EDGEWOOD ECBC-TR-611 QUANTITATIVE UV ABSORBANCE SPECTRA OF CHEMICAL AGENTS AND SIMULANTS CHEMICAL BIOLOGICAL CENTER

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1 EDGEWOOD CHEMICAL BIOLOGICAL CENTER U.S. ARMY RESEARCH, DEVELOPMENT AND ENGINEERING COMMAND ECBC-TR-611 QUANTITATIVE UV ABSORBANCE SPECTRA OF CHEMICAL AGENTS AND SIMULANTS J. Michael Lochner Aaron M. Hyre Steven D. Christesen Kristina R. Gonser RESEARCH AND TECHNOLOGY DIRECTORATE March 2008 Approved for public release; distribution Is unlimited. ' ABERDEEN PROVING GROUND, MD

2 Disclaimer The findings in this report are not to be construed as an official Department of the Army position unless so designated by other authorizing documents.

3 DEPARTMENT OF THE ARMY U.S. Army Edgewood Chemical Biological Center Aberdeen Proving Ground, Maryland ERRATUM SHEET 22 May 2008 REPORT NO. TITLE AUTHORS ECBC-TR-611 Quantitative UV Absorbance Spectra of Chemical Agents and Simulants J. Michael Lochner, Aaron M. Hyre, Steven D. Christesen, and Kristina R. Gonser DATE March 2008 REPORT CLASSIFICATION UNCLASSIFIED - Unlimited Please replace your copy of ECBC-TR-61 1, previously mailed to you, with the enclosed copy. SANDRA. Chief, Technical Releases Office Encl as

4 Form Approved REPORT DOCUMENTATION PAGE OMB No Public reporting burden for this colection of iomion is etinated to averae I hour per response, IncWlKd te ime lor reviewing Inskuctlons, swcnkg eltirg data soue, gellwing and maintaining the data needed, and completng and revw h collection of infonmatilon. Send commente repr&g tis burden estimate or any other aspect of h oolecliori k*on, Inkcxf suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for nonnatlon Operations and Reports ( ), 1215 Jefferson Davis Ighway, Suite 1204, Arlington, VA Respondents should be aware that notwithtstandlng any other provision of low. no peneon ihal be subct to any pene" for aing; to conl with a col on of information N It does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To) XX Final Jan Jul TITLE AND SUBTITLE 5a. CONTRACT NUMBER Quantitative UV Absorbance Spectra of Chemical Agents and Simulants 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Lochner, J. Michael; Hyre, Aaron M.; Christesen, Steven D.; Gonser, Kristina R BPO 5. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBER DIR, ECBC, ATTN: AMSRD-ECB-RT-CC/AMSRD-ECB-RT-DL, APG, MD ECBC-TR SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORIMONITOR'S ACRONYM(S) 11. SPONSOR/MONITOR'S REPORT NUMBER(S) 12. DISTRIBUTION I AVAILABILITY STATEMENT Approved for public release; distribution is unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT The quantitative UV absorption spectra of selected chemical agents and simulants have been measured for wavelengths in the near UV from 200 to 400 nm. Although these data are of interest in their own right, they are also necessary for predicting the sensitivity of UV Raman based detection systems. Of particular interest are the absorption values at nm and 262 nm as these correspond to excitation wavelengths used by UV Raman based surface contamination detectors currently under development. These wavelengths are produced by KrF excimer lasers and quadrupled Nd:YLF lasers, respectively. This report collates these data in a presentable form. 15. SUBJECT TERMS UV absorption Agents Molar absorptivities UV Raman Simulants Absorption cross sections 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER OF 19a. NAME OF RESPONSIBLE PERSON ABSTRACT PAGES Sandra J. Johnson a. REPORT b. ABSTRACT c. THIS PAGE 19b. TELEPHONE NUMBER (icude area code) U U U UL 39 (410) Standard Form 298 (Rev. 8-98) Prescribed by ANSI SM. Z39.18

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6 PREFACE The work described in this report was authorized under Project No BPO. The work was started in January 2004 and completed in July The use of either trade or manufacturers' names in this report does not constitute an official endorsement of any commercial products. This report may not be cited for purposes of advertisement. This report has been approved for public release. Registered users should request additional copies from the Defense Technical Information Center; unregistered users should direct such requests to the National Technical Information Service. 3

