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Gas Chromatographic Analysis of Sulfur Mustard inDiethyl Phthalate

Paul A. Lancaster

Combatant Protection and Nutrition Branch

Aeronautical and Maritime Research Laboratory

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ABSTRACT

A gas chromatographic method for the analysis of 2,2'-dichlorodiethyl sulfide(commonly known as Sulfur Mustard) that had been trapped in the solvent, diethyl

phthalate is described. The method utilises the improved sensitivity and selectivityoffered by the new Pulsed Flame Photometric Detector to detect routinely samplescontaining 0.25 g/mL of sulfur mustard in diethyl phthalate. The method is capableof fast and reliable analysis of samples containing 0.25-5.0 g/mL of sulfur mustard indiethyl phthalate. Quality control measures determined that the method calibrationwas still within 5% control limits after nearly 500 sample injections.

RELEASE LIMITATION

Approved for public release

D E P A R T M E N T O F D E F E N C E

!

DEFENCESCIENCEANDTECHNOLOGYORGANISATION

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Published by

DSTO Aeronautical and Maritime Research LaboratoryPO Box 4331 Melbourne Victoria 3001 Australia

Telephone: (03) 9626 7000Fax: (03) 9626 7999

Commonwealth of Australia 1998AR-010-603August 1998

APPROVED FOR PUBLIC RELEASE

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Gas Chromatographic Analysis of Sulfur

Mustard in Diethyl Phthalate

Executive Summary

The aim of the project was to develop a gas chromatographic method to analysesamples of the chemical warfare blister agent 2,2-dichlorodiethyl sulfide (commonlyknown as Sulfur Mustard or HD), that had been trapped in the solvent diethylphthalate (DEP). The samples were generated from chemical penetration experimentsperformed on protective clothing.

The technique involved:i. developing a gas chromatographic method that was capable of both meeting the

required detection limits and completing the analysis in a minimal time,ii. preparation of standards that are representative of the samples to be analysed,iii.establishing a quality control procedure to confirm the integrity of the method.

It was decided that, due to time constraints, the lowest possible detection limit would

not be an aim of this project. Instead a value of 0.5g/mL of sulfur mustard in DEPwas set as the lowest probable concentration that would be required to be detectedroutinely in the protective clothing penetration experiments. In order to prove that theGC method could routinely detect such levels, the concentration was halved and the

ability to detect 0.25 g/mL samples of sulfur mustard in DEP (or 0.35 ng of sulfurmustard injected on column) was set as the final goal. Improved detection of sulfurmustard was achieved by utilising a new design of gas chromatography detector(Pulsed Flame Photometric Detector) which offers increased selectivity for sulfur (andphosphorous) detection and improvements in sensitivity of up to 2 orders ofmagnitude above that of a normal flame photometric detector. The method developedwas found to not only meet the stated sensitivity requirements, but also exhibitexcellent reproducibility. Quality control measures established that the methodcalibration stayed within the 5% deviation control limits after analysis of almost 500samples.

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Authors

Paul A. LancasterCombatant, Protection and Nutrition Branch

Paul Lancaster, BAppSci (App Chem) is a Professional Officer at AMRL-Maribrynong. Before joining DSTO in 1994, he workedat La Trobe University School of Agriculture investigating the fertility status of crop and pasture soils. His work in DSTOincludes the development of procedures for using detection andmonitoring equipment for chemical warfare agents, bioaerosolsand other hazardous vapours.

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Contents

1. INTRODUCTION ..............................................................................................................1

2. INSTRUMENTATION......................................................................................................22.1 Pulsed Flame Photometric Detector (PFPD)..................................................................2

2.1.1 The flame pulsation cycle........................................................................................32.1.1.1 Gas flows/composition and chamber fill times ............................................32.1.2 Emission profiles ...................................................................................................... 42.1.3 Detector Sensitivity ..................................................................................................4

3. EXPERIMENTAL PROCEDURES...................................................................................53.1 Gas Chromatography Instrumentation and Conditions .............................................5

3.1.1 Varian 3400 GC Set Up. ........................................................................................... 53.1.2 Pulsed Flame Photometric Detector. ..................................................................... 5

3.1.2.1 Optimisation of PFPD. ...................................................................................... 63.1.3 Varian 8200 CX Auto Sampler................................................................................63.1.4 Star Chromatography Workstation. ......................................................................6

3.2 Quantification/ Preparation of Standards...................................................................... 7

4. RESULTS AND DISCUSSION........................................................................................8

5. CONCLUSION..................................................................................................................10

6. REFERENCES ....................................................................................................................11

7. ACKNOWLEDGMENTS ................................................................................................11

8. GLOSSARY OF ACRONYMS........................................................................................ 11

9. TABLES............................................................................................................................... 12

10. FIGURES............................................................................................................................. 14

APPENDIX 1: MSDS FOR DISTILLED MUSTARD (HD)............................................19

APPENDIX 2: CPNB VARIAN 3400/PFPD START UP PROCEDURE........................25

APPENDIX 3: PFPD MASS FLOW CONTROLLER CALIBRATION.........................27

APPENDIX 4: STAR CHROMATOGRAPHY WORKSTATION SETUP................... 28

APPENDIX 5: PURITY DETERMINATION OF SULFUR MUSTARD BY GC-MS. 29

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1. Introduction

In order to monitor samples of the chemical warfare blister agent 2,2-dichlorodiethylsulfide (or sulfur mustard), trapped in diethyl phthalate as a result of experimentsperformed on protective clothing, an improved analytical procedure which providedappropriate sensitivity in a realistic time was sought.

Although being clear and odourless when pure, sulfur mustard is normally an amberto black coloured liquid with a characteristic smell similar to garlic or rotten onions.At room temperature, mustard agent is a liquid with low volatility (vapour pressure0.11 mm Hg @ 25C) and is very stable during storage. Sulfur mustard is soluble infats and oils and can easily be dissolved in most organic solvents but has negligiblesolubility in water. In alkali solutions, sulfur mustard decomposes (hydrolyses) intonon-poisonous products. As sulfur mustard forms large globules that are suspendedin the alkali solution, with only the surface layer in contact with the alkali solution, thedecomposition process proceeds slowly. Usually sulfur mustard is disposed of byleaving it in a hypochlorite solution for approximately 24 hours (see appendix 1 fordisposal information).

