 34).

Thiodiglycol, thiodiglycol sulfone and their di-TMS derivatives

chromatographic/spectrometric data were confirmed with available authentic standards.

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DISCUSSION

DRES adopted the following general philosophy for the analysis of the nine samples

received for analysis. The following steps indicate the order of analysis at DRES:

a) Capillary column GC-FID was used to screen solvents (e.g., hexane,

dichloromethane and acetonitrile) used for extraction of samples. Capillary column

GC-FID and GC-FPD (and when required GC-MS) was employed to screen solvent

blank extracts to ascertain the levels of potential interference and the presence of

any CW relevant or unusual compounds.

b) Standard mixtures of CW relevant compounds were analysed daily by all the

techniques to assure both chromatographic and spectrometric quality prior to sample

extract analyses.

c) One sample (or group of samples) at a time was extracted and analysed by

capillary column GC with MS, MS/MS, FTIR, FID and FPD (simultaneous S/P)

detection. The order was painted panels (October 21, 1991) followed by concrete

(October 22, 1991) and rubber (October 23, 1991) samples.

d) CW relevant compounds were confirmed by comparison of chromatographic/

spectrometric data with authentic standard data. Thiodiglycol sulfone (the only

compound not available at DRES) was synthesized to meet this goal and the El-MS

data obtained for this synthesized standard and the di-TMS derivative of thiodiglycol

sulfone agreed with published data (E. R. J. Wils, Fresenius Z. Anal. Chem. 321,

471-474 (1985)). CI-MS and El-MS data for the sulfur containing vesicants found in

the samples have also been previously published (P. A. D'Agostino and L. R. Provost.

Biomed. Environ. Mass Spectrom., 15, 553-564 (1988)). Annex A contains the

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Synthesis and Reference Spectroscopic Data for lniodiglycol Sulfone.

e) Trimethylsilylation of sample extracts was performed to aid in the identification

of nonvolatile degradation products.

f) All sample extract components were screened for the presence of sulfur and

phosphorus atoms by GC-FPD. No phosphorus containing compounds were detected.

g) Capillary column GC-MS (El) chromatograms of all extracts of the samples were

screened for the presence of the common CW agents GB, GD, GA, GF, VX, H, Q

and T using reconstructed ion current chromatograms. Minor or trace sample

component El mass spectra were checked to be sure that they did represent, in the

best opinion of the laboratory, scheduled compounds. Only mustard related

compounds were found in the samples. Table II lists the compounds identified in the

samples and the techniques used to confirm the presence of each component.

h) A semi-quantitative estimate of major sample components was obtained using

capillary column GC-FID and/or GC-FPD data. Table III lists the semi-quantitative

results of the sample analyses.

i) The sample detection limit of GC-FTIR was greatly enhanced over previous round

robin exercises by the use of an 8 m retention gap. This allowed larger volume (50

AL) injections.

j) The high specificity of GC-MS/MS and GC-MS (ammonia CI) is clearly

demonstrated by comparison of sample extract chromatograms with either GC-FID

or GC-MS (El) chromatograms.

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CONCLUSIONS

Solvent extracts of the painted panels, concrete and rubber samples circulated for

analysis were analysed by capillary column GC-MS (El and ammonia CI), GC-MS/MS, GC-

FTIR, GC-FPD (simultaneous S/P) and GC-FID. Trimethylsilylation was performed on all

sample extracts in order to identify non-volatile degradation components.

Canada identified and confirmed the presence of the chemical warfare relevant

compounds, sesquimustard, bis[(2-chloroethylthio)ethyl]ether and 2-chloroethyl (2-

chloroethoxy)ethyl sulfide in the hexane extracts of two of the painted panel extracts. The

molecular weight of each of these sulfur vesicants were confirmed by the presence of

(M+NH 4)÷ ions during ammonia CI-MS analysis. Additional MS/MS data were obtained

by acquiring the daughter spectra of m/z 123 (an ion common to sulfur vesicants) for

sesquimustard, 2-chloroethyl (2-chloroethoxy)ethyl sulfide and bis[(2-

chloroethylthio)ethyllether.