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8 CONTENTS 1. INTRODUCTION BACKGROUND EXPERIMENTAL PROCEDURES RESULTS CONCLUSIONS APPENDIXES A - SAMPLE INFORMATION...1I B - UV ABSORPTION SPECTRA C - MOLAR ABSORPTIVITY DATA (L mole -1 cm

9 TABLES 1. Molar Absorptivities at and 262 nm Comparison to Literature Values: Absorption Cross Sections at 250 nm Comparison to Literature Values: Peak Absorption Cross Sections (cm 2 /m olecule)

10 QUANTITATIVE UV ABSORBANCE SPECTRA OF CHEMICAL AGENTS AND SIMULANTS 1. INTRODUCTION The quantitative ultraviolet (UV) absorption spectra of selected chemical agents and simulants have been measured for wavelengths in the near UV from 200 to 400 rnm. Although these data are of interest in their own right, they are also necessary for predicting the sensitivity of UV Raman based detection systems. The absorption values at and 262 nm are of particular interest as these correspond to excitation wavelengths used by UV Raman based surface contamination detectors currently under development. These wavelengths are produced by KrF excimer lasers and quadrupled Nd: YLF lasers, respectively. 2. BACKGROUND To calculate the Raman scattering intensity of a given chemical, it is necessary to know how much of the incident and scattered radiation are absorbed by the sample. For transparent samples, the absorbance is negligible and no correction is required. Many organic chemicals, however, have absorbance bands below 300 nm, and this absorbance must be taken into account when calculating Raman scattering cross sections. The amount of radiation absorbed by a molecule is described by the Beer-Lambert Law shown in its various forms in eqs 1 through 3. I=10 xl 0-1 (1) where Transmittance T= I e1d0 (2) 10 Absorbance A = -logt = Ecl (3) 0 = intensity of the incident radiation I = intensity of the transmitted radiation c = molar concentration of solute (M) 1= path length of the cell (cm), and E = molar extinction coefficient or molar absorptivity (L x mole - ' x cm-'). Experimentally, absorbance is measured as a function of wavelength for either neat chemicals or solutions of known concentration. When the UV spectrum of a sample is measured in solution, the absorbance of the dilutant chemical must also be taken into account. The UV spectrum of the pure dilutant is obtained and subtracted from that of the solution. This correction is often automatically performed in the spectrometer software during data collection. 7

11 When diluting a chemical, a solvent with a low UV cutoff wavelength is chosen. The UV cutoff wavelength is the wavelength at which the absorbance is unity when measured against air in a 1-cm matching cell. Acetonitrile and water have UV cutoff wavelengths of 190 nm, which makes them suitable for UV absorption measurements above 190 nm. The path length 1 is determined by the width of the cuvette containing the sample. The molar absorptivity is then calculated at a specific wavelength using eq EXPERIMENTAL PROCEDURES Absorbance data was collected for 29 chemical agents and simulants including the G agents, VX, and HD. The list of samples, along with information on their sources, is tabulated in Appendix A. Solutions were prepared using standard chemistry techniques and methodology. Surety samples were handled in accordance with appropriate standing operating procedures. The concentrations were chosen so that the resulting absorbances at 248 and 262 nm were between approximately 0.5 and 2. Absorbances of greater than roughly 3 (a transmission of 0.1%) could not be measured because of low signal to noise. Conversely, concentrations that yielded low absorbances were imprecise because the small errors in blank (dilutant + cell) subtraction could dominate the measured absorbance. In the cases where multiple spectra are shown for the UV absorbance in Appendix B, the higher concentration was used to calculate molar absorptivities in Table 1 and Appendix C. Except for methylphosphonic acid (MPA), all samples were used either neat or diluted with acetonitrile. The MPA, a solid, was dissolved in distilled and deionized water. The solutions were placed in rectangular Spectrosil Quartz fluorometer cells (Starna Cells, Inc). One centimeter pathlength cells were used except for GB where measurements were made in a 0.1 cm pathlength cell. The cells were filled at least 2/3 full. Data was collected using a Varian Cary 50 UV-VIS spectrometer using a xenon flash lamp light source. A beam splitter is incorporated to allow simultaneous reference beam correction. Several variables could be adjusted within the software. All data collection occurred at a scan rate of 300 nm/min over the wavelength range of nm with a measurement interval size of 0.5 nm. Spectra of dilutant chemicals were obtained at the start of each day prior to data collection (see examples in Appendix B). The appropriate spectrum was automatically subtracted from that of the solution during data collection. 4. RESULTS For each sample, absorbance data between 200 and 400 nm were recorded as a function of wavelength and used to calculate molar absorptivity values, as described above. These values, as a function of wavelength, appear in Appendixes B (spectra) and C (data tables). 8