The technique chosen for the detection of sulfur mustard involved a new design of gaschromatography (GC) detector (Pulsed Flame Photometric Detector - PFPD), that hasbeen claimed to provide increased selectivity and sensitivity to sulfur detection. Thestudy involved developing a GC method capable of performing the analysis in aminimal time, preparation of standards that are representative of the samples to beanalysed and establishment of a quality control procedure to confirm the integrity ofthe analysis.

Due to time constraints, attainment of the lowest possible detection limit was not

attempted. Instead a value of 0.5g/mL of sulfur mustard in DEP was set as thelowest probable concentration of sulfur mustard to be encountered in protectiveclothing penetration experiments. To demonstrate that this level could reliably bedetected using this technique, this concentration was halved and the ability to

routinely detect samples containing 0.25 g/mL of sulfur mustard in DEP was definedas a goal.

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2. Instrumentation

The sulfur mustard samples were analysed using a Varian 3400 Gas Chromatograph.The samples were introduced to the gas chromatograph using a Varian 8200-CX autosampler and, after separation had occurred, detected using a Varian Pulsed FlamePhotometric Detector (PFPD see 2.1). The detector signal was processed using the Starchromatography workstation (ver 4.51) data handling system. The main advantages ofusing the PFPD include improved detection sensitivity (approximately 2 orders ofmagnitude for S2) for sulfur and phosphorus, increased detection selectivity againsthydrocarbon molecules (approximately 3 orders of magnitude in the sulfur mode),lower gas consumption, reduced emission quenching, additional temporal informationand the ability to detect selectively other heteroatoms such as nitrogen, or thesimultaneous detection of sulfur and carbon.1

2.1 Pulsed Flame Photometric Detector (PFPD)

The Pulsed Flame Photometric Detector is a development of the Flame PhotometricDetector (FPD) that has long been the detector preferred for the selective measurementof sulfur and phosphorus compounds. The PFPD is a new design which employs apulsed-flame operation instead of the continuous-flame mode of detection. Thepulsed-flame mode is based on a flame source and combustible gas flow that cannot besustained. The combustible gases (H2 and air) are mixed in a small combustionchamber before entering an ignition chamber that contains a continuously-heatedigniter coil. The ignited flame then propagates back to the combustible mixture sourceand is self - terminated after the combustible gas mixture is consumed. Thecontinuous gas flow then exhausts the combustion products and refills the ignitionchamber creating an additional ignition when the mixture reaches the igniter coil. Thisprocess continues in a periodic fashion at a rate of about 2-4 Hz.

Due to the pulsing nature of the PFPD the processing electronics have been modifiedto work with pulsed signals. The derived emissions appear as discrete signalsseparated in time. These discrete signals are stored for each pulse and used to generatea peak (waveform). While this peak contains all the signal information from the

chromatographic peak it may or may not have an identical shape. Given this,quantification is normally based on peak areas which are less affected than peakheights by the pulsing nature of the detector and the processing electronics of theemission signal.

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2.1.1 The flame pulsation cycle.

This cycle involves four stages (Figure 1):

1. Fill: The air (Air 1) and hydrogen are mixed, before entering the combustorchamber through the interior (combining with the column effluent) and around theoutside of the quartz combustor tube. A split valve is employed to set the ratio ofair to hydrogen flow through and around the quartz combustor tube. Additionalair flow (Air 2) into the wall flow provides a means of adjusting the ratio of air tohydrogen and balancing the fill rate of the combustor and igniter chambers.

2. Ignition: The igniter chamber contains a continuously heated Ni/Cr wire igniter.When the combustible mixture makes contact with this coil ignition occurs.

3. Propagation: The ignited flame front then propagates downward to the gas sourcein the combustor chamber. This chamber contains the column effluent. The flameis self terminated once all of the combustible gas mixture present in the combustionpath is consumed. The combustion products are swept from the detector (a result ofthe continuous gas flow through the detector) via a vent located at the top of theigniter chamber. The fill stage then begins again and the process repeats itself.

4. Emission: During and after flame propagation, light is emitted by the excitedmolecules that result from the combustion of the column effluent. To gainmaximum sensitivity this must occur in the combustor chamber. The flamebackground emits light for less than 0.3 milliseconds after propagation, whereas

sulfur (and phosphorus) containing molecules will emit light over a longer period.It is this difference that adds to the selectivity and sensitivity of the PFPD.

2.1.1.1 Gas flows/composition and chamber fill times

The flow paths of gases entering and exiting the detector are shown in Figure 2. Thesensitivity and selectivity of the PFPD are dramatically affected by the relative flowrates of these gases. The flame pulsation rate is determined by the total flow of air andhydrogen entering the detector. When adjusting the gas mixture composition it isimportant to strike a balance between the time required to fill the combustor chamber

and the time required to fill the igniter chamber. If the combustor chamber does notfill slightly before the igniter chamber then the analyte response will be markedlydecreased due to the pulsed flame only propagating into the combustor on every otherpulse. This results in incomplete combustion of the sample before it vents from thedetector and greatly increased noise due to ignition occurring on alternate pulses(referred to as tick-tock mode). In the opposite situation, if the combustor chamberfills too quickly (relative to the igniter chamber), again a reduction in analyte responsewill result. This is due to a portion of the sample exiting the combustor chamberbefore complete combustion of the column effluent has occurred. The fill times of thetwo chambers can be adjusted by the air/hydrogen flow entering the detector.

