DETECTING AND MEASURING CHEMICAL WARFARE AGENTS IN REAL TIME USING THE TRACE ATMOSPHERIC GAS ANALYZER (TAGA)

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1 On-Scene Coordinator Readiness Conference Phoenix, AZ November 15-19, 2004 DETECTING AND MEASURING CHEMICAL WARFARE AGENTS IN REAL TIME USING THE TRACE ATMOSPHERIC GAS ANALYZER (TAGA) David B. Mickunas Chemist US EPA/ERTC

2 ACKNOWLEDGEMENTS Nancy H. Adams, Ph.D. Safe Buildings Program Director National Homeland Security Research Center Mr. Eric N. Koglin Contracting Officer Representative National Homeland Security Research Center Raj Mangaraj Donald Kenny Anne Gregg Battelle Memorial Institute

3 7. Establish/Demonstrate Sample Air Flow Operating System and Conditions to Ensure that No Less Than 85% of Material at the CWAs Quantitation Limit Passes Through the System TASKS 1. Develop Spectra and Calibration Curves for the CWAs 2. Develop Chemical Ionization Capabilities to Maximize Sensitivity for the CWAs 3. Determine and Verify Detection and Quantitation Limits for Each CWA 4. Determine Dynamic Linear Range for CWAs 5. Establish Surrogate Relative Response Factors 6. Determine if Other Materials Interfere with CWA Response

4 Task 1. Develop Spectra and Calibration Curves for the CWAs All experiments under this task order will be performed with the Perkin Elmer-SCIEX (PE-SCIEX) API-365. The CWAs to be used for this task are GA, GB, GD, GF, VX, HD, HN-1, HN-2, and HN-3. Prior to performance of operations using nitrogen mustards, all three nitrogen mustards will be converted from the hydrogen chloride salt forms (as obtained from the commercial vendors) to their freebase form.

5 Task 2. Develop Chemical Ionization Capabilities to Maximize Sensitivity for the CWAs The proton affinity of the G- and V-series CWAs are sufficiently higher than that of water to allow proton transfer from the H 3 O + and H 3 O(H 2 O) n+ reagent ions generated in the APCI source of the API-365. Therefore, ambient air APCI conditions in the positive ion mode will be used for ionization of all G- and V-series of agents for this study. The protonated water and associated water clusters under ambient air APCI conditions are not efficient for the ionization of sulfur mustard (HD). The sensitivity for HD is enhanced by the addition of a small amount (approx 0.03%) of benzene to the APCI inlet.

6 Task 2. Develop Chemical Ionization Capabilities to Maximize Sensitivity for the CWAs (continued) The addition of benzene alters the reagent ion chemistry so that charge transfer from (C 6 H 6 ) + is the dominant mechanism of ion production and the M + ion is the predominant precursor ion along with the associated 37 Cl isotopes at (M+2) + and (M+4) +. The benzene will be added by introducing a known flow of nitrogen or zero air through a benzene filled glass bubbler connected to the APCI source inlet. The flow rate of gas and type of benzene used will be documented. The most sensitive ionization mode for the nitrogen mustard species (HN-1, HN-2, and HN-3) will be examined using both positive ion APCI and benzene charge exchange ionization techniques. The most sensitive method will then be used for all subsequent testing of HN-1, HN-2, and HN-3.

7 Task 3. Determine and Verify Detection and Quantitation Limits for Each CWA The detection limit for each agent will be determined as three times the standard deviation of the ion pair s signal in the background (either room air or room air spiked with blank hexane) divided by the ion pair s response factor. The detection limit will be reported as the average of the individual ion pairs. The quantitation limit for a compound will be determined as ten times the standard deviation of the ion pair s signal in the background divided by the ion pair s response factor. The quantitation limit will be reported as the average of the individual ion pairs.

8 Task 3. Determine and Verify Detection and Quantitation Limits for Each CWA (continued) In order to verify the accuracy of the gas phase agent concentrations, Battelle will verify the concentration of the standard solutions used to generate the agents in the gas phase, via a gas chromatographic method using standard operating procedures (SOPs) in place. The assumption will be made that all of the standard solution will be vaporized into the API-365 s air sampling stream without degradation of the CWAs. If degradation were to occur during the vaporization process, the concentration in the air stream would be lower than the reported value. Thus, the actual detection limits would be lower than the reported values.