12 As mentioned above, the molar absorptivity values at and 262 nm are of special interest due to their importance in calculating UV Raman scattering cross-sections for UV Raman based surface detectors in development. These values are listed in Table 1. Table 1. Molar Absorptivities at and 262 nm Chemical Abbreviation E( o~ nm 262 nm 2-Chloroethyl ethyl sulfide CEES 1.6E E+00O 3-quinuclidinyl benzilate BZ 2.2E+02 Il-7E+02 Arsenic trichloride AsC13 2.3E E+01 Chloroacetophenone CN 9.6E+03 2.l1E+03 Chloropicrin (trichloronitromethane) PS 2.1 E+O E+O01 Cyclosarin GF 5.OE E+00 Diethyl malonate DEM 1.5E E-0OI Ethyl methylphosphonic acid EMiPA 1.11E F-02 Ethyldichloroarsine ED 9.OE E+02 Isopropyl methylphosphonic acid IMPA 1.9E Lewisite L 3.6E E+03 Methyl salicylate MES 1.3E E+02 Methyldichloroarsine MD 9.8E E+02 Nethylphosphonic acid MPA 1.6E E+00 N-mustard HN- I 4.OE E+00 -mnustard HN-3 2.4E E±00 D-Diisopropyl methylphosphonate DIMP 1.5E E-02 -Dimethyl methylphosphonate DMMP 1.2E-01 7.I1E-02 -ethyl-s-(2-isopropylaminoethyl)methyil V 7.6E E+02 phosphonothioate O-Triethylphosphate TEPO 4.9E-02 4.OE-02 Pheny1dichloroarsine PD 2.5E E+03 Phosgene Oxime Cx 2.8E E-0OI Pinacolyl methylphosphonic acid PMPA 1.2E E-0 I Sarin GB 7A4E E-0OI Soman GD 1.9E E-0-l Sulfur Mustard. HD 1.813± ±00 Tabun GA 1.8E E-01 Thiodigylcol TDG E-0OI T-mustard T E+00 9

13 As can be seen, the absorptivity of the samples varied widely. For the nerve agents, VX is much more highly absorbing at 248 nm than any of the G agents, which are relatively weak absorbers in the near UV. The molar absorptivity of the mustard agent and lewisite are also more than an order of magnitude larger than the G agents. In Tables 2 and 3, we compare our results to those published in the open literature by Rewick et al.* Our data has been converted to units of square centimeters/molecule to conform to the data in the reference.* The conversion from molar absorptivity in L*mole - '*cm - 1 to cross section is accomplished by multiplying by 1000/N 0, where No is Avagadro's number. Except for GA, the values agree reasonably well. Our results for GA are in line with the other G agents, while the Rewick's absorption cross section is two orders of magnitude larger than any of the other G agents. The reason for this discrepancy is unknown, but may be attributable to a highly absorbing impurity or degradation product in Rewick's sample. Table 2. Comparison to Literature Values: Absorption Cross Sections at 250 nm (cm 2 /molecule) Rewick' This Study Ratio GA 9.0E E GB 1.2E E GD 4.OE E VX 9.OE E HD 2.8E E L L.1E E CEES 3.1E-20 2.OE DMMP 2.1 E E Table 3. Comparison to Literature Values: Peak Absorption Cross Sections (cm 2 /molecule) Rewick' This Study Ratio HD (205 nm) 6.9E E L (215 nm) 3.1E E CONCLUSIONS The molar absorptivities were calculated for 29 chemical agents and simulants as a function of wavelength. The data collected during this project also alerts researchers to areas of possible challenge for detectors based on ultraviolet Raman scattering. Rewick, Robert T.; Schumacher, Mary L.; Haynes, Daniel L. The UV Absorption Spectra of Chemical Agents and Simulants. AppL. Spectrosc. 1986, 40 (2), pp