Two chemical warfare relevant compounds, mustard and bis(2-chloroethyl)disulfide

were found in the acetonitrile extracts of two rubber samples. The exact mass of the

molecular ion for both compounds was determined at 10,000 resolution during GC-MS (El)

analysis. Additional MS/MS data were obtained by acquiring the daughter spectrum of m/z

123 (an ion common to sulfur vesicants) for mustard. FTIR data were not obtained for

bis(2-chloroethyl)disulfide.

Two chemical warfare relevant compounds associated with mustard degradation,

thiodiglycol and thiodiglycol sulfone, were found in the acetonitrile extracts of two concrete

samples. The molecular weight and presence of each of the compounds was confirmed by

the presence of (M+H)' and/or (M+ NH 4)+ ions during GC-MS (ammonia CI) analysis.

Additional MS/MS data were obtained by acquiring the daughter spectrum of m/z 122

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(molecular ion) for thiodiglycol and the daughter spectrum of m/z 111 for thiodiglycol

sulfone. The trimethylsilyl (TMS) derivatives of thiodiglycol and thiodiglycol sulfone were

confirmed by capillary column GC-MS analysis of the concrete acetonitrile extracts. The

presence of sulfur in each of these compounds and their di-TMS derivatives was confirmed

during GC-FPD, and FTIR data were obtained for thiodiglycol, thiodiglycol sulfone and

their di-TMS derivatives.

Thiodiglycoi sulfone was synthesized to provide an authentic reference standard. The

EI-MS data obtained for this synthesized standard and the di-TMS derivative of thiodiglycol

sulfone agreed with published data. CI-MS and EI-MS data for mustard and other sulfur

containing vesicants found in the samples also agreed with published data.

Table II summarizes the mustard related compounds confirmed by DRES in the

painted panels, concrete and rubber samples. Only five of the participating laboratories

including Canada, identified all the spiked compounds. In addition to the spiked compounds

reported, some laboratories also reported false positives, or the presence of compounds

which were not deliberately spiked in the samples.

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Table I: Chemical Warfare and Related Compounds 16

Identified in the Third UN Round Robin

Chrom. STRUCTURE MoL Wt. CAS No.Peak No.

I1. CI 202 114811-38-0

2-chloro(2-chloroethoxy)ethyl sulfide

2. 218 3563-36-8sosquimustard

3. C s O s CI 262 63918-89-8

bisI(2-chloroethylthio)ethyllether

4. CI Vs Ct 158 505-60-2

mustard

5. C , ssS, ^c! 190 1002-41-1

bis(2-chloroethyl)disulfide

6. HO_ s_ OH 122 111-48-8

thiodiglycol

07. HO.ý OH 154 2580-77-0

II

0thiodiglycol sulfone

8. TMSO S,-, OTMS 266

di-TMS der. of thiodiglycol

09. TMSO S TMS 298

If0

di-TMS der. of thiodiglycol sulfone

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17

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UNCLASSIFIED

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Figure 1: Capillary column GC-FID chromatogram of the hexane extract of a) P46, b)P47 and c) P48 painted panels. Numbered components are listed in Table I.

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100 2 3a

8070605040302010_ .

02:00 4:00 6:00 8: 10:00 12:00 14:00 16:00 TIME169 339 509 679 849 1019 1189 1358 SCAN

100908070

2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 TIME169 339 509 679 848 1018 1188 1358 SCAN

100

90

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2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 TIME

169 339 509 679 849 1019 1189 1359 SCAN

Figure 2: Capillary column GC-MS (El) total-ion-current (400 to 40 u) chromatogramof the hexane extract of a) P46, b) P47 and c) P48 painted panels. Numberedcomponents are listed in Table I.

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[100 1f3 a90180o-

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Figure 3: Electron impact mass spectra of a) sesquimustard and b) bis[(2-

chloroethylthio)ethyl]ether (found in P46 and P48).

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10 1, 3'4 Mx

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Figure 4: Electron impact mass spectrum of 2-chloroethyl (2-chloroethoxy)ethyl sulfide(found in P46 and P48). This minor component co-elutel with anothercompound and only the ions marked with a triangle and the molecular ion atni/z 202 were due to 2-chloroethyl (2-chloroethoxy)ethyl sulfide.