9 Task 4. Determine Dynamic Linear Range for CWAs As stated in Task 1, the dynamic range of calibration will be determined by observing the signals obtained from the detection limit to the ion current at which the signal is no longer linear (i.e., saturation of the reagent ions). The dynamic range will be explored by varying the solution concentration and/or the rate of introduction via the syringe drive during the generation of calibration curves. These experiments will be performed for each agent in conjunction with the development of calibration curves in Task 1.

10 Task 5. Establish Surrogate Relative Response Factors Spectra and calibration curves for the surrogate compounds will be obtained using the same procedures as described in Task 1. Both native diisopropyl methyl phosphonate (DIMP) and deuterated diisopropyl methylphosphonate (d 14 -DIMP) will be used as surrogates for all of the G- and V-series agents. Chloroethylethylsulfide (CEES, halfmustard) will be used as the surrogate for the mustard agents. The relative response factors will be established by comparison of the response of the surrogate compound(s) to the response of the chemical warfare agents.

11 Task 6. Determine if Other Materials Interfere with CWA Response Evaluate the effect of two potential interferences (vehicle exhaust and bleach) at two interferent concentrations to be determined during testing. Room temperature and humidity will not be controlled beyond the normal operation of the HVAC system. Interferent test concentrations will be obtained by diluting a concentrated feed with air. Depending on the interferent, the concentrated feed will be provided by one of two methods. For bleach, delivery will involve purging the headspace of a large boiling flask containing approximately 100 ml of the bulk liquid of interferent. The amount of flow through the flask will determine the concentration of the interferent added.

12 Task 6. Determine if Other Materials Interfere with CWA Response (continued) For the simulated gasoline/diesel engine exhaust, a concentrated feed of interferent will be generated by using compressed gas cylinders. Due to the large number of CWAs being tested, consistent compositions of the interferent is important. Consistency can be maintained by providing a mixture in compressed gas cylinder. The composition of the gas cylinder will be characterized via a gas chromatographic method using standard operating procedures (SOPs).

13 Task 6. Determine if Other Materials Interfere with CWA Response (continued) A steady concentration of the CWAs (and surrogate compounds) will be introduced while recording the signal on the mass spectrometer. After a period of time, the interference will be introduced and any change in signal will be recorded, the concentration of the agent will be changed (via the syringe drive) and any change in the signal recorded. The concentration of the interference can then be changed (via an increase/decrease of the feed air) and record any change in the agent signal. The concentration of the agent can be changed back to the original concentration and any change in the signal recorded. This procedure will test two agent concentrations at two interferent concentrations. Results will be reported as change in response due to the presence of the interference.

14 Task 6. Determine if Other Materials Interfere with CWA Response (continued) A false positive test can be performed in the same manner without the introduction of the CWA and observing changes in the signals of the CWAs.

15 Task 7. Establish/Demonstrate Sample Air Flow Operating System and Conditions to Ensure that No Less Than 85% of Material at the CWAs Quantitation Limit Passes Through the System Safety concerns in using research dilute solution (RDS) levels of CWAs require that the syringe drive and vapor generator are placed in a chemical hood during the experiments. A doublewalled glass tube will extend out of the hood and into the ion source of the API-365. This tube is approximately three feet in length. In order to demonstrate an 85% transmission of the CWAs through the sampling line, initially a three-foot section will be used to obtain the baseline transmission and then add an additional three foot length to the sampling line (within the hood). The agents will be vaporized into the glass tubing as in previous tests at a known concentration and the percent transmission through the three- versus six-foot sampling lines will be compared.

16 Task 7. Establish/Demonstrate Sample Air Flow Operating System and Conditions to Ensure that No Less Than 85% of Material at the CWAs Quantitation Limit Passes Through the System (continued) If the percent transmission is greater than 85% in the six-foot tube when compared to the three-foot tube, it will be assumed that there is greater than 85% transmission through the original three-foot section of sampling tubing.