14 APPENDIX A SAMPLE INFORMATION A list of sample chemicals and their sources appears below. In the case of agents (in bold type) the Chemical Agent Standard Reference Material (CASARM) number is listed. All chemicals were laboratory grade. Abbv. Chemical Name CAS # LOT # ACN Acetonitrile J. T. BAKER #A03810 AsC13 Arsenic Trichloride STREM CHEMICALS # BZ 3-quinuclidinyl benzilate BZ-U-1057 CEES 2-Chloroethyl ethyl sulfide ADRICH #09226CY HY CN Chloroacetophenone ALDRICH #08222BA CX Phosgene Oxime DEM _Diethyl malonate FLUKA #39006/1 892 DIMP O-Diisopropyl 14-56JHSNM THY#23 methylphosphonate 14-56JHSNMTHY#23 DMMP 0-Dimethyl75-96ADIH#247B methylphosphonate 7-96ADIH#247B ED Ethyldichloroarsine MW EMPA_ Ethyl methylphosphonic acid ALDRICH #0351 7MY CR Tabun, Ethyl N,N- GA dimethylphosphor VIAL#50.amidocyanidate GB Sarin, 2-(fluoro-methylphosphoryl)oxypropane GB-U-9146-CTF VIAL #91/81 Soman, 3-(fluoro-methyl- GD phosphoryl)oxy GD-U-2323-CTF-N 2,2-dimethyl-butane GF Cyclosarin, (fluoro-methyl FS69-T-- p hosphoryl)oxycyclohexane 399- FS69-T-- HD Sulfur Mustard, Bis( chloroethyl) sulfide HD-U-9045-CTF-N Nitrogen Mustard, 2-chloro- HN-I N-(2-chloroethyl)-N-ethyl HN ethanamnine Nitrogen Mustard, 2-chloro- HN-3 N,N-bis( H1N3-92-CTF-N #130 chloroethyl)ethanamine IMPA Isopropyl methylphosphonic ECBC #14049 acid L Lewisite, LU62-T N chloroethenyldichloroarsine I--22-T 11

15 Abbv Chemical Name CAS # LOT # MD _Methyldichloroarsine MW MES _Methyl salicylate ALDRICH #121 15DY PZ MPA Methylphosphonic acid FLUKA # PD Phenyldichloroarsine MW PMPA Pinacolyl methylphosphonic ALDRICH #0371 ILY CR acid _ PS Chloropicrin ALDRICH #04222TB T T Mustard, bis[12(2- chloroethylthio)ethyll ether TDG Thiodigylcol FLUKA # TEPO_ 0-Triethylphosphate ECBC P36-CUT3 0-ethyl S-(2- VX diisopropylaminoethyl) VX-U-4308-CTF-N methylphosphonothiolate Water 18 mq deionized water APPENDIX A 12

16 APPENDIX B UV ABSORPTION SPECTRA O -E Figure B-1. Absorption Spectrum of Neat Water (upper trace) and Acetonitrile (lower trace) U Figure B-2. Absorption Spectrum of 8.59 X 10-2 M (upper trace) and 1.07 X 10-5 M (lower trace) CEES 13

17 U , Figure B-3. Absorption Spectrum of 5.88 X 10-3 M BZ w 2.0 e , Figure B-4. Absorption Spectrum of 3.95 X 10-3 M AsC1 3 APPENDIX B 14

18 M 0 1i.5 M Figure B-5. Absorption Spectrum of 1.48 X 1 04 M CN 3.0 C w ~1.5-0 M Figure B-6. Absorption Spectrum of X 10'1 M (upper trace) and 1.01 X 10-2 M (lower trace) PS APPENDIX B 15

19 ~ Figure B-7. Absorption Spectrum of 2.13 X 10-' M GF C 0.0 M w Figure B-8. Absorption Spectrum of 6.50 X 101 M (upper trace) and 6.52 X 10-3 M (lower trace) DEM APPENDIX B 16

20 2.5 - w2.0 - ~0 1l Figure B-9. Absorption Spectrum of 6.30 M (upper trace) and 1. 16X 10,2 M (lower trace) EMPA 0) 2.0 M M Figure B-10. Absorption Spectrum of 1.99 X 10-' M ED APPENDIX B 17

21 e S Figure B-l l. Absorption Spectrum of Neat (upper trace) and 7.94 X 10-2 M (lower trace) IMPA CD C w Figure B-12. Absorption Spectrum of 2.27 X M L APPENDIX B 18

22 I Figure B- 13. Absorption Spectrum of 7.72 X 10-4 M (upper trace) and 7.72 X 10-6 M (lower trace) MES 'U w (U L Figure Absorption Spectrum of X 10- M MD APPENDIX B 19

23 S1.5-0 to Cu Figure B- 15. Absorption Spectrum of 7.87 X 10-' M MPA w L Figure Absorption Spectrum of X 10-' M HN-D I APPENDIX B 20