UNCLAS1SFIED

UNCLASSIFIED

10042

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2:00 4:10'0 6':100 8:. 00 ..10:10,0 12:00 14:00 16:00'' TIME~169 339 509 679 849 1019 1189 1359 SCANJ

Figure 5: Capillary column GC-MS (ammonia Cl) total-ion-current (300 to 200 u)chromatogram of the hexane extract of P46 painted panel. Numberedcomponents are listed in Table I.

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100 2090 (M+NH 4 )+ a706050403020 69 83 100 123 167 18610 aJ 1111,1 4117

0 i 'l, IjJ= l . L J" I_,__._ _,

60 80 0i 1 2ic2i o 124 2 200 26/100 2

90 (M+NH 4 )+ b80

70 CI s60504030 123 18320 710 890 1 1, ,• [.... l.. ...L I..... ,L . .... I ..- .. h, i ... .... .I. . I... ... M I. i ll

6 80 0 10 20 2 40 02 M/100 2 0

90i (M+NH 4 )+ C8070 CII S "O s CI

50 12340302010 61 89

0 i. hL I . ..j, 1 3 3 1 6 7 1 8 6 2 2 7

60 8o' ' o 160 140 1it i-l6'6 2 160 26o o2 0 M/Z

Figure 6: Ammonia chemical ionization mass spectra of a) 2-chloroethyl (2-chloroethoxy)ethyl sulfide, b) sesquimustard and c) bis[(2-chlorocthylthio)-ethyllether (found in P46 and P48).

UNCLASSIFIED

UNCLASSIFIED

100 M--x20.00----- 3

95,90_

85:

80-

75-

70.

65:

60: 2

55_"

50_

45-

40_

35-

30.

25.

20.

15.

10

5.

5: 00 10: 00 120:00 TIME425 851 1277 1703 SCAN

Figure 7: Collisional activated dissociation capillary column GC-MS/MS chromatogramfor the daughters of m/z 123 of the hexane extract of P46 painted panel.Numbered components are listed in Table I.

UNCLASSIFIED

UNCLASSIFIED

100 1908070506040302010 63

5o0 6'0 70 80 '9'0o . 60 1i10 10Z 14o100 1390 b-807060 C I sS50403020o10 63

5'0 60 70 80 90... 161 1410 o M/z100 13

90C8070 ci Q%~%• •.dN• cI60150-40-30-20 6310

50 60 70 P 0 90 1o0 13o 1•0 1 0 14 M/Z

Figure 8: Daughter spectra (m/z 123) of a) 2-chloroethyl (2-chloroethoxy)ethyl sulfide,b) sesquimustard and c) bis[(2-chloroethylthio)ethyllether (found in P46 andP48). UNCLASSIFIED

UNCLASSIFIED

175000 2 31

0

3500-r-0151 101 15' 20'

175000- b(n4J

0C-

3500-t-'-0 51 101 j51 20'

175000- 2 3 C

0

3500- __K

of 51 1OI 15' 201

Time (min)

Figure 9: Capillary column GC-FPD (sulfur mode) chromatogram of the hexane extractof a) P46, b) P47 and c) P48 painted panels. Numbered components are listedin Table I.

UNCLASSIFIED

UNCLAS~IFIED0

0-4

z

q 00 3qq1* 2880 2 20 1760 1200 1*00

z

zCE~

'000 31*1* 2880 2k 20 160 1 00 q*0

z

T-ir-i

H0

q 00 341*0 2680 2320 17ý60 1 kO 61*0WHVE NUMBEF3

Figure 10: FTIR spectra of a) 2-chioroethyl (2-chloroethoxy)ethyl sulfide, b)sesquimustard and c) bis((2-chloroethylthio)ethyllether (found in P46 andP48). UNCLASSIFIED

UNCLASSIFIED

80000- a

U,4-)c

0

4 5

5000- "

0 51 101 151 20' 25' 30

80000- b

C:"-)

:3

04 5

5000 - "-- -- -A--"

0 51 1O0 15' 20' 25' 30

80000- C

4.)

0

5000-or 51 10, 15' 20' 251 30

Time (min)

Figure 11: Capillary column GC-FID chromatogram of the acetonitrile extract of a) R46,b) R47 and c) R48 rubber samples. Numbered components are listed in TableI.