17 Experimental Chamber

18 Vaporizer Unit

19 Calibration Unit

20 Trace Atmospheric Gas Analyzer Mobile Laboratory

21 Trace Atmospheric Gas Analyzer (TAGA)

22 Atmospheric Pressure Chemical Ionization (APCI) Source

23 TAGA Schematics

24 TAGA Operational Process

25 Chemical Agents Investigated GA Ethyl N-dimethylphosphoramidocyanidate GB Isopropyl methylphosphonofluoridate GD Pinacolyl methylphosphonofluoridate GF Cyclohexyl methylphosphonofluoridate VX O-Ethyl-S-[2-(diisopropylamino)ethyl] methyl phosphonothioate HD 2,2 -Di(chloroethyl)sulfide NH1 - N-Ethyl-2,2 -di(chloroethyl)amine NH2 - N-Methyl-2,2 -di(chloroethyl)amine NH3 2,2,2 -Tri(chloroethyl)amine

26 GA Ethyl N-dimethylphosphoramidocyanidate Molecular Weight 162 Parent Ion 163 Daughter Ions 135, 126, 117, 108, 90 H 3 C CH 2 O O P N C N H 3 C

27 +Q1: from 30JUL04A001 XGA MOL ION, centroided 7.0e5 6.5e5 6.0e5 5.5e5 5.0e5 O N C CH 2 P H 3 C O N H 3 C GA Ethyl N-dimethylphosphoramidocyanidate e5 cps 4.5e5 Intensity, cps 4.0e5 3.5e5 3.0e5 2.5e5 2.0e e e e m/z, amu

28 +Product (163): from 30JUL04A002 XGA PRODUCT, centroided 5.38e5 cps 5.0e5 4.5e5 H 3 C O CH 2 P O H 3 C C N N e5 GA Ethyl N-dimethylphosphoramidocyanidate e5 Intensity, cps 3.0e5 2.5e e5 1.5e5 1.0e e m/z, amu

29 XGA INFUSION signal intensity (icps) Excel Row 163> > > > >90

30 XGA CALIBRATION CURVE 163> Signal Intensity (icps) y = x + 54 R 2 = Source Concentration (ppbv) 163>135 LINEAR Linear (LINEAR)

31 GB Isopropyl methylphosphonofluoridate Molecular Weight 140 Parent Ion 141 Daughter Ions 117, 99, 97, 81, 79, 43 H 3 C CH O O P F

32 +Q1: from 30JUL04A006 XGB MOL ION, centroided 7.5e6 7.0e6 6.5e6 O CH P H 3 C O F e6 cps 6.0e6 GB Isopropyl methylphosphonofluoridate 5.5e6 5.0e6 4.5e6 Intensity, cps 4.0e6 3.5e6 3.0e6 2.5e6 2.0e6 1.5e6 1.0e e m/z, amu

33 +Product (141): from 30JUL04A007 XGB PRODUCT, centroided 7.0e5 6.5e5 6.0e5 O CH P H 3 C O F e5 cps 5.5e5 GB Isopropyl methylphosphonofluoridate 5.0e5 4.5e5 4.0e5 Intensity, cps 3.5e5 3.0e5 2.5e5 2.0e5 1.5e e5 5.0e m/z, amu

34 XGB INFUSION signal intensity (icps) Excel Row 141> >43 141>79 141>81 141>97 141>99

35 XGB CAL CURVE 141> Signal Intensity (icps) y = x + 66 R 2 = Source Concentration (ppbv)) 141>99 LINEAR Linear (LINEAR)

36 GD Pinacolyl methylphosphonofluoridate Molecular Weight 182 Parent Ion 183 Daughter Ions 99, 97, 57, 43, 41 H 3 C H 3 C C CH O O P F

37 +Q1: from 30JUL04A004 XGD MOL ION, centroided 1.99e7 cps 1.9e7 1.8e7 1.7e7 1.6e7 183 H 3 C H 3 C C O CH O P F 1.5e7 1.4e7 GD Pinacolyl methylphosphonofluoridate 1.3e7 1.2e7 Intensity, cps 1.1e7 1.0e7 9.0e6 8.0e6 7.0e6 6.0e6 5.0e6 4.0e e6 2.0e6 1.0e m/z, amu

38 +Product (183): from 30JUL04A005 XGD PRODUCT, centroided 1.62e5 cps 1.5e5 1.4e5 1.3e H 3 C H 3 C C O CH O P F 1.2e5 GD Pinacolyl methylphosphonofluoridate 1.1e5 1.0e5 Intensity, cps 9.0e4 8.0e4 7.0e4 6.0e4 5.0e4 4.0e4 3.0e4 2.0e e m/z, amu