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2.1.2 Emission profiles

The composition of the combustible gas mixture is a determining factor in thecharacter and intensity of the flame emission. Hydrogen rich flames operate at a lowertemperature that favours gas phase chemical reactions with products that emit light(background emission) in the blue region. Hydrocarbon-related emission, however, isvery short and its time scale is shorter than the time of pulsed-flame front propagationthrough the viewing zone.1 In contrast, products from sulfur containing species (S2)form later and have greater lifetimes than background species. Figure 3 shows thetime-dependant separation of the hydrocarbon and sulfur emission profiles. It can beseen that the OH, CH and C2 emissions in a hydrogen-rich flame occur and then decaywithin 4 milliseconds. From these emission profiles it is obvious that S2 emission isnegligible during OH emission and that the S2 emission reaches a maximum about 5-6milliseconds after the OH emission and lasts 2-6 times longer than the emission of thespecies responsible for background emission. This phenomenon allows the easyseparation of the sulfur emission from any residual hydrocarbon emissions. This timedependent separation is achieved by the use of a simple electronic amplifier thatintegrates the emission related current within a delayed time gate window. By tuningthe gate delay (the period between flame ignition and the start of integration of theemission) and gate width (the period over which integration occurs) to the needs ofspecific analysis, considerable improvements in the sensitivity and selectivity of sulfurand phosphorous containing species are possible.

2.1.3 Detector Sensitivity

The sensitivity of the PFPD is reliant upon the emission duration across the viewingwindow of the photomultiplier tube.1 The emission duration is dependent on theopening diameter of the viewing windows and the flame velocity. In general,increasing detector temperature increases the flame velocity, resulting in a decrease inthe emission duration and a reduction in the sensitivity of the detector. There arethree main reasons why the PFPD has a reported two orders of magnitude increase insensitivity:

Noise from the flame background and the photomultiplier tube issignificantly reduced by the delayed gated integration of the emission profile.

Increased brightness of the flame results from reduced total gases and asmaller flame volume. This results in an increase in the sulfur signal which isdependent on the square of the sulfur concentration. For this reason a narrowbore quartz combustor tube is used to increase sensitivity for sulfur analysis.

The increased selectivity allows the narrow band interference filter to bereplaced with the cheaper and more stable1 wide band coloured glass filter.This results in an increase in the heteroatom signal by one order ofmagnitude. Although the carbon response is significantly increased, thiseffect is removed by the time-delayed gate integration.

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3.Experimental Procedures

3.1 Gas Chromatography Instrumentation and Conditions

A Varian 3400 GC with a Varian 8200-CX auto sampler and Star chromatographyworkstation (ver 4.51) data handling system was used for the analysis. The gaschromatograph contained the Varian Pulsed Flame Photometric Detector (see 2.1). Theinstrument start up procedure is described in appendix 2.

3.1.1 Varian 3400 GC Set Up.

The Varian 3400 GC was set up as specified in Table 1. Samples were injected using aVarian 1041 universal injector with a capillary column adaptor fitted. A non-polarSGE 12QC5/BP1 (see Table 2) fused silica capillary column was used to separate thesamples. The carrier gas was high purity nitrogen (BOC Gases Australia) used at aflow rate of 3.0 mL/min.

The gas chromatograph temperature settings were as follows:

Injector 275C

Oven 230C

Detector 250C

Chromatograms (GC runs) were 0.65 minutes in length with the sulfur mustard peakhaving a retention time of approximately 0.4 minutes (see Figure 4). A two minuteequilibration time was programmed between each run.

3.1.2 Pulsed Flame Photometric Detector.

The PFPD has a large number of variables that all require optimisation (and re-optimisation) in order to achieve improved sensitivity. As changing one gas flow mayalter the balance of the detector chambers filling rate, the optimisation process has noregimented procedure except to employ a systematic approach of trial and error

adjustments. Firstly, the dial indicators on the flow controllers must be calibrated,noting that the flow controllers must have pressure applied for 24 hours beforeconstant flows are possible. This is achieved by closing all cylinders and flowcontrollers, then sequentially turning on the cylinder and increasing the flow controllerby increments of 100 units while noting the flow exiting the detector. This procedureis carried out for all flow controllers (for calibration curves see appendix 3). Foroptimum sulfur sensitivity it is recommend that the narrow bore quartz combustor isused along with a detector temperature of 200 C2, although after optimisation this wasset at 250C.

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3.1.2.1 Optimisation of PFPD.The flow controllers were set to the suggested gas flow 2 and the split valve adjusted so

that the detector was just out of tick-tock mode. The described procedure, however,did not achieve the expected detector response. This was overcome by first turning thesplit valve fully clockwise, and then turning it anti-clockwise (noting the number ofturns) until the irregular tick-tock pulse became regular again. The split valve wasadjusted turn anti-clockwise/clockwise and a standard sample injected noting thesulfur response. This procedure was repeated until a maximum sulfur response wasachieved. The response of the PFPD increases when hydrogen rich conditions areused. The H2 flow controller was therefore increased by ten units and then thestandard solution was injected 3 times to determine sulfur response (ie peak area). TheH2 flow is then increased (or decrease) until the sulfur response no longer increases. Ifthe pulse rate exceeds 4 pulses per second then the Air1 flow should be reduced by 10

units while continuing to increase the H2 flow. This adjustment should be repeated forthe Air1 and Air2 flow controllers, injecting a standard after each adjustment todetermine sulfur response. Once the Sulfur emission has been optimised the splitvalve must again be adjusted such that the detector is just out of tick-tock (seeabove). Finally the detector temperature should be adjusted in a similar manner tothat of the flow controllers (ie increase/decrease detector temperature by 20C theninject standard to determine Sulfur response). Optimum PFPD configuration for thismethod is detailed in Table 3.

3.1.3 Varian 8200 CX Auto Sampler.

The 8200 autosampler is a pneumatic/motor driven autosampler that allows theautomated analysis of up to 48 samples. The sampler is mounted directly over theinjector on the top cover of the 3400 GC. Samples may be injected using the presetmodes or, as in the case of this method, a user defined mode.Programmable parameters include:

Injection volume (0.1-5.0L) and rate (0.2-10L/sec)

Sample uptake rate

Syringe needle depth and solvent wash cycle

Residence time and hot needle timeThe settings of the 8200 autosampler used in this method are listed in Table 4. The

optimised injection volume of 1.4 L was determined by injecting increasing volumes

of a known standard and observing the detector response. A similar method ofoptimisation was used for determining the injection rate.