UNCLASSIFIED

UNCLASSIFIED

10090 a80706050403020 4 5100

5:00 10:00 15:00 20:00 25:00 TIME425 849 1274 1699 2124 SCAN100-90 7ib

80

706050403020o4 510-0

5:00 10:00 15:00 6 20:06 25':00 TIME424 849 1274 1699 2123 SCAN

10090 C

8070605040-302010

5:00 10 : 0 15:00 25:00 TIME424 849 1274 1698 2123 SCAN

Figure 12: Capillary column GC-MS (El) total-ion-current (400 to 40 u) chromatogramof the acetonitrile extract of a) R46, b) R47 and c) R48 rubber samples.Numbered components are listed in Table I.

UNCLASSIFIED

!UNCLASSIFIED

100- 119902

80-

70-

60_ Cl %.•S/N/Cl

50-

40_ 63

30-+

20- 45 59 158

10 7396 131

40 60 8'0 10 10 1410' 10. . ./Z100- 3 b

90

80

70

60

50 M t190

40

3 0 4 5992 128:45 59

20--7

1099 15549 141 394

40 60 80' 1 0 1 ` ' -,, . 0 "140•' ,. ,' ' 160 M/Z

Figure 13: Electron impact mass spectrum of a) mustard and b) bis(2-chloroethyl)-disulfide (found in R46 and R47).

UNCLASSIFIED

UNCLASSIFIED

1007 4

90'

85-[

80-

75-

70-

65-

6 0-

55-

50-

45:

40-

35-

3 0-

25-

20:

15-

10-

5

5: 00 10:00 15:00 20:00 25:00 TIM~425 851 1277 1703 2129 SCAN~

Figure 14: Collisional activated dissociation capillary column GC-MS/MS chromatogramfor the daughters of m/z 123 of the acetonitrile extract of R46 rubber sample.Numbered components are listed in Table 1.

-UNCLASSIFIED

UNCLASSIFIED

100-

95:

90-

85-

8 0-

75-

70-

65-

60-

55:

50.

45:

4 0-

3 5-

3 0-

25-

20'

15-63

10-

5

0. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

50' 60' 70 ... 80 90.ýO. 160 116 ~ 10 i40 'M/Z

Figure 15: Daughter spectrum (m/z 123) of mustard (found in R46 and R47).

UNCLASSIFIED

UNCLASSIFIED

175000-

0" 4

(I)

3 0 00 .1)1 --- L

0 5'• F0 15' 20

175000-

30-P

:3

3000-

015' 101 15

Time (min)

Figure 16: Capillary column GC-FPD (sulfur mode) chromatogram of the acetonitrile

extract of a) R46, b) R47 and c) R48 rubber samples. Numbered componentsare listed in Table I.

UNCLASSIFIED

UNCLASSIFIED

0I

LUz

- 0)

o7

Zr.

z f

H-

CA

•3800 3175 2550 1925 1300 675WAVENUMBER

Figure 17: FIIR spectrum of mustard (found in R46 and R47).

UNCLASSIFIED

UNCLASSIFIED

100000-

o

5000 .... .. ...o 55 10 5- 20 • 2 -F

100000-

4 -)

0

9000 _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _

5' O 1 20' 251

100000-

c-P

5000- ______

0- 10o 15T 20 25'Time (min)

Figure 18: Capillary column GC-FID chromatogram of the acetonitrile extract of a) C46,b) C47 and c) C48 concrete samples. Numbered components are listed inTable 1.

UNLSIFIED

UNCLASSIFIED

10079080706050

80

3020)107

0.5:010:0 15:-00 '20:00' TIME

10090 b80706050403062010

5:0010:00 100 200 TIME

Figure100 19: Cailr ounG-S(loa-o-urn 40 to 40u)croaogaof0 thCctntieetato )C6 )C7adc 4 oceesmlsNubrdcmoet9relse0nTbeI8N0SS~E

UNCLASSIFIED

100 61

95:

90-

85

80 K

75_

70

65-

60-

55 45

50-

45-:

40:

35_ 57

9130 104

25 71

20_

15-104 8 85

I 97 M5- 74122

01A40 50 60 70 80 90 10 10 1ý0 M/Z1

Figure 20: Electron impact mass spectrum of thiodiglycol (found in C47 and C48).

UNCLASSIFIED

UNCLASSIFIED

100_ 1a10

90o- (M+NH 4 )+

80-

70_.