39 XGD INFUSION signal intensity (icps) Excel Row 183>41 183>43 183>57 183>97 183>99

40 XGD CALIBRATION CURVE 183> Signal Intensity (icps) y = 8006x R 2 = Source Concentration (ppbv) 183>99 LINEAR Linear (LINEAR)

41 GF Cyclohexyl methylphosphonofluoridate Molecular Weight 180 Parent Ion 181 Daughter Ions 117, 99, 97, 55 O O P F

42 +Q1: from 30JUL040A008 XGF MOL ION, centroided 3.2e5 3.0e5 2.8e5 O O F P e5 cps 2.6e5 2.4e5 2.2e5 GF Cyclohexyl methylphosphonofluoridate e5 Intensity, cps 1.8e5 1.6e5 1.4e e5 1.0e e4 6.0e4 4.0e4 2.0e m/z, amu

43 +Product (181): from 30JUL04A009 XGF PRODUCT, centroided 1.0e5 9.0e4 8.0e4 O O F P e5 cps GF Cyclohexyl methylphosphonofluoridate 7.0e4 6.0e4 Intensity, cps 5.0e4 4.0e4 3.0e4 2.0e4 1.0e m/z, amu

44 XGF INFUSION signal intensity (icps) Excel Row 181> >55 181>97 181>99

45 XGF CALIBRATION CURVE 181> Signal Intensity (icps) y = 94145x R 2 = Source Concentration (ppbv) 181>99 LINEAR Linear (LINEAR)

46 VX O-Ethyl-S-[2-(diisopropylamino)ethyl] methyl phosphonothioate Molecular Weight 267 Parent Ion 268 Daughter Ions 128, 97, 86, 44 H 3 C CH 2 O O P S CH 2 CH 2 N HC H 3 C HC

47 +Q1: from 30JUL04A010 XVX MOL ION, centroided 1.1e6 H O 3 C CH 2 O P S e6 cps 1.0e6 CH 2 CH 2 N HC 9.0e5 H 3 C HC e5 VX O-Ethyl-S-[2-(diisopropylamino)ethyl] methyl phosphonothioate 7.0e5 Intensity, cps 6.0e5 5.0e5 4.0e5 3.0e e e m/z, amu

48 +Product (268): from 30JUL04A011 XVX PRODUCT, centroided H O 3 C CH 2 O P S CH 2 CH 2 N HC e4 cps H 3 C HC VX O-Ethyl-S-[2-(diisopropylamino)ethyl] methyl phosphonothioate Intensity, cps m/z, amu

49 XVX INFUSION signal intensity (icps) > >44 268>86 268> Excel Row

50 XVX CAL CURVE 268> y = x + 1 R 2 = Signal Intensity (icps) Source Concentration (ppbv) 268>128 LINEAR Linear (LINEAR)

51 HD 2,2 -Di(chloroethyl)sulfide Molecular Weight 158 Parent Ion 158 Daughter Ions 63, 109 CH 2 Cl H 2 C S CH 2 CH 2 Cl

52 +Q1 MCA (7 scans): from 30JUL04A015 XHD MOL ION2, centroided 1.0e7 CH 2 Cl H 2 C e7 cps 9.0e6 8.0e6 S CH 2 CH 2 Cl HD 2,2 Di(chloroethyl)sulfide e6 Intensity, cps 6.0e6 5.0e e6 3.0e6 2.0e e m/z, amu

53 +Product (158) MCA (5 scans): from 30JUL04A016 XHD PRODUCT2, centroided CH 2 Cl e5 cps 1.2e5 H 2 C 1.1e5 1.0e5 9.0e4 S CH 2 CH 2 Cl HD 2,2 -Di(chloroethyl)sulfide 8.0e4 Intensity, cps 7.0e4 6.0e4 5.0e4 4.0e4 3.0e4 2.0e4 1.0e m/z, amu

54 +Product (160) MCA (8 scans): from 30JUL04A017 XHD 160 PRODUCT2, centroided CH 2 Cl e4 cps H 2 C S CH CH 2 Cl HD 2,2 -Di(chloroethyl)sulfide Intensity, cps m/z, amu