3.1.4 Star Chromatography Workstation.

The Star Chromatography workstation, Version 4.51 (see Appendix 4 for methodsetup), is a software package for automated data acquisition, analysis, and reporting ofsamples analysed on Varian GC instruments. The system receives the detector output,storing the raw data on a Laboratory PC's hard disk before performing arithmeticalmanipulations and producing a detailed report page for individual injections.

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3.2 Quantification/ Preparation of Standards.

Quantification was accomplished by preparing standard solutions of sulfur mustard inpurified diethyl phthalate with a range of 0.25 to 5.0 g/mL. DEP was chosen as thesolvent as this is the solvent commonly used to trap sulfur mustard vapour inexperiments. Analytical standards were made from pure sulfur mustard diluted to100mL with DEP. In previous experiments this sample of sulfur mustard had beenfound to be 99.9% pure. To determine if significant degredation had occured since thisanalysis had been performed, the sulfur mustard was dissolved in dichloromethaneand analysed on a gas chromatograph linked to a mass spectrometer (GC-MS). Theresulting total ion chromatogram indicated that the sulfur mustard sample was greaterthan 99% pure (see appendix 5). This stock solution of sulfur mustard was then used

to make up a solution of DEP containing 50 g/mL sulfur mustard, which was then

diluted to make the working solutions (see Table 5). Experiments determined thatthese working solutions were valid for periods of up to 12 weeks. A period of 6 weekswas set as the maximium time that standards were to be used before replacement.Analytical working curves, that plot concentration of sulfur mustard standards

(g/mL) verses the peak area counts of the identified sulfur mustard peak, weregenerated by the Star Chromatography system. Figure 5 shows the chromatogramstypical of the standards that were used to generate such calibration curves. Theinstrument calibration was broken into standards of low and high concentrations of

sulfur mustard. The high concentration standard calibration curve (1.0-5.0g/mL) wasa cubic curve fit that forced the origin through zero (see Figure 6) and commonly had acorrelation coefficient greater than R2=0.995. The low level standard calibration curve

(0.25-1.0g/mL) was a linear curve fit that included the origin (see Figure 7). Againthe correlation coefficient was commonly greater than R2=0.995.

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4.Results and Discussion

The analytical method required many months of development before the aims of theproject were achieved. The long development period can be attributed to two mainreasons:

Firstly, there were a number of problems with the hardware of the GC system. Beforeattempting any method optimisation the GC components were completely overhauled.The injector and detector were thoroughly cleaned and the column was refitted andany leaks repaired. The peak areas of consecutive injections of the same sampleshowed a high degree of variation. This problem was traced to a faulty syringe in theautosampler, which was subsequently replaced, resulting in a marked improvement inreproducibility. A dramatic lack of sensitivity was significantly improved by

increasing the sample injection rate of the autosampler from 1 to 2L/second. Theserepairs and changes resulted in a 10 fold increase in sulfur mustard peak areas. Itshould be noted that with a detector as complicated as the PFPD, it can be verydifficult to troubleshoot during method development. It can be very time consumingtrying to optimise the detector when the problem resides in other components of theGC system. It is also very difficult to track down faults with other system componentswithout first optimising the detector, albeit it crudely.

The second issue was that the detector response did not follow that described in thePFPD Operators Manual. The manual suggests a detector operating temperature of200C and indicates that increasing this temperature will result in a decreased sulfurresponse2. While this may be true it was found that at lower temperatures, the peakareas did increase, but, the peaks also broadened and distorted so badly that poorreproducibility resulted. A detector temperature of 250C was found to provide thebest compromise between sensitivity and reproducibility. The manual alsorecommends use of a hydrogen rich flame, however it was found that this resulted inbroad sulfur mustard peaks that exhibited poor sensitivity. A leaner flame gave thebest compromise between high sensitivity and acceptable reproducibility. It was alsofound that baseline observations made while adjusting the Air-H2 needle valve (toestablish tick-tock - see 2.1.2) did not correspond to those described.2 As aconsequence the optimum setting of the Air-H2 needle valve was determined byperforming multiple injections of a standard sulfur mustard solution.

As DEP is one of the more viscous solvents that a chromatographer will encounter, along and complicated syringe filling regime is required to present a representativesample that contains no air bubbles to the injector. This regime increased the analysistime considerably. The syringe fill time, approximately 5 minutes, put tight limitationson the length of each chromatographic run. If a reasonable sample throughput was tobe maintained, the sample analysis would have to be as short as possible. For thisreason a short (12 meter) non-polar fused silica column was selected and was found toprovide excellent separation in less than one minute analysis time. To aid the injectionof larger volumes of the viscous sample on to the chromatographic column a megabore

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column (id=0.53mm) was the preferred option. This decision was made with fullknowledge that approximately one order of magnitude in sensitivity would besacrificed as a direct result of the increased column flow.1 It was hoped that this loss insensitivity would be compensated for by taking advantage of the ability of the PFPD tocope with large amounts of solvent (ie greater sample volumes). As the sulfurresponse is proportional to the square of the sulfur concentration it was consideredthat larger sample volumes would aid in the trace level detection of sulfur in DEP.

Previous flame photometric methods used to analyse samples of sulfur mustard in

DEP had detection limits of 0.5g/mL. One of the aims of this method developmentusing the PFPD was to be able to routinely analyse samples that contain less than

0.5g/mL of sulfur mustard. This was achieved using the described method with

standards that contain 0.25g/mL of sulfur mustard being analysed on a routine basis.

This sensitivity was achieved by optimising only the basic variables of the PFPD (ieflow rates, split valve, detector temperature, combustor tube).Greater sensitivity, however, should be achievable by optimising parameters such as:

Photomultiplier tube voltage

Gate delay Gate width

GainAt present, greater improvements in the sensitivity of the method are not considerednecessary, as the detection requirements have already been met.