60- HO:S/ QH

50-

40:

30_•

20o_ (M+H)+10: 69 77 86 100 123

60 70 8090 100 110 10 10 140 150 160 170 180 /Z100 1 2

97(M+NH 4)+80

700

60:50H: HO" SH

040-

30-

20 0 63 10010 84 88 96 118 138

60 70 80 90 11 0 "1~O 150 160 170 1 0 14 5

Figure 21: Ammonia chemical ionization mass spectra of a) thiodiglycol and b)thiodiglycol suifone (found in C47 and C48).

UNCLASSIFIED

UNCLASSIFIED

95-

90:OIE

852780-

70 H65-

6 0-

55-

50-

45:

40-

35:

30-

25:

20-

15

10-

5:00 10:00 15:00200 IE425 851 1277 1684 S CAN

Figure 22: Collisional activated dissociation capillary column GC-MS/MS chromatogramfor the daughters of m/z 122 of the acetonitrile extract of C48 concretesample. Numbered components are listed in Table I.

UNCLASSIFIED

UNCLASSIFIED

100- 1 4 122

95-

85:

8 0-

75-

70-

65-

55 svOH

50-

45:

40:

35:

30:

2 5:

2 0-

15"

10-

5- 60

0 _ _ _ _ _ _ _ _ _ _

s0 60 70 80 90 1 0 110 1 0 10 1,406 M,/Z

Figure 23: Daughter spectrum (m/z 122) of thiodiglycol (found in C47 and C48).

UNCLASSIFIED

UNCLASSIFIED

1007 7

95-

90-

85-

80:

75-

70:

65-

60-

55:

50-

45:

40

35-

3 0-

25-

20:

15-

10

5-

06:00 7: 00 8: 0 :00 10:00 T'IME511 596 681 767 852 SCAN

Figure 24: Collisional activated dissociation capillary column CC-MS/MS chromatogramfor the daughters of m/z 111 of the acetonitrile extract of C48 concretesample. Numbered components are listed in Table 1.

UNCLASSIFIED

UNCLASSIFIED

100 11

95:

90.

85-

8 0-

75_

70:

65 6

60 0 o0S OH

55- 0

50-

45:

40-

35-93

30:

25-

20-

15-

10- 63

5-

0---i.

50 60 70 80 90 10 ~ a 1Hi0'1o 140 '/z

Figure 25: Daughter spectrum (m/z 111) of thiodiglycol sulfone (found in C47 and C48).

UNCLASSIFIED

UNCLASSIFIED

300000-

C')

00

5000-o 51, 15' 20' 25' 30

300000- 8

(r)%4-)9

0

5000 "__

0- 5i 10i 15' 201 25' 3

300000-

4j)CZY00

5000-0 51 101 151 201 25'

Time (min)

Figure 26: Capillary column GC-FID chromatogram of trimethylsilylated acetonitrileextract of a) C46, b) C47 and c) C48 concrete samples. Numberedcomponents are listed in Table I.

UNCLASSIFIED

UNCLASSIFIED

100a90807060504030201 0

02:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 TIME170 340 510 679 849 1019 1189 1359 SCAN

100 8 b

8070

2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:600 TM169 339 509 679 849 1019 1189 1359 SCAN

100

90ur 97 ailr oun CM E)ttlio-urn 40tC4 )crmtga

807060

2.. :00 4: 0'0' '6':'0'0 8:0 -10':00 12:0014:00 16:00 TM169 339 509 679 849 1019 1189 1358 SCAN

of trimethylsilylated acetonitrile extract of a) C46, b) C47 and c) C48 concretesamples. Numbered components are listed in Table I.

UNCLASSIFIED

UNCLASSIFIED

100- a90

80 116

70

60147

501: TMSO,,-,--,S OTMS103

40

30-

20 87 133 176

10 1 191 251

5o 10 .0 260 20o 360 .. 35') ,/Z

100 7390 b80

70 028360 TMSO% .. ,ý OTMS

60:

50- 0

40

30 117

20.. 9 101 147: 59

S87 133 239 -

50 10 150 20 250 30 350 M/Z

Figure 28: Electron impact mass spectra of a) di-TMS derivative of thiodiglycol and b)di-TMS derivative of thiodiglycol sulfone (found in C47 and C48).

UNCLASSIFIED