55 XHD INFUSION signal intensity (icps) Excel Row 158> >63 160> >65

56 XHD CALIBRATION CURVE 158> y = x + 2 R 2 = Signal Intensity (icps) Source Concentration (ppbv) 158>109 LINEAR Linear (LINEAR)

57 NH1 - N-Ethyl-2,2 -di(chloroethyl)amine Molecular Weight 169 Parent Ion 170 Daughter Ions 63, 106, 142 ClH 2 C CH 2 N CH 2 H 2 C CH 2 Cl

58 +Product (170): from 04AUG04A002 HN1 PRODUCT, centroided 1.1e5 ClH 2 C CH 2 N CH e5 cps 1.0e5 H 2 C 9.0e4 8.0e4 CH 2 Cl NH1 - N-Ethyl-2,2 -di(chloroethyl)amine 7.0e4 Intensity, cps 6.0e4 5.0e4 4.0e e e4 1.0e m/z, amu 154

59 +Product (172): from 04AUG04A003 HN1 172 PRODUCT, centroided ClH 2 C CH 2 N CH 2 H 2 C e4 cps 172 CH 2 Cl NH1 - N-Ethyl-2,2 -di(chloroethyl)amine Intensity, cps m/z, amu

60 HN1 INFUSION signal intensity (icps) Excel Row 170> > >63 172> > >65

61 HN1 CAL CURVE 170> Signal Intensity (icps) y = x R 2 = Source Concentration (ppbv) 170>63 LINEAR Linear (LINEAR)

62 NH2 - N-Methyl-2,2 -di(chloroethyl)amine Molecular Weight 155 Parent Ion 156 Daughter Ions 58, 63, 92, 128 ClH 2 C CH 2 H 2 C N CH 2 Cl

63 +Q1: from 04AUG04A001 HN1 MOL ION2, centroided 1.3e7 1.2e7 ClH 2 C CH 2 N CH 2 H 2 C e7 cps 1.1e7 CH 2 Cl 1.0e7 NH2 - N-Methyl-2,2 -di(chloroethyl)amine 9.0e e6 Intensity, cps 7.0e6 6.0e6 5.0e6 4.0e6 3.0e6 2.0e e m/z, amu

64 +Q1: from 04AUG04A004 HN2 MOL ION, centroided 1.0e7 ClH 2 C CH 2 N e7 cps 9.0e6 8.0e6 7.0e6 H 2 C CH 2 Cl NH2 - N-Methyl-2,2 -di(chloroethyl)amine e6 Intensity, cps 5.0e6 4.0e6 3.0e6 2.0e6 1.0e m/z, amu

65 +Product (156): from 04AUG04A005 HN2 PRODUCT, centroided 1.7e5 ClH 2 C e5 cps 1.6e5 1.5e5 1.4e5 1.3e5 1.2e5 CH 2 N H 2 C CH 2 Cl NH2 - N-Methyl-2,2 -di(chloroethyl)amine 1.1e5 1.0e5 Intensity, cps 9.0e4 8.0e4 7.0e4 6.0e4 5.0e4 4.0e e e4 1.0e m/z, amu

66 +Product (158): from 04AUG04A006 HN2 158 PRODUCT, centroided ClH 2 C CH 2 N H 2 C e4 cps CH 2 Cl NH2 - N-Methyl-2,2 -di(chloroethyl)amine Intensity, cps m/z, amu

67 HN2 INFUSION signal intensity (icps) Excel Row 156> >58 156>63 156>92 158> >65 158>94

68 HN2 CAL CURVE 156> Average Signal Intensity (icps) y = 13574x R 2 = Source Concentration (ppbv) 156>63 LINEAR Linear (LINEAR)

69 NH3 2,2,2 -Tri(chloroethyl)amine Molecular Weight 203 Parent Ion 204 Daughter Ions 63, 106 ClH 2 C CH 2 H 2 C N CH 2 CH 2 Cl CH 2 Cl

70 +Q1 MCA (9 scans): from 04AUG04A007 HN3 MOL ION, centroided 1.05e8 cps 1.0e ClH 2 C 9.0e7 CH 2 H 2 C N CH 2 CH 2 Cl 8.0e7 CH 2 Cl NH3 2,2,2 -Tri(chloroethyl)amine 7.0e7 6.0e7 Intensity, cps 5.0e7 4.0e7 3.0e e7 1.0e m/z, amu