To provide an indication of the robustness of the method, the ability to maintain

calibration levels within preset limits was investigated. The low level method wascalibrated, then used to analyse a large number of samples that had been generatedfrom clothing penetration tests. All samples were injected four times as standard

practice, then the 0.975 g/mL sulfur mustard standard, used to calibrate the method,was injected in triplicate every 8 samples, or 32 injections. This procedure wasrepeated for a total of 490 injections and carried out over a period of 17 days. Theresulting control chart (Figure 8) shows that of the 42 times that the verificationstandard was injected (during the 490 total injections) the deviation of the calculatedconcentration, from the known concentration of the standard, exceeded the 5% controllimit only 5 times. Furthermore, all injections that fell outside the control limit werestill within 6% of the known concentration of the standard. The control chart also

shows that at no time did the average value for the verification standard (the dashedline in the control chart ) fall outside the 5% control limits. This indicates that thecalibration curve will remain valid for at least two weeks or 500 injections. This isconsistent with the work load that the system would be expected to undertake duringnormal operations without requiring maintenance. For the method development,stringent control limits of 5% were considered appropriate.

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For quality control during routine analysis a standard sample would be injected intriplicate every 8 samples (or 32 injections) to verify the integrity of the calibrationcurve. It was decided that a 10% control limit was suitable as the alarm point thatwould alert the operator to recalibrate the method. This alarm can be pre-set in theverification setup of the Star Chromatography Workstation, by setting the deviationtolerance to 10%. When verification injections fall between the 5 and 10% controllimits, results should be viewed critically and the method calibration carefullymonitored.

5.Conclusion

A gas chromatographic procedure has been developed that analyses samples of DEPcontaining varying amounts of the chemical warfare agent sulfur mustard. Thesesamples are typical of those generated during clothing penetration studies. Theprocedure utilises a new design of GC detector based on a pulsed version of thecommonly used flame photometric detector. The system provides the selectivity andsensitivity required to fulfil the goal of routine analysis of samples containing 0.25

g/mL of sulfur mustard in DEP. This concentration equates to 0.35 ng of sulfurmustard injected on to the GC column. Although the initial set up and detectoroptimisation were found to be time consuming, once running, the detector requiresminimal maintenance.

The procedure was found to be robust with the method calibration able to bemaintained within a stringent 5% error tolerance for long periods. It is recommendedthat the method be recalibrated every 2 weeks or 500 sample injections, which evercomes first. It is further recommended that a quality control program be introducedinto the analysis. This would involve injecting (in triplicate) a standard sample every32 injections. If any of the three standard injections fall outside 10% control limits themethod should be recalibrated immediately. If two or more of the injections shouldfall between the 5% and 10% control limits then the results should be criticallyanalysed.

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6.References

1 Cheskis S, Atar E & Amirav A. Pulsed-Flame Photometer: A Novel GasChromatography Detector.Anal. Chem. 65, 539-555, 1993.

2 Varian Chromatography Systems. Pulsed Flame Photometric Detector: - OperatorsManual. Varian Associates, Inc. 1995.

7.AcknowledgmentsEric Mattsson for performing GC-MS analysis to determine the purity of the sulfurmustard used to make up standard solutions.

Bernie Gray for providing samples of sulfur mustard that had been generated duringclothing trials performed in the Combatant Protection & Nutrition Branch.

Denys Amos for providing editorial advice in the preparation of this report.

8.Glossary of Acronyms

CPNB Combatant Protection and Nutrition BranchDEP diethyl phthalateDSTO The Defence Science and Technology OrganisationFPD Flame Photometric DetectorGC gas chromatographyGC/MS gas chromatography/mass spectrometerHD Sulfur Mustard: 2,2'-dichlorodiethyl sulphideHz hertz

kPa kilopascalmL millilitresng nanogramsPFPD Pulsed Flame Photometric Detectorg micrograms

L microlitres

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9.Tables

Table 1. Setup for Varian 3400 GC.

Column: SGE 12QC5/BP1 1.0Oven: 230C, isocratic (for 0.65 minutes) run time

with a 2 minute stabilisation time between injectionsInjector: 1041, 275CDetector: Varian PFPD, 250C (Att=1; Range=10)Auto Sampler: Varian 8200CXData System: Varian Star Workstation ver 4.51Carrier: Nitrogen, 3.0 mL/minInjections: 1.4 L of sample at a rate of 2.0 L/sec.

Table 2. Column Specifications for: SGE 12QC5/BP1 1.0.

Length 12 MeterFilm Thickness 1.0 mInternal Diameter 0.53 mmOutside Diameter 0.68 mmType Bonded PhaseMaterial Fused SilicaPhase Dimethyl siloxane (non-polar)Operating Temperatures -60 to 315 C

Table 3. Setup for PFPD.

H2: 11.87 mL/min (Dial Setting=775a)Air-1: 14.76 mL/min (Dial Setting=630a)Air-2: 10.02 mL/min (Dial Setting=450a)Quartz Combustor tube Narrow boreAttenuation 1Range 10Full Scale 10 VoltsBunch Rate 8 Points (5.0 Hz)Noise Monitor Length 64 Bunched Points (12.8 seconds)Photomultiplier tube high voltage 550 VoltsPulse Rate 2-4 HzGate Width 1.0 millisecondsGate Delay 1.0 millisecondsTrigger Level 200 millivoltsAir1/H2 split valve 4.375 turns anti-clockwisea for flow controller calibration charts see appendix 3

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Table 4. 8200 Autosampler Settings.

Mode User Defined

Syringe Wash Solvent Wash A (EtOH) then B( CH2Cl2)Solvent Wash Time 10 secondsVial Needle Depth 90%Uptake Speed 1.0 L/secPause Time 10 secondsInject Rate 2.0 L/secInjection Volume 1.4 L

Table 5. Preparation of Standard Solutions.Mass of sulfur mustard Volume of DEP

Stock Solution" 1 drop (30-50mg) of HD 100 mL

50g/mL Std Solution# appropriate mass of" 25 mL

5g/mL Std Solution 2.5g of# 25 mL

4g/mL Std Solution 2.0 of# 25 mL




0.5g/mL Std Solution 0.25 of# 25 mL

0.25g/mL Std Solution 0.125 of#

25 mL

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10. Figures

Figure 1: Stages of the Pulsed Flame Photometric Detectors pulsed-flame operation2.