24 ~, Figure B-17. Absorption Spectrum of 5.98 X 10-' M HN (D 2.0 C M Figure Absorption Spectrum of Neat DIMP APPENDIX B 21

25 U Figure B-19. Absorption Spectrum of Neat DMMP M Figure B-20. Absorption Spectrum of 1.69 X 10-3 M (upper trace) and 1.13 X 10-4 M (lower trace) VX APPENDIX B 22

26 2.5 S Figure B-2 1. Absorption Spectrum of Neat (upper trace) and 5.82 X 10-2 M (lower trace) TEPO C 0 S ~, i Figure B-22. Absorption Spectrum of 7.38 X M PD APPENDIX B 23

27 w2.0- C.0 ~ Figure B-23. Absorption Spectrum of 7.42 X 10-' M CX w Figure B-24. Absorption Spectrum of 1.43 M (upper trace) and 5.67 X 10-2 M (lower trace) PMPA APPENDIX B 24

28 o Figure B-25. Absorption Spectrum of Neat GB 0 C w Figure B-26. Absorption Spectrum of 5.10 X 101 M (upper trace) and 2.74 X 10-2 M (lower trace) GD APPENDIX B 25

29 * I, I o (Ū Figure B-27. Absorption Spectrum of 9.74 X 10" M (solid line), 7.75 X 10-3 M (dotted line), and 4.28 X 10-2 M (dashed line) HD 3.0, (U Figure B-28. Absorption Spectrum of 6.64 X 101 M (upper trace) and 6.81 X 10-3 M (lower trace) GA APPENDIX B 26

30 2.0 1l.5 0 U) Figure B-29. Absorption Spectrum of 3.22 X 10-1 M (upper trace) and 9.98 X 104 M (lower trace) TDG ~, Figure B-30. Absorption Spectrum of 4.67 X 10-' M T APPENDIX B 27

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32 APPENDIX C MOLAR ABSORPTIVITY DATA (L mole-' cm t ) Wavelength (nm) CEES BZ AsC3 CN PS GF E E E E E E E E E E E E E E E E E E E E E E E E E E E E E IE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E IE E E E E E IE E E E E E E E E E E E E E E E E E E E E E+0G 4.62E E E E E E E E E E E E E E OE E E E E-01 I1.50E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-02 3.OOE E E E E E E E E E E E E E E E E E E E E E E E E+00 I.11E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E+O1 3.14E+00 29

33 Wavelength (nm) CEES BZ AsCI3 CN PS GF E E E E E E E E E E E E E E E E E E E E OE E E E E E E E+01I 3.35E E E E E E E E-01I 5.OOE E E E+0 I 3.47E E E E E E E E E E E E+01I 3.59E E-01 6.I1OE E E E E E E E E E E E-0 I 7.30E E+O0I 1.08E l E E E E E+s E+01I 3.87E E E E E E+01I 3.93E E-01I 1.08E E+t E E+01I 3.99E E E E E E E E E E E+s01 4.I11E E E E E E E E OOE+0 I 1.42E E+O1I 4.19E E E E+01I 1.63E E E E E E E E+01I 4.29E E E E E E E E E E E E+01I 4.43E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+01I 5.69E E E E E E E E E OE E E E E E E E+O I 7.28E E E E E E E E E E E E+01I 8.49E E E E E E E E E E E E E E E E E E E E E E+01I 9.89E E E E E E+01 1.OOE+01I E E E E E+01 1.O1E E E E E E+01 I1.03E I E E E E+01 I1.06E E+t E E E E+01I 1.09E E E E E E E+0I E E E E E+01I 1.25E E E E E E E E E E+01I 4.65E E E E E I1 4.36E E E E E+01I APPENDIX C 30

34 Wavelength (nm) CEES BZ AsC3 CN PS GF E OE E E E E+01 Wavelength (nm) DEM EMPA ED IMPA L MES E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-06 9.OOE E E E E OE E E E E E E E E E E E E E E E E E E IE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OOE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OOE E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E-0I 7.72E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+03 APPENDIX C 31