71 +Product (204): from 04AUG04A008 HN3 PRODUCT, centroided e5 1.2e5 1.1e5 ClH 2 C CH 2 H 2 C 1.38e5 cps CH 2 N CH 2 Cl CH 2 Cl 1.0e5 NH3 2,2,2 -Tri(chloroethyl)amine 9.0e4 8.0e4 Intensity, cps 7.0e4 6.0e e4 4.0e4 3.0e4 2.0e e m/z, amu

72 +Product (206): from 04AUG04A009 HN3 206 PRODUCT, centroided 9.65e4 cps ClH 2 C CH 2 N CH 2 CH 2 Cl H 2 C CH 2 Cl NH3 2,2,2 -Tri(chloroethyl)amine Intensity, cps m/z, amu 178

73 +Product (208): from 04AUG04A010 HN3 208 PRODUCT, centroided 3.09e4 cps ClH 2 C CH 2 N CH 2 CH 2 Cl H 2 C CH 2 Cl NH3 2,2,2 -Tri(chloroethyl)amine Intensity, cps m/z, amu

74 HN3 CAL CURVE 204> Average Signal Intensity (icps) y = 24333x + 2 R 2 = Source Concentration (ppbv) 204>106 LINEAR Linear (LINEAR)

75 Diisopropropyl methyl phosphonate Molecular Weight 180 Parent Ion 181 Daughter Ions 79, 97, 115 C H 3 CH3 H 3 C CH O O P HC O

76 +Q1: from 29JUL04A001 DIMP MOL ION2, centroided 7.5e5 7.0e5 6.5e5 6.0e5 5.5e5 H 3 C CH O C H 3 O P HC O CH3 Diisopropropyl methyl phosphonate e5 cps 5.0e5 4.5e5 Intensity, cps 4.0e5 3.5e5 3.0e5 2.5e e5 1.5e5 1.0e e m/z, amu

77 +Product (181): from 29JUL04A002 DIMP PRODUCT, centroided 1.3e5 1.2e5 1.1e5 1.0e5 H 3 C CH O C H 3 O P HC O CH3 Diisopropropyl methyl phosphonate e5 cps 9.0e4 8.0e4 Intensity, cps 7.0e4 6.0e4 5.0e4 4.0e4 3.0e4 2.0e4 1.0e m/z, amu

78 DIMP INFUSION signal intensity (icps) Excel Row 181>79 181>97 181>115

79 DIMP CALIBRATION CURVE 181> Signal Intensity (icps) y = 67804x + 16 R 2 = Source Concentration (ppbv) 181>97 "LINEAR PORTION" Linear ("LINEAR PORTION")

80 D-14 Diisopropropyl methyl phosphonate Molecular Weight 194 Parent Ion 195 Daughter Ions 79, 80, 99, 117 D 3 C CD 3 D 3 C CD 3 CD O O P DC O

81 +Q1: from 29JUL04A005 DIMP-d14 MOL ION, centroided 1.7e7 1.6e7 1.5e7 1.4e7 CD 3 O CD P D 3 C O D 3 C CD 3 DC O e7 cps 1.3e7 D-14 Diisopropropyl methyl phosphonate 1.2e7 1.1e7 1.0e7 Intensity, cps 9.0e6 8.0e6 7.0e6 6.0e6 5.0e6 4.0e6 3.0e e6 1.0e m/z, amu

82 +Product (195): from 29JUL04A006 DIMP-D14 PRODUCT, centroided 4.0e5 3.5e5 CD 3 O CD P D 3 C O D 3 C CD 3 DC O e5 cps 3.0e5 D-14 Diisopropropyl methyl phosphonate 2.5e5 Intensity, cps 2.0e5 1.5e5 1.0e5 5.0e m/z, amu

83 DIMP-d14 INFUSION Signal Intensity (icps) Scan #

84 DIMP-d14 CAL CURVE 195> y = 26137x + 2 R 2 = Signal Intensity (icps) Source Concentration (ppbv) 195>99 LINEAR Linear (LINEAR)