Figure 2: Schematic of the Pulsed Flame Photometric Detector2.

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Figure 3: Hydrocarbon and S2 flame emission profile, as a function of time1

Figure 4: Chromatogram of 0.25 g/mL Sulfur Mustard standard. Sulfur mustard peakelutes at 0.402 minutes

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Figure 5: Overlay of chromatograms of the standards used to calibrate this method. Standards

ranged from 0.25-5.0g/mL of Sulfur Mustard in diethyl phthalate.

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Figure 6: High concentration method calibration curve. (1.0-5.0 g/mL HD in DEP)

Figure 7: Low concentration calibration curve. (0.0-1.0 g/mL HD in DEP)

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Figure 8: Control Chart with control limit set at 5% deviation from the calculated value of the

standard used. In this case the 0.9749 g/mL HD standard, used to calibrate themethod, was analysed (three injections) after every 32 sample injections. Thedashed line represents the average of the three injections. The calibration curvewas still found to be accurate (within the 5% control limits) after nearly 500injections had been made.

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Appendix 1: MSDS for Distilled Mustard (HD)

Note: This is an abridged version of the full MSDS that can be found at:http://www.apgea.army.mil/safety/msds/hd1.html

SECTION I - GENERAL INFORMATION

DATE: 22 September 1988REVISED: 28 February 1996

MANUFACTURER'S ADDRESS:

U.S. ARMY CHEMICAL BIOLOGICAL DEFENSE COMMAND

EDGEWOOD RESEARCH DEVELOPMENT, AND ENGINEERING CENTER (ERDEC)

CAS REGISTRY NUMBERS: 505-60-2, 39472-40-7, 68157-62-0

CHEMICAL NAME: bis-(2-chloroethyl)sulfide

TRADE NAMES AND SYNONYMS:

Sulfide, bis (2-chloroethyl)Bis(beta-chloroethyl)sulfide1,1'-thiobis(2-chloroethane)

1-chloro-2(beta-chloroethylthio)ethaneBeta, beta'-dichlorodiethyl sulfide2,2'dichlorodiethyl sulfideDi-2-chloroethyl sulfideBeta, beta'-dichloroethyl sulfide2,2'-dichloroethyl sulfideH; HD; HSIpritKampstoff "Lost"; LostMustard GasS-Lost; S-yperite; Schewefel-lost

Sulfur mustard; Sulphur mustard gasYellow Cross LiquidYperite

CHEMICAL FAMILY: Chlorinated sulfur compound

FORMULA/CHEMICAL STRUCTURE: C4H8Cl2S

ClCH2CH2-S-CH2CH2Cl

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SECTION II - HAZARDOUS INGREDIENTS

INGREDIENTSNAME

FORMULA PERCENTAGE BYWEIGHT

AIRBORNEEXPOSURE LIMIT

(AEL)

Sulfur Mustard C4H8Cl2S 100 0.003 mg/m3

SECTION III - PHYSICAL DATA

BOILING POINT: 217 C (422 F)

VAPOR PRESSURE (mm Hg): 0.072 mm Hg @ 20 C0.11 mm Hg @ 25 C

VAPOR DENSITY (AIR=1): 5.5

SOLUBILITY IN WATER: Negligible. Soluble in fats and oils, gasoline, kerosene,acetone, carbon tetrachloride, alcohol, tetrachloroethane, ethylbenzoate, and ether.Miscible with the organophosphorus nerve agents.

SPECIFIC GRAVITY (H2O=1): 1.27 @ 20 C

FREEZING POINT: 14.45 C

LIQUID DENSITY (g/cc): 1.268 @ 25 C1.27 @ 20 C

PERCENTAGE VOLATILE BY VOLUME:610 mg/m3 @ 20 C920 mg/m3 @ 25 C

APPEARANCE AND ODOR:

Normally amber to black colored liquid with garlic or a horseradish odor. Water clearif pure. The odor threshold for HD is 0.6 mg/m3 (.0006 mg/L).

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SECTION IV - FIRE AND EXPLOSION DATA

FLASHPOINT: 105 C (Can be ignited by large explosive charges)

FLAMMABILITY LIMITS (% by volume): Unknown

EXTINGUISHING MEDIA: Water, fog, foam, CO2. Avoid use of extinguishingmethods that will cause splashing or spreading of HD.

SECTION V - HEALTH HAZARD DATA

AIRBORNE EXPOSURE LIMIT (AEL): The AEL for HD is 0.003 mg/m3 as found in"AR 40-173, Occupational Health Guidelines for the Evaluation and Control ofOccupational Exposure to Mustard Agents H, HD, HT." To date, the OccupationalSafety and Health Administration (OSHA) has not promulgated a permissibleexposure concentration for HD.

EFFECTS OF OVEREXPOSURE: HD is a vesicant (causing blisters) and alkylatingagent producing cytotoxic action on the hematopoietic (blood-forming) tissues which

are especially sensitive. The rate of detoxification of HD in the body is very slow andrepeated exposures produce a cumulative effect. HD has been found to be a humancarcinogen by the International Agency for Research on Cancer (IARC).

Median doses of HD in man are:

LD50 (skin) = 100 mg/kgICt50 (skin) = 2000 mg-min/m3 at 21-27C (70 - 80 F - humid environment)

= 1000 mg-min/m3 at 32 C (90 F - dry environment)

ICt50 (eyes) = 200 mg-min/m3

ICt50 (inhalation) = 1500 mg-min/m3 (Ct unchanged with time)

LD50 (oral) = 0.7 mg/kg

Maximum safe Ct for skin and eyes are 5 and 2 mg-min/m3, respectively.

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ACUTE PHYSIOLOGICAL ACTION OF HD IS CLASSIFIEDAS LOCAL AND SYSTEMIC.