35 Wavelength (nm) DEM EMPA ED IMPA L MES E E E E E E E I11E IE E E E E E E E E E OO E E E-02 L.00E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-01I 3.50E E E E E E E E E E E E-0lI 3.78E E E E E E-0lI 3.87E E+01I 7.73E E E E-0lI 3.96E E E E E E-0lI 4.06E E E E E E E E E E E E E E E E E E E E E-02 1.OOE E E E E E E E E E E-0lI 1.39E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-01I 9.01E E-0lI 3.65E E E E E E E E E E E E E E E+I OE E E E E E E E E E E E E E E E+I E E E E E E E E E E E-0lI 6.74E E E E-0lI 9.76E E E E E E E E-01I 7.97E E E E E E E E E E E E E E E-0l E E E E E E E E E-0lI l.ooe E E l1 5.22E E-0lI 1.02E E E E l 1I.03E E E-0 I 5.52E E E E E E E E E E-0lI 6.87E E-0l I1.03E E E E-0l E E E E E E E E E E E+03 APPENDIX C 32

36 Wavelength (nm) DEM EMPA ED IMPA L MES E E E E E E E E E E E E+03 Wavelength (nm) MD MPA HN-I HN-3 DIMP DMMP E E E E E E E-01 6.OOE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E IE IE E E E E E E E E E IE E+O0 8.75E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E IE E+O0 1.32E E E E E E E E E E E E E E E E E E E IE E E E E E E E E E E E E E E E E E E E-0l 5.96E E E-0I 1.81E E E E E E E E E IE E+00 1.OOE E E E E E E E E E E E E E E E E E E E E E E E+O0 1.36E E E E E E E E E E+00 2.I1E E E E E E E E E E E-01 APPENDIX C 33

37 Wavelength (nm) MD MPA HN-1 HN-3 DIMP DMMP E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+00 2.OOE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+O1 4.60E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-01 APPENDIX C 34

38 Wavelength (nm) MD MPA HN-1 HN-3 DIMP DMMP E E E E E E E E E E E E E E E E E E-01 Wavelength (nm) VX TEPO PD CX PMPA GB E E E E E E E E E E E E IE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+00 2.OOE E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E IE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-0I 2.77E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE-0 I APPENDIX C 35

39 Wavelength (nm) VX TEPO PD CX PMPA GB E E E E E E E E E+O1I 1.45E E E E E E E E E E E E+01I 1.67E OE-01I 3.29E E E E+01I 1.81E E E E E E E E E E E E E E E E E E E E-0 I 3.55E E E OE+01I 2.57E E E-01I E E E E E-0 I 3.72E E E E E E E E+01I 3.01E E E E E-0 I E E E E E E E E E E E E E+' E E E E E E E E E E E E E E E E E E E E E E E E E E E-0 I 5.07E E E E E E E E E-0! 7.86E E E E E E E-01I 5.43E E E E E E E E E E-01I 7.59E E E E E E E E E E E E E E E E E-01I 6.09E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E OE E E E E E OE+00 1.O1E E E E E E E E OE E E E E E OE E E E E OE E E E E OE E E+03 1.O1E E E OE E E E-01I 3.77E E OE E E E-01I 3.59E E E E E OE E E E E OE E E E E E OE E E E E E OE E E E E E OE+I E E E-01I 4.07E E OE± E E E-01I 4.07E E OE+00 2.OOE+00 APPENDIX C 36

40 Wavelength (nm) VX TEPO PD CX PMPA GB E E E E OE E E E E E E E E E E E E E E E E E E E+00 Wavelength (nm) GD HD GA TDG T E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E OE E E E E E E E E IE E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+00 APPENDIX C 37

41 Wavelength (nm) GD HD GA TDG T E-02 L.OOE E E O E E E E E E E E E E E E-01I 3.68E E E E E E I E E I1 1.80E E E E IE IE E E-01I 1.13E E E E E E-01I 3.76E E-0l E E-01I 4.20E E E-01I 4.62E E-01I 4.61E E-0 I 3.24E-0 I 4.95E E E-O E-01 5.I E-0 I 1.44E E-0 I 5.23E lE-0OI 5.35E E E-01I 4.68E E E E-01I 5.05E E E E-0 I 7.66E E-0 I 5.67E E-01 I1.05E E E E E E-0 I 7.06E-01I 5.88E E E E-0 I 8.19E E E E E E E E E E E E E E E E E E E E+s E E E E E E E E E E E E E E+00 5.OOE+00 2.OOE E E+0lI 2.57E E E E+01I 3.30E E E E E+01I 4.33E E E E E E E E E E E E E E E E E E E E E+01I 4.52E E E E E E E E E E E E E E E E+0I E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E+01 APPENDIX C 38

42 Wavelength (nm) GD HD GA TDG T E E E E E E E E E E E E E E E E E E E E E E E E E+01 APPENDIX C 39