85 CEES - 2-Chloroethyl ethyl sulfide Molecular Weight 124 Parent Ion 124 Daughter Ions 47, 75 H 2 C S CH 2 CH 2 Cl

86 +Q1: from 29JUL04A010 CEES MOL ION, centroided e6 cps 1.2e6 H 2 C 1.1e6 1.0e6 S CH 2 CH 2 Cl 2-Chloroethyl ethyl sulfide 9.0e e5 Intensity, cps 7.0e5 6.0e5 5.0e e e5 2.0e e m/z, amu

87 +Product (124) MCA (5 scans): from 29JUL04A011 CEES PRODUCT, centroided e4 cps H 2 C S CH CH 2 Cl 2-Chloroethyl ethyl sulfide Intensity, cps m/z, amu 109

88 +Product (124): from 29JUL04A012 CEES PRODUCT2, centroided e4 cps H 2 C S CH 2 CH 2 Cl Chloroethyl ethyl sulfide Intensity, cps m/z, amu

89 CEES CALIBRATION CURVE 124> y = x R 2 = Signal Intensity (icps) Source Concentration (ppbv) 124>75 Linear (124>75)

90 CEES 0.2 nd >75 CEES CEES >109 HD DIMP >79 d 14 -DIMP DIMP >79 DIMP DIMP >63 HN DIMP >65 HN DIMP >106 HN DIMP 156 nd >86 VX DIMP >97 GF DIMP >43 GD DIMP >97 GB DIMP >117 GA Relative Response Factor Surrogate Response Factor (icps/pptv) Surrogate Analyte Response Factor (icps/pptv) Limits of Linearity (ppbv) Method Quantitation Limit (ppvt) Method Detection Limit (pptv) Primary Ion Transition Acronym

91 Acronym Percutaneous Vapor Toxcity (pptv) Immediately Dangerous to Life and Health (pptv) Less than Acute Exposure Guideline Limit (pptv) Method Detection Limit (pptv) Method Quantitation Limit (ppvt) Limits of Linearity (ppbv) 10 Minute 30 Minute 60 Minute 240 Minute 480 Minute GA GB GD GF VX nd HN1* n.a HN2* n.a HN3* n.a DIMP n.a. n.a. n.a. n.a. n.a. n.a. n.a d-14 - DIMP n.a. n.a. n.a. n.a. n.a. n.a. n.a HD n.a CEES n.a. n.a. n.a. n.a. n.a. n.a. n.a nd * = Used HD Values n.a. = Not Available

92 Acronym Percutaneous Vapor Toxcity (pptv) Immediately Dangerous to Life and Health (pptv) Molecular Weight Specific 25 o C Vapor Density Boiling Point ( o C) Melting Point ( o C) Vapor Pressure mm 25 o C 25 o C (pptv) TAGA Method Detection Limit (pptv) GA E GB E GD E GF a E VX E HN1* n.a E HN2* n.a E HN3* n.a E DIMP n.a. n.a n.a b n.a E d-14 - DIMP n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a HD n.a E CEES n.a. n.a a n.a E * = Based on HD values n.a. = Not Available nd = Not Determined a temp=20 o C b 10 mm Hg

93 For additional information concerning the capabilities and applications of the TAGA, call or me at or

94 O N + O - Parathion Malathion S O P O S H 2 C O C CH 2 CH S O H 2 C P O O CH 2 O O - N + O O H 2 C C O S Methyl Parathion O P O H 3 C O

95 Tetrachloroethene (ARMN022) 30 A B C D E F G H I J K L M N O 25 Units in ppbv QL 0 DL Time in minutes Wind: 10 mph/050 o Figure 18a Mobile Monitoring Path Two, ARMN022

96 Units in ppbv QL DL Tetrachloroethene (ARMN009) ABCD EF GH I J KL MN OP QR S TUV WX Y ZAACC BB Time in minutes Wind: Variable Hauling to the East Figure 17a Mobile Monitoring Path One, ARMN009

David B. Mickunas, U.S. EPA/ERTC Work Assignment Manager SUBJECT: DOCUMENT TRANSMITTAL UNDER WORK ASSIGNMENT #0-298

DATE: 25 July 2003 TO: THROUGH: FROM: David B. Mickunas, U.S. EPA/ERTC Work Assignment Manager Dennis A. Miller, REAC Program Manager Danielle McCall, REAC Task Leader SUBJECT: DOCUMENT TRANSMITTAL UNDER