LOCAL ACTIONS: HD effects both the eyes and the skin. SKIN damage occurs afterpercutaneous absorption. Being lipid soluble, HD can be absorbed into all organs.Skin penetration is rapid without skin irritation. Swelling (blisters) and reddening(erythema) of the skin occurs after a latency period of 4-24 hours following theexposure, depending on degree of exposure and individual sensitivity. The skinhealing process is very slow. Tender skin, mucous membrane and perspiration-covered skin are more sensitive to the effects of HD. HD's effect on the skin, however,is less than on the eyes. Local action on the eyes produces severe necrotic damage andloss of eyesight. Exposure of eyes to HD vapor or aerosol produces lacrimation,photophobia, and inflammation of the conjunctiva and cornea.

SYSTEMIC ACTIONS: Occurs primarily through inhalation and ingestion. The HDvapor or aerosol is less toxic to the skin or eyes than the liquid form. When inhaled,the upper respiratory tract (nose, throat, tracheae) is inflamed after a few hours latencyperiod, accompanied by sneezing, coughing, and bronchitis, loss of appetite, diarrhea,fever, and apathy. Exposure to nearly lethal doses of HD can produce injury to bonemarrow, lymph nodes, and spleen as showed by a drop in white blood cell count, thusresulting in increased susceptibility to local and systemic infections. Ingestion of HDwill produce severe stomach pains, vomiting, and bloody stools after a 15-20 minutelatency period.

CHRONIC EXPOSURE: HD can cause sensitization, chronic lung impairment,(cough, shortness of breath, chest pain), cancer of the mouth, throat, respiratory tractand skin, and leukemia. It may also cause birth defects.

EMERGENCY AND FIRST AID PROCEDURES:

INHALATION: Hold breath until respiratory protective mask is donned. Removefrom the source IMMEDIATELY. If breathing is difficult, administer oxygen. Ifbreathing has stopped, give artificial respiration. Mouth-to-mouth resuscitationshould be used when approved mask-bag or oxygen delivery systems are notavailable. Do not use mouth-to-mouth resuscitation when facial contamination exits.

Seek medical attention IMMEDIATELY.

EYE CONTACT: Speed in decontaminating the eyes is absolutely essential. Removethe person from the liquid source, flush the eyes immediately with water for at least 15minutes by tilting the head to the side, pulling the eyelids apart with the fingers andpouring water slowly into the eyes. Do not cover eyes with bandages but, if necessary,protect eyes by means of dark or opaque goggles. Transfer the patient to a medicalfacility IMMEDIATELY.

SKIN CONTACT: Don respiratory protective mask. Remove the victim from agentsources immediately. Immediately wash skin and clothes with 5% solution of sodium

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hypochlorite or liquid household bleach within one minute. Cut and removecontaminated clothing, flush contaminated skin area again with 5% sodiumhypochlorite solution, then wash contaminated skin area with soap and water. Seekmedical attention IMMEDIATELY.

INGESTION: Do not induce vomiting. Give victim milk to drink. Seek medicalattention IMMEDIATELY.

SECTION VI - REACTIVITY DATA

STABILITY: Stable at ambient temperatures. Decomposition temperature is 149 C to177 C. Mustard is a persistent agent depending on pH and moisture, and has been

known to remain active for up to three years in soil.

INCOMPATIBILITY: Rapidly corrosive to brass @ 65 C. Will corrode steel at a rate of.0001 in. of steel per month @ 65 C.

HAZARDOUS DECOMPOSITION: Mustard will hydrolyze to form HCl andthiodiglycol.

HAZARDOUS POLYMERIZATION: Does not occur.

SECTION VII - SPILL, LEAK, AND DISPOSAL PROCEDURES

STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If spillsor leaks occur, only personnel in full protective clothing will remain in the area. Incase of personnel contamination See Section V for emergency and first aid instructions.

RECOMMENDED FIELD PROCEDURES: The HD should be contained usingvermiculite, diatomaceous earth, clay or fine sand and neutralized as soon as possibleusing copious amounts of 5.25% sodium hypochlorite solution. Scoop up all materialand clothing and place in a approved DOT container. Cover the contents of the

container with decontaminating solution as above. The exterior of the container willbe decontaminated and labelled according with EPA and DOT regulations. All leakingcontainers will be over packed with vermiculite placed between the interior andexterior containers. Decontaminate and label in accordance with EPA and DOTregulations. Dispose of the material in accordance with Federal, state and localregulations. Conduct general area monitoring with an approved monitor to confirmthat the atmospheric concentrations do not exceed the airborne exposure limits.

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SECTION VIII - SPECIAL PROTECTION INFORMATION

RESPIRATORY PROTECTION:

CONCENTRATION RESPIRATORY PROTECTIVE EQUIPMENT.< 0.003 mg/m3 A full face piece, chemical canister, air purifying

protective mask will be on hand for escape.(The M9-, M17-, or M40-series masks areacceptable for this purpose. Other maskscertified as equivalent may be used)

> 0.003 mg/m3A NIOSH/MSHA approved pressure demand fullface piece SCBA suitable for use in high agent

concentrations with protective ensemble.(See DA PAM 385-61 for examples).

PROTECTIVE GLOVES: Butyl Rubber Gloves M3 and M4 Norton, ChemicalProtective Glove Set

EYE PROTECTION: As a minimum, chemical goggles will be worn. For splashhazards use goggles and face shield.

OTHER PROTECTIVE EQUIPMENT: For laboratory operations, wear lab coats,gloves and have mask readily accessible. In addition, daily clean smocks, foot covers,

and head covers will be required when handling contaminated lab animals.

MONITORING: Available monitoring equipment for agent HD is the M8/M9detector paper, blue band tube, M256/M256A1 kits, bubbler, Depot Area AirMonitoring System (DAMMS), Automated Continuous Air Monitoring System(ACAMS),CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), theMiniature Chemical Agent Monitor (MINICAM), and Real Time Analytical Platform(RTAP).

SECTION IX - SPECIAL PRECAUTIONS

PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: When handlingagents, the buddy system will be incorporated. No smoking, eating, or drinking inareas containing agents is permitted. Containers should be periodically inspected forleaks, (either visually or using a detector kit). Stringent control over all personnelpractices must be exercised. Decontaminating equipment will be conveniently placed.Exits must be designed to permit rapid evacuation. Chemical showers, eyewashstations, and personal cleanliness facilities must be provided.

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Appendix 2: CPNB Varian 3400/PFPD start up

procedure.

Pneumatics: Turn on the appropriate cylinders, on the east wall outside of Rm 417.Hydrogen: 330 kPaNitrogen: 500 kPaAir: 500 kPaAir (for 8200): 440 kPa

3400 GC:

Action ResultTurn on GC(toggle switch at back of GC, top LHS)

The display reads:WARM START UP OCCURED

Turn on Auto Sampler(switch at back of auto sampler, bottom LHS)

Green light on front of autosamplerwill light up.

Press the activate key(in the Operations Section of the key pad)

The display reads:SELECT METHOD OR TABLE

Press the method 1 key(in the Method Section of the key pad)

The display reads:UNDER REMOTE CONTROL

Press the GC configure key(in the GC control section of the key pad)

The display reads:SET TIMES OR DATE? NO

Press the enter key(in the Entry Section of the key pad continueuntil the Hardware On-Off line appears)

The display reads:TURN HARDWARE ON-OFF? NO

Press the yes key(in the Entry Section of the key pad)Then press the enter key

The display reads:DETECTOR B ON? NO


The display reads:DETECTOR OVEN ON? NO


The display reads:INJECTOR OVEN ON? NO


The display reads:AUXILIARY OVEN ON? YES

Press the no then enter keys(in the Entry Section of the key pad)Until the GC config complete line appears.

The display reads:GC CONFIG COMPLETE

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PC/Star Workstation

Action ResultSwitch ON Computer, wait until programsload then minimize Program Manager

Screen displays:Star Software

Click on System Control/Automationthen wait for software to load.

Screen displays:System Control Configuration

Click on Instrumentthen PFPD in drop down menu

Screen displays:System Control PFPD

ACTIVATE METHOD:Click of File, then Method File in the dropdown menu, then activate.

Screen displays:Activate a System Control MethodFile dialogue box

Click on the method you want activated.(C:\Star\PAL\Pal.mth or Pal-low.mth)then OK

Screen displays:System Control

Click on inject Screen displays:Active Method Box

Once Active Method Box letters darken,close window.


ACTIVATE SAMPLE LIST:Click of File, then Sample List File in the dropdown menu, then activate.

Screen displays:Activate a System Control SampleList dialogue box

Click on the sample list you want activated.

(C:\Star\PAL\analysis.smp or Calib.smp)then OK

Screen displays:

Sample List Window

Minimize sample list windowNote: samples may be added, deleted ormodified through this window


ACTIVATE SEQUENCE FILE:Click of File, then Sequence File in the dropdown menu, then activate

Screen displays:Activate a System Control SequenceFile dialogue box

Click on the sequence file you want activated.(C:\Star\PAL\analysis.seq or Calib.seq)then OK

Screen displays:Active Sequence List Window

Minimize sequence windowNote: the sequence of events may be modifiedthrough this window


Click on Automation, then begin. Screen displays:Instrument 1 Parameters

Click on OK Screen displays:System Control

Click on OK Screen displays:System Control PFPD

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Appendix 3: PFPD Mass Flow Controller Calibration

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Appendix 4: Star Chromatography Workstation Setup

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Appendix 5: Purity Determination of Sulfur Mustard

by GC-MSAcquired on05-Feb-1998at13:52:34

4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0

Retention time min

0

100

%

322

Scan EI+ TIC

5.53e6 Scan

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Page classification: UNCLASSIFIED

DEFENCE SCIENCE AND TECHNOLOGY ORGANISATION

DOCUMENT CONTROL DATA 1. PRIVACY MARKING/CAVEAT (OFDOCUMENT)

2. TITLE

Gas Chromatographic Analysis of Sulfur Mustard in Diethyl

Phthalate

3. SECURITY CLASSIFICATION (FOR UNCLASSIFIED REPORTSTHAT ARE LIMITED RELEASE USE (L) NEXT TO DOCUMENTCLASSIFICATION)

Document (U)Title (U)Abstract (U)

4. AUTHOR(S)

Paul A Lancaster

5. CORPORATE AUTHOR

Aeronautical and Maritime Research LaboratoryPO Box 4331Melbourne Vic 3001 Australia

6a. DSTO NUMBER

DSTO-TR-07036b. AR NUMBER

AR-010-6036c. TYPE OF REPORT

Technical Report7. DOCUMENT DATE

August 1998

8. FILE NUMBER510/207/0896

9. TASK NUMBERADF 95/065

10. TASK SPONSORSGADF

11. NO. OF PAGES29

12. NO. OFREFERENCES

213. DOWNGRADING/DELIMITING INSTRUCTIONS 14. RELEASE AUTHORITY

Director Aeronautical and Maritime Research Laboratory

15. SECONDARY RELEASE STATEMENT OF THIS DOCUMENT

Approved for public release

OVERSEAS ENQUIRIES OUTSIDE STATED LIMITATIONS SHOULD BE REFERRED THROUGH DOCUMENT EXCHANGE CENTRE, DIS NETWORK OFFICE,DEPT OF DEFENCE, CAMPBELL PARK OFFICES, CANBERRA ACT 2600

16. DELIBERATE ANNOUNCEMENT

No Limitations

17. CASUAL ANNOUNCEMENT Yes

18. DEFTEST DESCRIPTORS

Gas Chromatography, Pulsed Flame Photometric Detector, Sulfur Mustard

19. ABSTRACT

A gas chromatographic method for the analysis of 2,2'-dichlorodiethyl sulfide (commonly known asSulfur Mustard or HD) that had been trapped in the solvent, diethyl phthalate (DEP) is described. The

method utilises the improved sensitivity and selectivity offered by the new Pulsed Flame PhotometricDetector to detect routinely samples containing 0.25 g/mL of sulfur mustard in DEP. The method iscapable of fast and reliable analysis of samples containing 0.25-5.0 g/mL of sulfur mustard in DEP.Quality control measures determined that the method calibration was still within 5% control limits afternearly 500 sample injections.

Page classification: UNCLASSIFIED

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